Design, Fabrication, and Characterization of Carbon Nanotube Field Emission Devices For Advanced Applications

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Design, Fabrication, and Characterization of

Carbon Nanotube Field Emission Devices for
Advanced Applications
Thesis · January 2015

DOI: 10.13140/RG.2.2.16376.85767
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Design, Fabrication, and Characterization of Carbon
Nanotube Field Emission Devices for Advanced Applications
by
Erich Justin Radauscher
Department of Electrical and Computer Engineering

Duke University
Date:_______________________
Approved:
___________________________
Jeffrey T. Glass, Supervisor
___________________________
Brian R. Stoner
___________________________
Adrienne D. Stiff-Roberts
___________________________
Aaron D. Franklin
___________________________
Martin A. Brooke
Dissertation submitted in partial fulfillment of

the requirements for the degree of Doctor
of Philosophy in the Department of
Electrical and Computer Engineering in the Graduate School
of Duke University
2016
v
ABSTRACT
Design, Fabrication, and Characterization of Carbon
Nanotube Field Emission Devices for Advanced Applications
by
Department of Electrical and Computer Engineering

Duke University
Date:_______________________
Approved:
___________________________
Jeffrey T. Glass, Supervisor
___________________________
Brian R. Stoner
___________________________
Adrienne D. Stiff-Roberts
___________________________
Aaron D. Franklin
___________________________
Martin A. Brooke
An abstract of a dissertation submitted in partial fulfillment of

the requirements for the degree of Doctor
of Philosophy in the Department of
Electrical and Computer Engineering in the Graduate School
of Duke University
2016
Copyright by
2016
Abstract
Carbon nanotubes (CNTs) have recently emerged as promising candidates for
electron field emission (FE) cathodes in integrated FE devices. These nanostructured
carbon materials possess exceptional properties and their synthesis can be thoroughly
controlled. Their integration into advanced electronic devices, including not only FE
cathodes, but sensors, energy storage devices, and circuit components, has seen rapid
growth in recent years. The results of the studies presented here demonstrate that the
CNT field emitter is an excellent candidate for next generation vacuum microelectronics
and related electron emission devices in several advanced applications.
The work presented in this study addresses determining factors that currently
confine the performance and application of CNT-FE devices. Characterization studies
and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical
Systems (MEMS) design and fabrication, were utilized in achieving these goals.
Important performance limiting parameters, including emitter lifetime and failure from
poor substrate adhesion, are examined. The compatibility and integration of CNT
emitters with the governing MEMS substrate (i.e., polycrystalline silicon), and its impact
on these performance limiting parameters, are reported. CNT growth mechanisms and
kinetics were investigated and compared to silicon (100) to improve the design of CNT
iv
emitter integrated MEMS based electronic devices, specifically in vacuum
microelectronic device (VMD) applications.
Improved growth allowed for design and development of novel cold-cathode FE
devices utilizing CNT field emitters. A chemical ionization (CI) source based on a CNT-
FE electron source was developed and evaluated in a commercial desktop mass
spectrometer for explosives trace detection. This work demonstrated the first reported
use of a CNT-based ion source capable of collecting CI mass spectra. The CNT-FE source
demonstrated low power requirements, pulsing capabilities, and average lifetimes of
over 320 hours when operated in constant emission mode under elevated pressures,
without sacrificing performance. Additionally, a novel packaged ion source for
miniature mass spectrometer applications using CNT emitters, a MEMS based Nier-type
geometry, and a Low Temperature Cofired Ceramic (LTCC) 3D scaffold with integrated
ion optics were developed and characterized. While previous research has shown other
devices capable of collecting ion currents on chip, this LTCC packaged MEMS micro-ion
source demonstrated improvements in energy and angular dispersion as well as the
ability to direct the ions out of the packaged source and towards a mass analyzer.
Simulations and experimental design, fabrication, and characterization were used to
make these improvements.
Finally, novel CNT-FE devices were developed to investigate their potential to
perform as active circuit elements in VMD circuits. Difficulty integrating devices at
v
micron-scales has hindered the use of vacuum electronic devices in integrated circuits,
despite the unique advantages they offer in select applications. Using a combination of
particle trajectory simulation and experimental characterization, device performance in
an integrated platform was investigated. Solutions to the difficulties in operating
multiple devices in close proximity and enhancing electron transmission (i.e., reducing
grid loss) are explored in detail. A systematic and iterative process was used to develop
isolation structures that reduced crosstalk between neighboring devices from 15% on
average, to nearly zero. Innovative geometries and a new operational mode reduced
grid loss by nearly threefold, thereby improving transmission of the emitted cathode
current to the anode from 25% in initial designs to 70% on average. These performance
enhancements are important enablers for larger scale integration and for the realization
of complex vacuum microelectronic circuits.
vi
Dedicated to my dearest wife, Rebecca
To my beloved parents, Erich and Sandra, and brother, Matthew
And
To my amazing baby boy, Aiden
vii
Table of Contents
Abstract .........................................................................................................................................iv
Table of Contents ...................................................................................................................... viii
List of Tables ...............................................................................................................................xiv
List of Figures .............................................................................................................................. xv
List of Symbols and Abbreviations ........................................................................................xxii
Acknowledgements ................................................................................................................ xxiii
1. General Introduction ................................................................................................................ 1
1.1 Electronic Materials for Cold Cathode Field Emission ............................................... 2
1.2 Vacuum Microelectronics Overview ............................................................................. 7
1.3 Motivation and Objectives of this Research................................................................ 11
1.4 Dissertation Outline ....................................................................................................... 12
2. Background - Carbon Nanotubes (CNT), Field Emission (FE), FE Vacuum

Microelectronic Devices (FE-VMDs), and Mass Spectrometry (MS) ................................... 15
2.1 Introduction..................................................................................................................... 15
2.2 Carbon Nanotubes ......................................................................................................... 15
2.2.1 Significance of CNT Research .................................................................................. 16
2.2.2 Structure ..................................................................................................................... 17
2.2.3 Growth Mechanisms of CNTs ................................................................................. 19
2.2.4 Properties of CNTs .................................................................................................... 21
2.2.4.1 Mechanical .......................................................................................................... 21
2.2.4.2 Electronic ............................................................................................................. 22
viii
2.2.5 CNT Applications...................................................................................................... 24
2.3 Field Emission Fundamentals....................................................................................... 25
2.3.1 Electron Emission ...................................................................................................... 26
2.3.1.1 Probability of Escape ......................................................................................... 26
2.3.1.2 Emission Processes ............................................................................................ 28
2.3.1.3 Emission Metrics Specific to FE ....................................................................... 31
2.3.2 The Fowler-Nordheim Theory ................................................................................ 32
2.3.2.1 Correction to the F-N Equation ........................................................................ 37
2.3.3 Field Emission from CNTs ....................................................................................... 38
2.3.3.1 Unique FE Properties of CNTs ......................................................................... 38
2.4 Field Emission Devices .................................................................................................. 42
2.4.1 FE Device Classifications .......................................................................................... 43
2.4.1.1 Spindt Cathode ................................................................................................... 43
2.4.1.2 Silicon Field Emitters ......................................................................................... 44
2.4.1.3 Carbon Field Emitters........................................................................................ 45
2.4.2 VMD Operating Modes ............................................................................................ 47
2.4.2.1 Vacuum Diodes .................................................................................................. 47
2.4.2.2 Vacuum Triodes ................................................................................................. 48
2.4.3 Present VMD Challenges ......................................................................................... 48
2.4.4 Duke/RTI MEMS VMD ............................................................................................. 49
2.4.4.1 Vertical and Lateral VMDs ............................................................................... 50
2.4.4.2 History and Previous Work .............................................................................. 50
ix
2.4.4.3 Microelectromechanical Systems (MEMS) ..................................................... 52
2.4.4.4 Device Assembly ................................................................................................ 53
2.4.4.5 Device Testing .................................................................................................... 54
2.5 Mass Spectrometry (MS)................................................................................................ 55
2.5.1 Introduction to Basic Concepts................................................................................ 56
2.5.2 Ionization Processes .................................................................................................. 57
2.5.2.1 Electron Ionization ............................................................................................. 57
2.5.2.2 Chemical Ionization ........................................................................................... 58
2.5.2.3 CNT Emitters for Mass Spectrometry ............................................................. 59
3. Chemical Ionization Mass Spectrometry Using Carbon Nanotube Field Emission

Electron Sources .......................................................................................................................... 61
3.1 Introduction..................................................................................................................... 63
3.2 Experimental Methods................................................................................................... 66
3.3 Results and Discussion .................................................................................................. 70
3.3.1 Ex-Situ Characterization ........................................................................................... 70
3.3.2 Integration into the Desktop Mass Spectrometer ................................................. 74
3.3.3 Evidence for Chemical Ionization ........................................................................... 76
3.4 Conclusion ....................................................................................................................... 80
4. Integrating Carbon Nanotube Forests into Polysilicon MEMS: Growth Kinetics,

Mechanisms, and Adhesion ...................................................................................................... 82
4.1 Introduction..................................................................................................................... 84
4.2 Experimental ................................................................................................................... 87
4.2.1 Substrate Preparation................................................................................................ 87
x
4.2.2 Carbon Nanotube Growth ....................................................................................... 89
4.2.3 Characterization Techniques ................................................................................... 90
4.2.4 Adhesion Testing....................................................................................................... 91
4.3 Results and Discussion .................................................................................................. 92
4.3.1 CNT Growth Kinetics and Activation Energies .................................................... 92
4.3.2 Diffusion Mechanisms .............................................................................................. 98
4.3.3 Causes of Reduced Diffusivity for CNTs grown on Polysilicon ...................... 105
4.3.4 Improving CNT Adhesion to Polysilicon ............................................................ 108
4.4 Conclusions ................................................................................................................... 111
5. Improved Performance of Field Emission Vacuum Microelectronic Devices for

Integrated Circuits .................................................................................................................... 113
5.1 Introduction................................................................................................................... 114
5.2 Experimental Methods................................................................................................. 118
5.3 Results and Discussion ................................................................................................ 121
5.3.1 Determination of Proximity Effects ...................................................................... 121
5.3.2 Simulation Guided Analysis and Redesign ......................................................... 124
5.3.3 Simulation for Electron Transmission Analysis and Redesign ......................... 128
5.3.4 Experimental Confirmation ................................................................................... 130
5.4 Conclusion ..................................................................................................................... 133
6. Low Temperature Co-fired Ceramic Packaged MEMS Micro-ion Source for Miniature
Mass Spectrometry Applications ............................................................................................ 135
6.1 Introduction................................................................................................................... 137
6.2 Design and simulation ................................................................................................. 140
xi
6.2.1 Components of a Nier-type Ion Source ................................................................ 140
6.2.2 High Performance Ion Source Characteristics..................................................... 141
6.2.2.1 Ionization Volume Impact on Resolution ..................................................... 142
6.2.2.2 Parallel Equipotential Surfaces ...................................................................... 143
6.2.3 Proposed Solution ................................................................................................... 144
6.2.3.1 MEMS ................................................................................................................ 144
6.2.3.2 LTCC .................................................................................................................. 146
6.3 Design Details ............................................................................................................... 149
6.3.1 MEMS ........................................................................................................................ 149
6.3.1.1 Observed Failure Mechanisms and Mitigation Techniques ...................... 150
6.3.1.2 Cathode and Grid ............................................................................................ 154
6.3.1.3 Repeller (i.e., Floor) .......................................................................................... 155
6.3.1.4 Wire Bonding Pads .......................................................................................... 156
6.3.1.5 Latches ............................................................................................................... 156
6.3.2 LTCC ......................................................................................................................... 157
6.3.2.1 LTCC Layer Specifics ...................................................................................... 157
6.3.2.2 Assembly Details.............................................................................................. 160
6.3.2.3 First Generation ................................................................................................ 161
6.3.2.4 Second Generation ........................................................................................... 162
6.4 Characterization of Packaged Micro-ion Source ...................................................... 165
6.4.1 Electrical Characterization ..................................................................................... 165
6.4.1.1 Electrons ............................................................................................................ 165
xii
6.4.1.2 Ions ..................................................................................................................... 168
6.4.2 Dispersion Measurements...................................................................................... 169
6.4.2.1 Simulation ......................................................................................................... 169
6.4.2.2 Experimental..................................................................................................... 170
6.5 Conclusion ..................................................................................................................... 173
7. Summary and Recommendations for Future Work ......................................................... 174
7.1 CIMS CNT Electron Source ......................................................................................... 174
7.1.1 Recommendations for Further Investigation ...................................................... 175
7.2 CNTs and Poly-Si: Kinetics, Mechanisms, Adhesion .............................................. 178
7.3 Improved Performance of FE-VMDs for IC.............................................................. 180
7.4 LTCC Packaged MEMS Micro-ion Source ................................................................ 183
Appendix A................................................................................................................................ 187
Appendix B ................................................................................................................................ 193
References .................................................................................................................................. 197
Biography ................................................................................................................................... 227
xiii
List of Tables
Table 1: Comparing threshold electric field requirements for different materials;
reproduced from [98].................................................................................................................. 42
Table 2: Primary FE Device Applications ................................................................................ 43
xiv
List of Figures
Figure 2.1: Bonding structure of a carbon nanotube. The sp2 hybridized bond (s bond)
and the out of plane orbital p bond are shown. Diagram derived from [43]. ................... 18
Figure 2.2: (a) TEM image of the tips of one MWCNT with bamboo structure,
reproduced from [58]; (b) schematic diagram of the 915 MHz MPECVD system used to
grow vertically aligned MWCNTs in this study, reproduced from [57]............................. 21
Figure 2.3: A free electron (red sphere in diagram) possesses a lower energy inside a
metal than in vacuum, the work function is the amount of energy needed by the electron
to escape into vacuum. Adapted from [88] with relevant modifications. .......................... 27
Figure 2.4: Various electron emission processes; adapted and modified from [91]. ......... 29
Figure 2.5: CNT field emitter characterization as reported by [98]. Electron emission
current versus applied field characteristics for a CNT field emission sample (inset). The
F-N plot, as derived by equation 10, is shown........................................................................ 37
Figure 2.6: (a) schematic showing the spatial distribution of an electric field potential
around a sharp tip, (b) SEM of high aspect ratio CNT emitters with tips shown in the
inset, (c) tungsten field emitter from a SEM reproduced from [108]. .................................. 39
Figure 2.7: Potential-energy diagram illustrating the effect an applied electric field has
on the energy barrier of a planar emitter versus a micro-tip emitter. ................................. 40
Figure 2.8: (a) Spindt-type field emitter. SEM of single emitter shown; reproduced from
[2]; (b) Deep reactive ion etched (DRIE) silicon field emitter arrays; reproduced from
[117]. .............................................................................................................................................. 44
Figure 2.9: (a) SEM of a microfabricated nanodiamond lateral FE diode reproduced from
[15]; (b) SEM of a CNT emitter array utilized in this work. .................................................. 46
Figure 2.10: Schematic diagrams representing electrode type and placement in a simple
diode and triode configuration. ................................................................................................ 47
Figure 2.11: SEM’s showing evolving development of the Duke/RTI VMD platform; (a)
original concept as fabricated with MEMS platform and CNT emitters, (b) adoption of
CNT FE-VMD as an ion source with ion collection on chip laterally, (c) adoption of the
CNT FE-VMD for dual-charge carrier operation; reproduced from [145, 146, 148, 151]. . 52
xv
Figure 2.12: (a) PolyMUMPS process flow with assembly; (b) device on test board. ....... 54
Figure 2.13: UHV test system used for field emission device testing. ................................. 55
Figure 2.14: Schematic diagram of a mass spectrometer. ...................................................... 57
Figure 2.15: Schematic diagrams showing the ionization process in both, (a) electron
ionization, (b) and chemical ionization. ................................................................................... 59
Figure 3.1 Images of the CNT electron source components (a) SEM image of CNT field
emitters as grown on the substrate, (b) photograph of the Duke/FLIR CNT electron
source platform set inside its wiring harness mount, (c) photograph of CNT field
emitters mounted into the platform. The source is shown before and after placement of
extraction mesh. .......................................................................................................................... 68
Figure 3.2 Electrical characteristics of the carbon nanotube electron source (a) I-V
characteristics showing three consecutive and increasing voltage sweeps, (b) Fowler-
Nordheim plot of I-V curve #3 with nonlinearity of the slope attributed to a nonlinear
field enhancement factor, (c) Lifetime analysis operating at a pressure of 1x10-2 Pa (1x10-4
Torr) of room air and a fixed 5 µA CNT emission current. .................................................. 71
Figure 3.3 Integration of the carbon nanotube electron source into the explosive trace
detection mass spectrometer. (a) Schematic of the ionization region showing source
location, (b) photograph of the desktop mass spectrometer, (c) a magnified photograph
of the ionization region showing the CNT field emission electron source installed......... 75
Figure 3.4: Trace explosive chemical ionization spectra collected using both the CNT
field emission (left column) and the filament thermionic emission (right column) sources
in the explosive trace detection desktop MS. The spectra for TNT are shown in (a) and
(d), the spectra for RDX are shown in (b) and (e), and the spectra for PETN are shown in
(c) and (f). ..................................................................................................................................... 80
Figure 4.1 Morphology of carbon nanotubes simultaneously grown on a) Si (100) and b)

polysilicon imaged by SEM. c) TEM micrograph of a CNT with bamboo-type inner
walls, with inset depicting a catalyst iron nanoparticle embedded within the CNT base;
d) schematic of field emission test chamber to determine poor CNT adhesion. ............... 90
Figure 4.2: Arrhenius plot used to determine activation energies corresponding to the
linear and parabolic regions of CNT growth. The slope of the linear region for both
substrates is quite similar and corresponds to bulk diffusion of carbon precursor into the
xvi
γ-Fe catalyst nanoparticles. The slope in the parabolic region differs between CNTs on
Si (100) and polysilicon, leading to different activation energies for the diffusion-limited
phase of growth. .......................................................................................................................... 95
Figure 4.3: CNT forest height kinetics at 850 °C. The solid curves correspond to the fit to
the Deal and Grove expression, with A and B values listed. ................................................ 97
Figure 4.4: CNT forest height as a function of growth temperature on polysilicon MEMS
devices. All CNT forests were grown for 150 s.................................................................... 100
Figure 4.5: Raman spectra of CNTs grown on Si (100) and polysilicon substrates. The
crystallite size is 66 Å for CNT on Si (100) and 201 Å for CNTs on polysilicon. ............. 102
Figure 4.6: Plan view SEM micrograph of graphenated CNTs and b) higher
magnification image of a g-CNT. Inset: TEM micrograph of a few-layered graphene
foliate terminating in 3-5 graphene layers............................................................................. 104
Figure 4.7: Catalyst nanoparticle arrays produced by dewetting at 850 °C in an ammonia

plasma environment on a) Si(100) and b) polysilicon. A typical particle size of 65 nm
was observed on Si (100) and at the top of polysilicon grains, and smaller nanoparticles
of approximately 25 nm diameter were observed at the polysilicon grain boundaries. 107
Figure 4.8: (a) Si (100) and (b) poly-Si. The CNTs on poly-Si appear to display a higher
degree of tortuosity, which could explain why the diffusivity is markedly lower for
growth on polysilicon and the parabolic activation energy is larger. ............................... 108
Figure 4.9: Average reflectance from the underlying substrate as measured by

spectrophotometer for CNTs grown using various metallic interlayers. The error bars
represent standard deviation. An adhesion improvement of approximately 1.3x was
observed for Mo interlayers, and approximately 2.5x for Ti interlayers compared with
the control sample of CNTs grown on Fe-coated poly-Si. .................................................. 111
Figure 5.1: (a) schematic diagram of dual CNT FE-VMD illustrating the physical layout
of panel electrodes with device #1 (left) and device #2 (right), location of CNT emitters,
and the biasing method. The labeled IN’s and OUT represent the potential inputs/output
for logic circuit realization; (b) SEM image of the fabricated device with electrode panels
rotated up and locked in place as described in [147, 271]. An SEM image of the CNT field
emitter arrays as grown on the cathode are shown in the inset. ........................................ 120
xvii
Figure 5.2: Current-voltage characteristics of a dual CNT FE-VMD revealing the
undesired proximity effects; (a) both devices are operating in the ON state (0 V on the
cathode, 200 V on the anode, and extraction potentials on the grids swept) with no
adverse effects; (b) device 1 in ON state with ground potential on the cathode, 200 V on
the anode, and the extraction potential on the grid swept from 0 V to 95 V, device 2
(inset) is in the nominally OFF state with 0 V on the cathode and 0 V on the grid; the
signal observed at the anode of device 2 is due to crosstalk (i.e. current from device 1’s
emitters being pulled across the vacuum channel). ............................................................. 124
Figure 5.3: A schematic diagram illustrating the potentials on each electrode and the
SIMION® simulation demonstrating the proximity effects experienced by the dual CNT
FE-VMD; (a) device 1 is biased for field emission (ON state) and device 2’s grid is
grounded, rendering it in a nominally OFF state; (b) simulation results show that even
though device 2 is OFF, its anode is receiving 10-15% of the electron current from device
1 (similar to experimental results) resulting in an undesired ON state signal at anode 2.
..................................................................................................................................................... 126
Figure 5.4: SIMION® simulation modeling with optimized center shielding electrode to
eliminate the crosstalk between neighboring devices; (a) two proximal devices with the
shielding electrode off and crosstalk taking place from the ON device 1 (left) to the OFF
device 2 (right); (b) same design with the shielding electrode grounded, effectively
shielding the devices and their corresponding vacuum channels from one another.
Operating the shielding electrode at ground potential provided the best shielding
without interfering with individual device performance. .................................................. 127
Figure 5.5: SIMION® simulation modeling of electron transmission properties of the

CNT FE-VMDs; (a) Simulated electron trajectories in the original microtriode device
with an average transmission of 25% (electrons passing through grid and collecting at
anode); (b) simulation showing equipotential lines of new geometry designed to create
pre-lens effect around CNT emitter bundles thereby enhancing focusing properties; (c)
simulated electron trajectories of new geometry showing an increased grid
transmission of 80%. ................................................................................................................. 130
Figure 5.6: (a) schematic diagram illustrating new physical layout of panel electrodes
with device #1 (left) and device #2 (right), location of CNT emitters, biasing method, and
new potential inputs/outputs for logic circuit realization with decoupled cathode and
extraction grid; (b) SEM image of redesigned fabricated device with electrode panels
rotated up and locked in place and center shielding electrode flat on the substrate
between the devices. ................................................................................................................. 131
xviii
Figure 5.7: Center shielding electrode effect on proximity effects. Left device is ON and
the right device is OFF; (a) with shielding electrode grounded, crosstalk current on the
order of 10-15% is measured at the anode of the OFF device; (b) with the shielding
electrode electrically grounded the crosstalk current measured at the anode of the OFF
device is decreased by an order of magnitude (1-2% on average). .................................... 132
Figure 5.8: (a) original 3-panel microtriode operated with cathode = 0V, extraction grid
swept (0-140 V), and anode = 150 V. Pie chart inset shows average distribution of
emitted current at maximum extraction potential (25% reached the anode, 58%
intercepted by the grid, and 17% lost); (b) 4-panel geometry driven in the new operating
mode with cathode = 0V, screening electrode = 20 V, extraction grid swept (0-125 V), and
anode = 150 V. On average, 67% of the current reached the anode, 23% was intercepted
by the grid, and 10% was lost. ................................................................................................. 133
Figure 6.1: Schematic diagram of a Nier-type geometry ion source. ................................. 140
Figure 6.2: schematic showing the two important characteristics of a high performance
ion source; (a) ions should be formed in a region of small potential difference, or zero
electric field, in order to reduce energy dispersion; (b) the equipotential field lines above
the ionization region should be flat in order to minimize angular dispersion. ............... 144
Figure 6.3: SEM failure analysis of microtriodes; (a) spring failure due to overcurrent, (b)
panel snapping from high fields or mechanical failure, (c) loss of CNT adhesion and
cathode-grid shorting, (d) latch failure with panel snapping............................................. 151
Figure 6.4: (a) Top-down schematic of new micro ion source; (b) SEM of fully assembled
symmetric micro ion source; CNT field emitters (inset) are synthesized to specific
lengths directly on cathode prior to assembly; (c) SEM image of precise alignment
between CNT emitter bundles and grid holes; (d) SEM image showing thicker latch
arms (current carriers) and improved electrical contact point. .......................................... 155
Figure 6.5: (a) Exported CAD image showing exploded view of the LTCC layers with
labels indicating various components, (b) cutaway view of the assembled LTCC
package. ...................................................................................................................................... 158
Figure 6.6: Exploded view of the 2nd generation of the LTCC scaffold with labels ......... 159
Figure 6.7: (a) Magnified image of the 1st layer with MEMS micro-ion source secured
within the cavity, SEM images of source given; (b) cutaway view of the complete
xix
scaffold with locations of apertures shown, SEM images of extraction and coded
aperture shown.......................................................................................................................... 160
Figure 6.8: Optical images of the 1st generation of the packaged miniature ion source; (a)
device secured in the cavity and wire bonded to the 2nd layer of the LTCC, (b) bottom
half of LTCC secured onto test board, (c) after capping with final two layers, packaged
device is mounted upside down on PCB and bonded for testing, (d) a copper plate is
used to collect emitted ions, (e) the UHV testbed used. ...................................................... 162
Figure 6.9: Optical image of the 2nd generation of the LTCC scaffold prior to the 1st and
2nd stage of electrical characterization; a) before capping; b) after capping. .................... 163
Figure 6.10: simulation results of 2nd generation miniature ion source; (a), (c), and €
provide a side view; (b), (d), and (f) provide a view from the center of the floor looking
towards a grid; (a) and (c) show the device with no field lines or ions plotted; (c) and (d)
show the field lines plotted; (e) and (f) show field lines and simulated ion trajectories
plotted; (g) and (h) are top down views with field lines and ion spatial mapping through
the coded spatial filter, respectively. ...................................................................................... 164
Figure 6.11: Electrical characterization performed on a device prior to capping; (a) IV

characteristics; (b) Triode characteristics; (c) Fowler-Nordheim model fitted to IV data to
verify field emission. ................................................................................................................ 166
Figure 6.12: These three plots illustrate the process of burn-in on a device; (a) An initial I-
V curve is taken showing a VTO of approximately 160 V, (b) a one hour burn-in is
conducted where the VTO is reduced, (c) improved I-V curve after burn-in. ................... 167
Figure 6.13: Electrical characterization plots of a packaged MEM micro-ion source; both
turn-on and threshold voltage I-V analysis plots are shown.............................................. 168
Figure 6.14: Ion current measurements from a packaged micro-ion source. Chamber
pressure was increased until ion current was detected. Repeller and extraction aperture
voltages were then cycled to establish a periodic measurement of ions........................... 169
Figure 6.15: SIMION energy and angular dispersion results for the packaged device. Ion
trajectories, plotted in tan, are focused vertically off-chip and through the series of
apertures and through the outlet which would lead to a mass analyzer. The energy
dispersion is 14 +/- 4 eV. Angular dispersion is approximately 13 degrees. .................... 170
xx
Figure 6.16: Dispersion measurements of the packaged micro-ion source; (top) schematic
diagram showing arrangement of electrodes on the MEMS device, apertures, and
orientation with the detector, and camera picture of the packaged micro-ion source
secured in the aluminum mount; (middle) magnified camera packaged source directed
at the detector for dispersion measurements, and image of the ion exit point showing the
strike points on the detector during angular dispersion measurements; (bottom) angular
dispersion data on the detector showing the average angular dispersion of 13 degrees,
and energy dispersion data showing ion current on detector on the left y-axis, sweeping
retarding grid potential on the x-axis, and the derivative of the stopping potential data
on the right y-axis. Average energy of the ions was 22 eV with an average energy
dispersion of 6 eV...................................................................................................................... 172
Figure 7.1: (top left and right) Camera and SEM images of several embodiments of the
preliminary device fabricated on Si substrates; (bottom left and right) electrical
characterization shows performance capabilities of 8-10x better than previous design. 178
Figure 7.2: (a) Schematic diagram of logic OR gate configuration for CNT-FE VMD; (b)
microscope image of designed/fabricated quad logic device test platform; (c) SEM image
of designed/fabricated oscillator circuit composed of four CNT-FE VMDs..................... 183
Figure 7.3: (top left) Schematic diagram of ion trajectories leaving the packaged ion
source and traveling a cycloidal path within the electric sector due to the orthogonal
uniform electric and magnetic field; (top right) CAD image of electric sector, cutaway
view shown; (bottom left) CAD image of electric sector situated in its guide with the
detector in place; (bottom right) entire assembly placed inside a vacuum manifold; the
magnet (not shown) wraps around the vacuum manifold. ................................................ 186
B.1: PFTBA spectra collected in the explosive trace detection mass spectrometer with the
CNT field emission source (left column) and the filament thermionic emission source
(right column). Three modes are illustrated, including an initial electron ionization (EI)
mode to test for proper source operation, followed by both negative and positive
chemical ionization (NCI and PCI) modes. (a) EI spectra with CNT source (b) NCI
spectra with CNT source (c) PCI spectra with CNT source (d) EI spectra with filament
source (e) NCI spectra with filament source (f) PCI spectra with filament source.
Analysis shows spectra are nearly identical for both EI and NCI modes, whereas PCI
mode is visually different, with several indications that chemical ionization is occurring.
For example, signal peaks at m/z 502 exceed that of both m/z 131 and m/z 69. .............. 196
B.2: A calibration curve of desorbed TNT is shown and is linear, as expected. Trace
explosive amounts were consistent with trace standards in the security field. ............... 196
xxi
List of Symbols and Abbreviations
CNT: Carbon Nanotube
SWNT: Single-walled Carbon nanotube
MWNT: Multi-walled Carbon Nanotube
VMD: Vacuum Microelectronic Device
MEMS: Micro-Electro-Mechanical Systems
FE: Field Emission
F-N: Fowler-Nordheim
MS: Mass spectrometry
EI / CI: Electron Ionization / Chemical Ionization
CIMS: Chemical Ionization Mass Spectrometry
UHV: Ultra High Vacuum
I-V: Current-Voltage
MUMPs®: Multi-User-MEMS-Processes
Vto / Vth: Turn-On Voltage / Threshold Voltage
LTCC: Low Temperature Cofired Ceramic
CAD: Computer-Aided Design
xxii
Acknowledgements
First and foremost I would to wholeheartedly thank my advisor, Dr. Jeffrey Glass
for believing in me and giving me the opportunity to work with him and the amazing
research group he has developed. The laboratory environment that he has fostered with
brilliant peers, mentors, and state-of-the-art facilities is clearly the reason for my
personal accomplishments. His proficiency to always be available for motivation,
encouragement, and support, as well as his ability to impart unvarying positive work
energy and excitement, has instilled in me values that I will carry throughout my entire
career and life. I am a better scientist and professional having worked for him. He has
truly been a great mentor and friend, and I will certainly miss my time in the group.
I would like to thank Dr. Charles Parker for being so supportive throughout my
time at Duke. He consistently went above and beyond the role of lab manager and his
mentorship, both professionally and personally, is equally as important to my success at
Duke University. I appreciate every opportunity and all the advice he provided me
when constructing manuscripts and proposals, and mentoring students. Most
importantly, I will miss all of our conversations. Whether it consisted of professional
recommendations, personal and family advice, or even the friendly banter of Android
versus Apple. Because of him, I leave the NTFL with three things instilled in my mind:
1) never mix fonts on a presentation, 2) I will never have a better cup of coffee than one
brewed by Charles Parker, 3) there is an RSS feed for everything, yes, even Florida.
xxiii
I would like to thank Dr. Brian Stoner, Dr. Jeffrey Piascik, and Dr. Kristin
Gilchrist of RTI International, Engineering and Applied Physics Division. They provided
me with an amazing opportunity to join RTI as an intern upon first arriving here at
Duke University. The professional development and growth that I gained from my
experience working under their advisement and mentorship is priceless. Not a day
passed that I did not feel blessed to have the opportunity as a graduate student to
simultaneously gain industry experience and work with such a talented group of
scientists. I thank them for every meeting, every minute of their time assisting with
publications, and the opportunity to learn from them all.
I would like to thank Dr. Jason Amsden and Dr. Matt Kirley for always being
available for inspirational conversation and ideas throughout the time we spent together
in the NTFL. Their assistance with project and personnel management, as well as project
organization and success, is more than appreciated.
I am certainly very grateful to all of the members of my Ph.D. committee: Dr.
Brian Stoner, Prof. Adrienne D. Stiff-Roberts, Prof. Aaron Franklin, and Prof. Martin
Brooke. They were all individually important to my success here at Duke. I am truly
thankful for all of their teachings, professional and research input, and your passion to
help me grow as a scientist and make the most out of my time as a graduate student.
I would like to thank my entire research group and all of the individuals, both
past and present, within and outside our lab that I have had the pleasure of working
xxiv
with. I leave Duke having grown not only academically and professionally, but also
with many friends that I will certainly never forget. Whether inside the lab, on the soccer
field, or “off-site,” I value all of the time we had together. I truly believe I am a better
person and leave having learned many things from my colleagues and friends.
I would like to thank Steve Hall at RTI International. It was an absolute pleasure
to work alongside Steve on so many amazing projects. Not a day went by that Steve was
not willing to assist me with anything I needed for a project, publication, or conference.
We shared many great conversations, both professional and personal, and I value all of
the advice and input I received from him over our years working together.
I would also like to thank Dr. Stephen Saddow, Dr. Christopher Locke, and Dr.
Christopher Frewin of the University of South Florida, my alma mater. Dr. Saddow gave
a young sophomore engineering undergraduate the opportunity to volunteer in his
research lab, and it forever changed my outlook on research and my career. I can’t thank
him enough for allowing me to join his research team and gain valuable experience
when I needed it the most. That experience, without a doubt, gave me the chance to
come to Duke. Dr. Locke and Dr. Frewin were two of the most amazing mentors that an
aspiring researcher could ever ask for. They spent many hours working by my side,
training me, letting me work with them during long hours in the clean room or growing
SiC thin films, and of course, accompanying them to Mr. Dunderbak’s to “discuss
science.”
xxv
Last, but certainly not least, I would like to say thank you, from the bottom of my
heart, to my family for always being there for me. Words cannot begin to describe how
important they are to my success as a scientist, and as the person I am today. The
support I received throughout my entire academic career is more than any one person
deserves. My dearest wife, Rebecca, who has stood by my side from the very beginning
and supported me through all of the wonderful, and challenging, times. I love her very
much for all that she has done to make this possible. And words cannot explain the love
I have for the son that she has blessed me, it is my goal to provide him with the most
amazing life possible. Rebecca has been my tower of strength through it all, and I know
that our growing family will only benefit from the work that “both of us” put into
making this a reality. To my amazing mother and father, I will never forget the sacrifices
that they made to get me to this point in my life. From every science project they stayed
up all night perfecting with me, to each second they spent pushing me to be the best
student, and person, that I could be. I could spend a lifetime remembering all of the
important events, which led up to this point, that were a direct result of their constant
support, motivation, and desire to create the best opportunities they could for Matthew
and I. This achievement is shared by both of them. And to my amazing brother, who
has been there for me more than he will ever know. He has been my best friend for my
entire life, and he has inspired me in so many ways. From every game of golf, to every
hug of support, I cannot thank him enough for everything he has done.
xxvi
1. General Introduction
Nanotechnology is transforming the way we live. Not only are electronic devices
and computers growing in number and capability but other fields of science are
benefiting from our ability to understand and work at the atomic level. Where
established technologies see boundaries, nanostructured materials and the advanced
devices they produce, bridge the gap between molecular science and applied physics.
With new and present day micro and nanostructures continuing to demonstrate their
impressive properties, it is important we remember to combine continuous progression
in discovery with focused research on existing concepts; thereby leading to improved
understandings and applications.
While much research is dedicated to the continued development of
nanostructured materials, understanding and developing methods towards integration
with existing technology is also of great importance. Whether it be for microelectronic
development or another unique employment, if nanostructured materials are to be
realized in practical applications, the challenges associated with integrating materials,
and the work required to integrate them, cannot be disregarded. Nevertheless, the field
of microelectronics has already shown, and is primed to continue benefitting
significantly, from nanostructured material contribution.
One category in particular, cathode development, has seen an influx of exciting
and novel advancements through the incorporation of nanomaterials. Not only have
1
existing technologies been enhanced through their incorporation, but innovative and
novel nanostructured materials have been used to realize new possibilities in cathode
development. As a result, new application space has been developed and long-standing
technologies are remerging with new capabilities.
This chapter begins with a brief introduction into the electronic materials
currently investigated for cathode development, specifically in field emission
microelectronic device development, a subject that will be discussed in more detail in
section 2.3. Next, the emergence of the field of vacuum microelectronics, whose roots are
ultimately derived from the traditional vacuum tube, and a brief overview of vacuum
microelectronics and governing principles will be discussed. Additionally, this chapter
introduces the motivation and objectives of the research herein and concludes with a
brief outline and arrangement of the work.
1.1 Electronic Materials for Cold Cathode Field Emission

Undergraduate electronic materials courses teach us that there are three basic
classes of materials: conductors, insulators, and semiconductors. Conductors permit the
flow of electrons, insulators block the flow of electrons, and semiconductors fall in
between as a “part-time” conductor whose conductivity can be controlled. Electronic
materials have been investigated as source materials in vacuum electronics since their
development. The traditional vacuum tube, developed from conductive metal
electrodes, operates on the premise of thermionic emission. In this process, electrons
2
overcome the surface potential barrier (work function) of a material and are emitted into
vacuum because their internal thermal energy is raised via the application of very high
temperatures. Cold cathode field emitters do not provide emitted electrons through the
application of high temperatures; instead they use electric fields to allow the electrons to
overcome the surface potential barrier. Early cold cathode field emitters were
developed from basic conductive metals, similar to vacuum tubes. They have since
evolved to utilize a wide variety of electronic materials. Characteristically field emitters
are now developed from a micro/nanostructured material with excellent electronic and
additional properties. The process of generating electrons using electric fields is referred
to as field emission; and while at its core the process is fundamentally dissimilar to
thermionic emission, both processes accomplish the same goal of extracting electrons to
move through the device. The fundamentals and specifics of electron field emission as
proposed by Fowler and Nordheim will be discussed in detail in Chapter 2. Briefly, the
intense electric field is applied across a vacuum on a solid to extract the electrons [1, 2].
The electrons within the solid undergo the quantum mechanical process of tunneling
through the surface barrier of the material/vacuum interface and are emitted into the
vacuum channel. When compared to thermionic emission, field emission is able to
generate higher current densities which leads to its higher power applications. Electrons
are extracted from a material when the electric field is approximately one gigavolt per
meter (or 0.5 volts per angstrom) at the surface of a metal [1, 2]; there is also a strong
3
dependence on the geometrical properties and work function of the material as well. It is
this large field requirement that renders field emission from a flat surface impossible for
practical applications. However, the smaller the emitting material is fabricated (a sharp
needle like structure for example), the more efficient it becomes in terms of the required
applied voltage. This is because the field is concentrated, or enhanced, at the sharp tip
which is otherwise known as the emission site. As a result, smaller tips require
substantially less applied voltages [1, 2]. The specifics of enhancements experienced by
nanostructures will also be discussed in detail in Chapter 2.
It is motivating to see that cold cathode field emitters do currently exist in some
commercial products, primarily in the display market with field emission displays
(FEDs) [3-5]. However, like most technologies, a number of challenges still remain to
further commercial applications. Present day research tends to focus on new field
emission materials or cathode structures. Field emitting materials require specific
properties, and often times the more easily fabricated emitters suffer from a collection of
unsatisfactory properties. For example, there are often instability concerns with the
emitted current in most materials due to the comparatively larger field emitted currents.
Additionally, lifetime and failure concerns vary with material. While several materials
have been explored to date, there are still concerns with many of them and a perfect
material has not yet emerged. Simply put, present day emitter materials require high
operating voltages and their emission current is far from perfectly stable and reliable.
4
These factors are a large barrier for practical applications and thus much research into
controlled fabrication techniques and development of low work function materials have
been conducted. It is these reasons that have led to the very limited commercial
applications of field emission based instruments [6].
Early field emission research began with metal structures. However, large
voltage requirements caused by the inability to develop ideal geometries, high material
work functions, and regular impurity adsorption on metal surfaces leading to large
current instabilities rendered their development limited. From there we saw the
development of the Spindt cathode [7], which employed the most common material
available in the semiconductor fabrication industry as a platform, silicon. Well
understood IC fabrication techniques were used to conduct microfabrication and
develop sharp tip field emitters made out of molybdenum. Over the years, as
microfabrication processes improved and developed into nanofabrication possibilities,
the structures became smaller with greater aspect ratios. Consequently, field emission
properties of the structures improved. Fast forwarding in time, numerous materials
have been developed and investigated for their field emission properties, ranging from
silicon fibers and nanowires [8, 9], gallium arsenide (GaAs) [10], gallium nitride (GaN)
[10, 11], boron nitride (BN) [10, 12], silicon carbide (SiC) [13, 14], and diamond [14-17].
While they all have their benefits, these materials as electron field emitters have had
difficulty reporting performance metrics suitable for promising practical application.
5
The ideal field emitter needs to offer several key properties: high durability and lifetime
(i.e., resistance to sputtering by residual gases in the emitting environment), low turn-on
voltages (i.e., the threshold voltage required to initiate electron field emission), the
capability of producing large current densities if the application requires it, and an
overall stable and low noise operating ability.
Recently, field emission from another class of nanostructured carbon materials
including carbon nanofibers, both single-wall and multi-wall carbon nanotubes
(SWCNT and MWCNTs respectively), as well as graphitic like carbon [18-22] have been
investigated in great detail. In short, the considerable extent of research on these
structures have shown that carbon nanostructures encompass many of those attractive
qualities discussed in the previous paragraph. On the subject of durability, the sputter
yield for carbon is the lowest among all solids making it much less susceptible to
ambient gas bombardment damage. Because of the very high aspect ratios found in
carbon nanostructures, the field enhancement at their tips is very strong resulting in
very large local electric fields and ultimately low turn-on voltages. And in regards to
current density, the top current-density values to date for carbon based field emitters,
held by a CNT emitter array as reported by Fursey [2], are approaching the free-electron
limit (i.e., when the work function barrier is completely compensated by the external
field) at a value of nearly 1011 A/cm2 (at an area of 1013 cm2). This assemblage of reasons
6
and achievements have revealed the potential of carbon nanotube field emitters, thus
recognizing them as one of the most promising field emitters currently available.
1.2 Vacuum Microelectronics Overview

Emerging vacuum microelectronic devices continue to be a prime candidate for
applications where advanced micro and nanostructures are integrated with novel
platform materials, such as field emission cathodes, and typically benefit from novel
packaging solutions. Their interest, widely due to their numerous unique properties, is
also driven by the wide variety of practical applications. The original thermionic
vacuum tube, invented in 1904 by John Ambrose Fleming [23] and respectively termed
the Fleming Diode, or Fleming Valve, led to the establishment of several advanced
technologies throughout the early 1900’s. Three years after Fleming introduced his tube,
primarily used for rectifiers in tube amps, Lee DeForest invented the triode vacuum tube
[24] and introduced the concept of amplification. It took some time for the amplification
properties of the triode device to become well understood. Shortly following, electronic
device development in radio and telephone, television, and even more complex
applications including microwave radar, analog, and digital computer were transformed
considerably [25]. The vacuum tube offered these technologies a path forward to
practical application along with the ability to scale and spread globally.
These early electronic vacuum devices weren’t without their shortcomings,
however. The mere fact that a strict vacuum and a cathode heated to 1000 °C were basic
7
requirements simply to generate electrons meant that power consumption and overall
efficiency weighed heavy on the technology. Additionally, their physically large size
and high operating voltage requirements added to the longing for a better solution.
Relatively speaking, it wasn’t long thereafter that many believed the inadequacies of the
vacuum tube were slowly being overcome with the invention of the solid-state transistor
in 1947 [26], and soon after the integrated circuit (IC) [27, 28]. The once frail, sizable, and
not very efficient vacuum tube now stood in the shadow of the small, high-speed, and
mostly reliable solid-state counterpart.
It goes without saying that the solid-state electronics era has certainly brought
forth many advancements in a wide variety of applications and fields. However, the
vacuum tube lives on. In fact its “rebirth”, if you will, can indeed be attributed to the
advancements in processing techniques that were developed for solid-state electronic
production. There are, however, certain properties, or new applications, where solid-
state unfortunately falls short. For example, the need for high frequency and/or high
power operation; or applications that require transistor-like performance while
maintaining a small form factor, but require environmental immunity (e.g., extreme
temperature or radiation hardness). An example would be certain aeronautical and
industrial applications where the ideal location for sensor placement would be in, or on,
a high temperature structure [29, 30]. A common problem with using a solid-state device
is the undesirable generation of thermally induced carriers in the channel; an issue that
8
is not of concern in a vacuum channel. Modern day practice sacrifices accuracy for
reliability by locating sensors at ideal distances and making connections with wiring
[31].
When radiation heavy regions are of interest for sensor and circuit placement, a
great deal of expense is invested in radiation hardening the devices. This process not
only ads significant costs, but also sacrifices efficiency as rudimentary circuits must be
utilized to gain maximum radiation protection [29, 32]. Even still, radiation hardening
simply delays the inevitable demise of the device to a variety of failure modes related to
ion irradiation and subsequent damage to the channel in the SSDs; this again, is not a
concern when vacuum channels are utilized. Additionally, the operating speeds of solid-
state devices is directly proportional (i.e., constrained) by the carrier saturation velocity
in the material. The lifetime of SSDs is also problematic.
Utilizing a vacuum channel device as an active circuit element brings about
advantages in speed and lifetime due to the ballistic transport in the vacuum channel [2,
33]. The elimination of signal scattering in the channel material means the devices can
be operated at elevated frequencies with much higher efficiency. Therefore it is no
surprise that the renewed interests in the utilization of vacuum devices to meet these
growing needs has grown steadily in the last 50-60 years, spawning a new field of study
centered on vacuum microelectronics. Vacuum microelectronic devices (VMDs) are
typically fabricated using advanced semiconductor microfabrication processes and can
9
operate at room temperatures. VMDs demonstrate amplification, switching, and control
because ultimately they are analogous to the conventional vacuum tube. Because they
too incorporate the vacuum channel as the medium for carrier transport, similar to the
vacuum tube, they retain the temperature and radiation tolerance, as well as the longer
lifetimes and slightly higher reliability [2]. Additionally, higher operating speeds are
attained not only because of the vacuum channel, but also just by the nature that the
electrons are having to transmit over much shorter distances [33]. Developing a
“junction-less” small form factor vacuum device, immune to temperature and radiation
concerns, and with the added benefit of longer lifetimes and higher operating speeds,
has been the goal for researchers in the field.
Additionally, VMDs have shown great potential as the electron source within an
ion source; in mass spectrometry applications for example. Traditional mass
spectrometer ion sources typically utilize filament thermionic emitters which required
high temperatures to provide enough electron current to generate significant ion
current. Cold cathode field emitters offer many advantages over their thermionic emitter
counterparts. Specifically, cold cathodes can be cycled on and off rapidly without the
degradation disadvantage seen with thermionic emitters. This is advantageous for
power concerns in an instrument. In the absence of thermal distortions the hot
thermionic emitting cathodes, the extraction grids can be placed close to the cathode
which gives further operating speed and energy benefits. Field emission sources can also
10
be operated in pulsed mode. Thermionic emitters do not traditionally scale down in size
well, a fundamental limit if miniaturization of the ion source is desired. Finally, field
emission sources provide benefits in the emitted energy spread of the electrons.
Typically field emission energy spread is an order of magnitude less than thermionic
emitters. This is why field emission sources are often used in scanning electron
microscopes (SEM) to achieve improved resolution.
1.3 Motivation and Objectives of this Research

The united ambition to arrive at a scalable, batch-fabricated, micron-sized
miniature vacuum tube-like device is undoubtedly shared among all researchers in the
field. Despite all of the research in today’s innovative vacuum microelectronic platforms
and field emission based cathode structures, there exists a need to better understand the
challenges experienced with integrating these two key components. It is clear that the
application space for VMDs, and specifically FE-VMDs, is plentiful. Continued
development in either of the two key areas, emitter improvement and integrable
packaging, could see progress in many application categories: electron and ion sources,
power amplifier and IC’s, as well as novel instrumentation that has yet to be
investigated. Application driven research towards utilizing the community established
CNT field emitter arrays alongside existing technologies that allow for packaging and
implementation is needed. As is the case in most situations, addressing the fundamental
lack of information on dependent aspects is also important when moving towards
11
complete device realization; it is these knowledge gaps that illustrate the demand for
more studies. The primary goal of this work is to address the important challenges
related to emitter lifetime, emitter and substrate/package integration difficulties, the
ability to incorporate VMDs into instrumentation, and undesired effects that limit
performance in specific applications. Addressing these key topics is important if the
technology is to progress towards achieving a widely adopted commercial application
goal. It is this primary interest that sets the precedence for the research presented here.
1.4 Dissertation Outline

The work herein is organized as follows:
Chapter 2: The fundamental background on carbon nanotubes and carbon
nanotube emitters, the basic and advanced principles of electron field emission,
necessary background on field emission vacuum microelectronic devices (FE-VMDs),
and the required background details of mass spectrometry will be discussed.
Chapter 3: Even though carbon nanotubes, and the FE arrays they produce
through integration with complementary components, have established themselves as a
primary candidate for next-generation cathode structures, many challenges with the
CNT emitters themselves and their integration into a packaged and scalable device
remain. Chapter 3 addresses the lifetime concerns of the CNT field emitter array.
Growth, fabrication, and testing processes towards improving overall emitter and device
lifetime will be discussed. Additionally, the ability to integrate the improved CNT
12
emitters into a scalable platform was investigated. Finally, the commercial viability of
the fabricated CNT-FE devices was investigated through their utilization as an
electron/ion source in a commercially available portable mass spectrometer where they
were compared against a standard filament thermionic emission source in an
instrument. The devices were fully characterized and mass spectra was collected and
analyzed to investigate the benefits of the source.
Chapter 4: Microelectromechanical systems (MEMS) offer unique packaging and
platform options for emerging CNT field emission VMDs. Polysilicon is the primary
material used to fabricate MEMS structures, and while many groups have investigated
CNT growth on single crystal silicon, there has been little to no analysis on CNT emitter
growth on polysilicon substrates. In order to better understand and control emitter
fabrication, it is important to understand the growth and interaction properties between
emitter and substrate. Chapter 4 discusses these integration challenges and provides
insight into improving control of CNT emitters grown on polysilicon. Details on the
substrate preparation, CNT deposition, characterization, and CNT-to-substrate adhesion
are analyzed. The growth kinetics, activation energies, diffusion mechanisms, and
causes for reduced diffusivity for CNT emitters grown on polysilicon substrates are also
investigated.
Chapter 5: The integrated circuit abilities of CNT FE-VMDs through the
development of MEMS microfabricated active circuit element structures are discussed.
13
The design is derived from work previously investigated by our group where devices
were used in other operating modes. The work reported here designs, characterizes,
fabricates, and evaluates improved adoptions, and assesses two key integrated circuit
performance restrictors. The first entails an investigation into crosstalk that takes place
between devices placed in close proximity, a must for VMD integrated circuit
considerations. Crosstalk was investigated and mitigated using both simulations and
experimental validation. The second was overall transmission of the emitted electrons
from the cathode (i.e., CNTs) to the anode. Grid loss reduction, charged particle
trajectory focusing, and resulting performance metrics are discussed.
Chapters 6: The fabrication of a novel drop-in packaged MEMS micro-ion source
for miniature mass spectrometer applications is investigated. The integration of the three
key ion source components is discussed: MEMS platform, CNT field emitters, and a low
temperature co-fired ceramic (LTCC) 3D scaffold with integrated ion optics. This
chapter focuses around geometrical designs, failure mitigation, and operating modes for
the CNT based MEMS VMDs. Additionally, a complete packaging option with
integrated extraction and focusing apertures was designed and tested experimentally to
validate theoretical simulation work. The fully packaged MEMS micro-ion source was
tested and characterized.
Chapter 7: A summary of contributions and conclusion with brief discussions of
future work to continue the research outlined in this dissertation will be discussed.
14
2. Background - Carbon Nanotubes (CNT), Field
Emission (FE), FE Vacuum Microelectronic Devices (FE-
VMDs), and Mass Spectrometry (MS)
2.1 Introduction
This chapter provides background and supporting information for the four key
constituents of the research presented in this work. Section 2.2 gives insight into the
importance of carbon nanotube (CNT) research and introduces essential structure,
growth mechanisms, properties, and applications. Section 2.3 introduces the theory of
field emission and relevant concepts including: work function and Fermi level
significance, emission processes, the Fowler-Nordheim (F-N) model, and emission from
various electronic materials (including CNTs). Section 2.4 focuses on history and
operating dynamics of vacuum microelectronic devices, explicitly the field emission
vacuum microelectronic device (VMD). Additionally, essential literature outlining the
device platform that the work in chapters 5 and 6 are built upon is summarized,
including work done in collaboration with RTI International. Finally, section 2.5 briefly
introduces the basic concepts of mass spectrometry with emphasis on the ionization
source component of the instrument. This is relevant to chapters 3 and 6 where the
fabricated device targets mass spectrometry applications.
2.2 Carbon Nanotubes

With thousands of publications released annually on carbon nanotubes, the
continuous, and increasing interest in the subject by researchers worldwide is clear.
15
Recent years have seen a sharp rise in work discussing fabrication methods, efforts to
fully characterize the chemical and physical properties of the material, and the search to
find the most attractive applications [34-38]. CNTs exemplify an appealing area of study
for many micro and nanotechnology applications as they embody many desired
properties of a material: stability (thermal, chemical, and mechanical), ideal electrical
properties, and their extremely small size.
2.2.1 Significance of CNT Research
With only around 25 years since their discovery in 1991 and 1992 by S. Iijima [39]
and Ebbesen [40], and even fewer years for the discovery of some of their properties and
applications, CNTs are just beginning to emerge in the application space. The realization
of the importance of CNT research began to emerge when researchers demonstrated that
CNTs exhibited many of the same desired properties that existed in graphite, specifically
intra-plan graphite [39, 41, 42]. The added benefit of CNTs oriented in a near ideal one-
dimensional structure, as well as their ability to be either semiconducting or metallic,
offers further considerations for research and development. To date, CNTs have been
integrated into a variety of industries. Report statistics [35] pertaining to forecasts of the
technology application predict a market increase to over $2.8 billion by 2023. Areas of
current and predicted application include: photovoltaics, sensors, semiconductor
devices, displays, conductors, smart textiles and energy conversion devices (e.g., fuel
cells, harvesters and batteries) [35]. And while the technology application opportunities
16
and their market drivers are plentiful, the challenges and pathway to commercialization
are also important considerations.
2.2.2 Structure
The structure of a CNT is well understood by considering the structure and
bonding of graphene as the CNT can be considered to be a sheet of graphene seamlessly
rolled up on itself. With six electrons (2 core 1s orbital and 4 valance electrons residing
in the 2s and 2p orbitals), carbon is the basis for numerous organic compounds. The
hexagonal structure of graphene is a consequence of three sp2 hybridized bonds (s
bonds) giving it the traditional honeycomb shape. A hybridized sp2 bond occurs when
the 2s electrons(s) are raised to the 2p energy level thereby hybridizing with the existent
2p state electrons. This occurs in other carbon based structures as well. Diamond for
example, is made up of four tetrahedral bonds which are derived from four equal sp3
hybrid orbitals. With graphene, we also see a weak out of plane p bond derived from
the fourth valence electron that is utilized in the 0.34 nm interlayer bond in graphite. The
C-C triple bond at 0.14 nm length is considered to be the strongest and shortest single
bond in nature [20]. Similar to graphene, CNTs are also comprised of sp2 hybridized
bonds and the out of plane orbital p bond. However, unique to CNTs, the curvature of
the structure gives rise to a combination of sp2 and sp3 bonds in order to reduce the
overall stress along the curves. It is this unique bonding, along with their high aspect
17
ratio, that give CNTs some of their exceptional properties. Figure 2.1 illustrates the
covalent bonds within a carbon nanotube structure. The s and p bonds are shown.
Figure 2.1: Bonding structure of a carbon nanotube. The sp2 hybridized bond (s bond)
and the out of plane orbital p bond are shown. Diagram derived from [43].
CNTs are typically categorized by the number of walls that exist in the structure.
Classifications include: single wall carbon nanotubes (SWCNT) with a diameter on the
order of 0.4 to 3 nm [44], multi wall carbon nanotubes (MWCNT) which include several
concentric SWCNTs with an average inter-wall spacing of 0.34 nm (identical to that of
graphene) [45, 46] and a range of diameters, and sometimes few walled carbon nanotube
(FWCNT) which is a term for structures with only two to a few walls [47]. In the case of
MWCNTs, the inter-wall spacing can be an inverse function of diameter, increasing as
diameter decreases as a result of wall curvature [48]. The electronic properties of the
18
nanotube can vary depending on the number of walls thereby shifting the material into
a metallic (finite value of carriers in the density of states at the Fermi energy) or
semiconducting state (no charge carriers in the density of states at the Fermi energy)
[49]. A defect free 1D CNT could theoretically benefit from ballistic transport (i.e.,
conductive at room temperature with electrons moving freely across the structure
without scattering effects). However, during synthesis it is common for defects in the
walls to emerge. These defects can alter the properties of the CNT, which can be
detrimental or beneficial depending on the application and has been researched in detail
[49-51].
2.2.3 Growth Mechanisms of CNTs
Carbon nanotubes are catalytically grown structures and have been studied in
great detail [52]. To summarize the important growth mechanisms utilized in their
synthesis, three primary methods are available. The arc-discharge method, which uses
electric arcs at very high temperatures (approx.. 4,000 °C) to evaporate graphite
electrodes was the method used by Iijima in their initial discovery [39]. The process
produces well crystalized but highly impure (large content of amorphous carbon and
metallic constituents) CNTs. Laser-vaporization, another method developed subsequent
to arc-discharge [53], utilizes high temperatures and high powered lasers to evaporate
high-purity graphite. Laser-vaporization is also a high purity process, however the
overall yield of production is very low. Cassell, et al [54], first reported chemical vapor
19
deposition of CNTs, currently the most popular method of growth due to its low-cost
and scalability. The catalyst-assisted process utilizes thermal energy to achieve
decomposition of the hydrocarbon precursors. CNTs grow on the catalyst which is
typically loaded onto a substrate (Si for example). Numerous variations of the process
have been explored that alter the growth, such as; type of hydrocarbon precursor
species, growth pressure, temperature used to dissociate the hydrocarbons, flow-rate of
the hydrocarbons, and time. Variations of CVD also exist. Plasma enhanced CVD
(PECVD), the synthesis method used in this work, employs a plasma to assist in
dissociation of the hydrocarbons. CNTs can be synthesized with vertical alignment as
they are aligned with the electric field lines present in the plasma sheath. PECVD is the
most common synthesis method for vertically aligned nanotubes (VA-CNTs) and the
process has been heavily studied [55]. A microwave PECVD (MPECVD) was explicitly
used for the growth of the carbon nanotube field emitters in this work; a schematic
diagram of the 915 MHz MPECVD system used in this study is given in Figure 2.2b. The
aligned MWCNTs that were utilized in this study were grown following a process and
model similar to that reported and proposed by B. Stoner and colleagues [56]. The
MWCNTs grown were of periodic bamboo-like structure with repeating hollow conical
segments similar to the structure shown in Figure 2.2a. Additional details on the growth
process and structure of the MWCNTs has been reported previously [57].
20
Figure 2.2: (a) TEM image of the tips of one MWCNT with bamboo structure,
reproduced from [58]; (b) schematic diagram of the 915 MHz MPECVD system used to
grow vertically aligned MWCNTs in this study, reproduced from [57].
2.2.4 Properties of CNTs
2.2.4.1 Mechanical
The mechanical properties of CNTs are of great interest. Widely studied, both
experimentally (when possible due to their small size) and also theoretically, CNTs have
reported Young’s modulus, tensile strength values, and fatigue strength several times
larger than steel with nearly four times lower mass density. However, these properties
are measured per unit area value and thereby remains relative and thereby they cannot
always be scaled for practical applications. Nonetheless, the mechanical properties have
proved themselves valuable in applications where composites are fabricated for
structural reinforcement [59]. Comparison of theoretically calculated stress and strain
values of SWCNTs with varying diameters show that large gains are possible with small
changes in the CNT diameter. This is seen when comparing micrographs of SWCNTs,
21
whose structures tend to have high tortuosity (very twisted), to those of MWCNTs who
remain relatively straight on a relative nano scale [37]. Tensile strength measurements,
again both theoretically and experimentally, have also shown that CNTs exhibit values
fifty times those of steel [37, 60-62]. Not only does this place CNTs as the strongest and
stiffest material in existence, it indicates why CNTs offer superior performance when
used in applications that apply large tensile forces. An example of this is field emission
from CNTs, where electric fields administer large forces on the structures. It has been
shown previously [37, 63-66], as well as in this work, that the mechanical failure
associated with CNTs as emitters is mostly failure at the CNT-substrate adhesion point,
and not along the CNT structure itself.
2.2.4.2 Electronic
Full details on the electronic properties have been reported and studied in detail
[34, 67, 68]. Certainly the most unique property of CNTs is their ability to exist as
semiconducting or metallic. The distinction is determined solely by their chiral structure.
Their conductivity is understood through modification of graphene’s band structure.
The aforementioned π orbitals overlap along the hexagonal planes resulting in very
high mobility. Graphene has a zero band gap, whereas CNTs electronic properties are
realized by modifying graphene’s available electronic states in the radial direction [37].
The enormous aspect ratio of the CNT structure results in a multitude of available
electronic states in the axial direction, with almost no electronic states along their
22
circumference. It is true that the curvature of CNT walls, and the resulting sp3
hybridization does have effects on the band structure, however, it has been shown that
this only affects CNTs with diameters less than 20 nm (i.e., SWCNTs) [37]. Also, the
band gaps of CNTs are highly sensitive to the environment. It has been shown that the
transition from n-type, to intrinsic, to p-type due to the absorption of impurities, gases,
and trapped charges, can have an impact on the conductivity by orders of magnitude
[46, 69]. Early work demonstrating large current capacity in CNTs without substantial
heating by de Heer, et al. showed evidence of the one dimensional quantum conduction
properties of CNTs. The charge transport in CNTs was found to be ballistic in nature, as
opposed to conventional conductors whose length would directly impact scattering,
electron flow resistance, and thus the energy dissipated in the conductor [70, 71].
Furthermore, degradation by electromigration, a common unfavorable affliction to
lifetime in conventional metal conductors, is mostly nonexistent in CNTs [37]. It is these
reasons that literature has reported current carrying capabilities of CNTs three orders of
magnitude higher than copper (109 A/cm2 versus 106 A/cm2). Specifically to MWCNTs,
the aforementioned work by de Heer, et al. [70] and others have shown that in the case
of MWCNTS, the current is primarily conducted by the outermost walls. Furthermore,
traditional metal conductors display continuous degradation when evaluating current
carrying lifetime. However, MWCNTs have shown their electrical breakdown is
dependent on the sequential failure of the individual walls [72]. The ability to exist as
23
semiconducting or metallic, adjust band gap energy without the need for doping, and
possess superb conductive properties, provides an understanding of why CNTs are
under strong consideration for various electronic applications.
2.2.5 CNT Applications
It is a widely accepted theory that fundamental scaling limits of silicon
technology and silicon devices are nearly at an end [73]. Reduction in size has been the
driving force for increased performance (and reduced power consumption) since the
early works of integrated circuit development. Much research has been dedicated to
new materials that can supplement, or replace, silicon; CNTs being one of them. CNTs
have numerous applications in the electronics industry. The properties discussed in
section 2.1.4, including their ballistic transport and current carrying capacity, inspire
continued development as these properties correlate directly to those properties desired
in electronic devices (i.e. low power dissipation and scalability). CNTs have also been
investigated for related applications such as interconnects and thermal management
structures [74-77]. Energy applications have also received interest due to the respectable
chemical stability in combination with the electrical conductivity. Fabrication of
electrodes from CNTs, as well as their integration in batteries, photovoltaics, and fuel
cells have also been investigated in detail [78-83]. One popular research direction has
been CNT sensor development [84, 85]. Section 2.1.4 eluded to the capabilities to
transition a CNT from n-type to p-type via the absorption of impurities and gases. This
24
absorption has an impact on the conductivity and this shifting ability can be tapped for
sensor development by exploiting the CNTs ability to yield a conductance change when
absorbing environmental gases. Additionally, the low power consumption characteristic
is ideal for a portable instrument, or an instrument that desires low operating energy
overhead. Finally, CNTs have shown to be an excellent candidate as an electron field
emitter in field emission applications. This is primarily due to their very large aspect
ratio and small diameter tips. Additionally, their ability to support large currents,
withstand high temperatures, and resist degradation better than traditional field
emission materials further supports their consideration to supplement or replace metal
field emitters. CNTs as field emitters, and pertinent references, are discussed in detail in
section 2.3.3.
2.3 Field Emission Fundamentals

Field emission is a growing area of research, and it is beginning to gain ground
in commercial applications establishing itself as a significant field of research [2, 4, 22,
86]. A wide literature search including all related terminology (i.e., field emission, field
emitters, etc.) reveals a consistent increase year after year in research publications. Some
of the more well established and required instruments in scientific research and
commercial fabrication (i.e., semiconductor fab) rely on field emitters as their source of
electrons to achieve the desired performance (e.g., scanning electron and transmission
electron micrographs). Historically, thermionic emission (or the Richardson-Dushman
25
effect) and cold electron field emission were independently studied from the late 1800’s
to the early 1900’s (approx.. 1880 to 1930). Both emission processes, important in their
own respect, pioneered the development of numerous modern day electronics and
instrumentation. This section will introduce the key concepts of electron emission, give a
brief overview of additional electron emission mechanisms, discuss the governing F-N
theory for field emission, and close with a discussion about field emission from CNTs.
2.3.1 Electron Emission
At its core, the term electron emission is associated with a process that allows
electrons to leave the surface of a solid or liquid and transfer into another phase
(typically vacuum). For free electrons, this behavior is best described by the electron gas
or Drude model [87]. The free electrons inside a condensed phase have a lower energy
than the vacuum and therefore the emission of electrons from a surface is only possible
if sufficient energy is provided.
2.3.1.1 Probability of Escape
To understand the energy of the electrons more specifically, we use a quantum
mechanics enhanced theory of solids which shows us that the multitude of energy bands
in a metal will actually overlap to form a single energy band [88]. Within that energy
band there exists several discrete energy levels that become occupied by the valence (i.e.,
free) electrons. If a material were to be held at absolute zero, all energy levels up to the
Fermi level (EF) would be filled. The energy difference from this Fermi level to vacuum
26
level is referred to as the work function (Φ) of the material and it is equal to the energy
required to excite the electron from Fermi to vacuum so it can leave the surface/material.
The work function is the surface potential barrier that holds the electrons within the
material. Figure 2.3 gives a schematic energy diagram for metals, the work function is
shown.
Figure 2.3: A free electron (red sphere in diagram) possesses a lower energy inside a
metal than in vacuum, the work function is the amount of energy needed by the
electron to escape into vacuum. Adapted from [88] with relevant modifications.
The aforementioned electron energy state distribution is fully described by the
density of states (DOS) equation. Because the energy at the bottom of the band (Ebottom) is
equal to zero, the states that exist from the bottom of the band to the middle can be
represented by the following DOS equation:
8𝜋√2
𝑔(𝐸) = 𝑚∗3/2 √𝐸 [1]
ℎ3
where Planck’s constant (h) equals 6.6.3 x 10-34 J.s and m* is the electron mass. Similarly, if
we take equation 1 and replace √𝐸 with √(𝐸𝑡𝑜𝑝 − 𝐸) than we have the DOS equation
representing states from the top of the band to the center. The number of states that exist
27
in the energy interval described (E to E+dE) is found by multiplying g(E) by dE. In order
to find the probability that an electron will reside at a specific energy level, we use the
Fermi-Dirac distribution function:
1
𝑓(𝐸) = 𝐸−𝐸𝐹 [2]
1+exp⁡( )
𝑘𝑇
where Boltzmann’s constant (k) is 1.38 x 10-23 J.K-1 and EF is the Fermi energy.
Multiplying g(E) by f(E) gives the number of electrons per unit energy. The energy
required for electron emission, which we have defined above as the work function, is the
specific energy that must be provided to each electron within the material.
2.3.1.2 Emission Processes
The capacity and process by which electron emission takes place relies heavily on the
properties of the material from which the electrons are emitting. Geometry, electronic
structure, and work function are examples of a few of those properties and must be
considered in each case [1]. The following are brief summaries of the four principal
methods of obtaining electron emission: thermionic/photo emission, secondary
emission, Schottky emission, and field emission. In thermionic emission, sufficient
energy is provided through heat (typically greater than 2,500 °C) in order to overcome
the surface potential barrier [89]. The quantity of electrons emitted is directly
proportional to the temperature applied. In photoemission, the incidence of
electromagnetic waves, or more specifically the impinging photons, transfer energy
larger than the work function allowing electrons to emit from the surface. The number of
28
electrons emitted is proportional to the intensity of the light on the surface [89, 90].
Secondary emission is more an after effect that occurs when the surface of the material is
struck by a high energy particle (electron or ion) and sufficient energy (i.e., more than
the work function) is transferred to the electrons on the material surface. Schottky
emission is slightly different in the sense that energy is not transferred to the electrons
[90]. Instead, the effective barrier is lowered by a specific amount (ΔΦ) through a
combination of vacuum level bending due to an electric field, and what is known as the
image charge effect [90]. With the lowered barrier, electrons with sufficient energy can
escape (emit into vacuum). Figure 2.4 illustrates the emission mechanisms with a
schematic diagram comparing thermionic/photo emission, Schottky emission, and field
emission.
Figure 2.4: Various electron emission processes; adapted and modified from [91].
Field emission, the final electron emission mechanism, will be discussed in more
detail as it describes the emission process utilized in this work. Fundamentally, electron
29
field emission is a quantum-mechanical phenomenon where the electrons at the Fermi
level tunnel through the surface potential barrier due to the application of an external
electric field to thin the vacuum level barrier. A higher applied field correlates to a
thinner barrier. In order to generate electron emission from a flat metal surface, a local
field on the order of 3-5 x 107 V/cm is required. Using a simple metal with work function
Φ, we can resolve the minimum barrier width (d) and additional required conditions
needed for tunneling (i.e., field emission to occur). If we assume the electron is given
kinetic energy equal to that of its work function, we can calculate its uncertainty of
momentum and using Heisenberg’s uncertainty principle we find the uncertainty in
position to be:
ℏ
Δ𝑥 = 2(2𝑚Φ)1/2 [3]
In the presence of an applied field (F), the following equation
𝑃𝐸(𝑥) = 𝐸𝐹 + Φ − 𝑒𝐹 [4]
represents the potential energy just outside the metals surface, thereby allowing the
potential barrier (d) to be given by the following equation:
Φ
𝑑 = 𝑒𝐹 [5]
This simply shows that by applying high electric fields, the barrier width can be
reduced. More specifically, by nature of the wave mechanics of electrons, if the barrier
width is smaller (or equal) to the calculated uncertainty position from equation 3, it is
possible for an electron to tunnel through the barrier creating field emission. It can also
30
be shown that materials with higher work functions require higher applied electric fields
to enable field emission. Recalling that Schottky emission takes place due to the bending
of the vacuum level enough so that electrons can “spill” over the top, we can now set an
upper limit on the applied field before tunneling current dominates the total
contribution to emitted current density. It has been reported that this field strength is
approximately 106 V/cm [92]. This indicates that there is a transition region where both
Schottky and field emission will be contributing to the total emission current, but
specific details are beyond the scope of this work. Additional details into the
fundamentals of field emission are discussed in section 2.3.2, F-N theory, the governing
theory that describes the field emission phenomena.
2.3.1.3 Emission Metrics Specific to FE
In the field of electron emission, and more specifically, electron emitter
characterization and application, there exists a list of common specifications and
performance metrics that emitters are characterized to. While these measurements are
certainly case and process dependent, it is appropriate to define the most common as
reported in literature for field emission as it is the primary process utilized in this work.
Because field emission is dependent on an applied electric field in order to
generate emission, it is common to report two efficiency measurements related to this
applied electric field. These two metrics were developed in the electronic display
industry where the current densities needed to turn on and saturate a pixel were
31
referred to as the turn-on and threshold voltage, respectively. Therefore, for field
emission, turn-on voltage (VTO) is the voltage needed to commence emission. This is
usually recorded when the emitted current is measured at 1 nA, or potentially 1 nA/cm2
if reporting in current density. Depending on instrument resolution, it could be taken
when the I-V characteristic plot becomes exponential. The threshold voltage (VTH), is the
applied voltage required to reach a specific emission current value or density. This
value varies widely in literature, but for the purposes of this work, VTH is the voltage
needed to emit 1 µA of current. Reporting VTO and VTH provide a means to compare
performance between different emitting structures or devices. Current density in field
emission is analogous to current density reporting in similar fields of research. It is
defined as the current output from the emitter per unit area of the emitter.
The lifetime and stability of the emitter are the final two metrics of interest.
Lifetime is defined as the length of time the emitter can continue to perform. Lifetime
testing is often conducted using constant or pulsed measurements. Stability is a
measurement of the fluctuation on the emitted current over time given a fixed voltage.
Degradation leads to changes in stability and ultimately failure.
2.3.2 The Fowler-Nordheim Theory
Schottky in the 1920’s first reported experimentally that electron emission could
occur under the presence of large electric fields [93, 94]. However, it was Fowler and
Nordheim in 1928 who utilized wave mechanics and some approximations to develop a
32
theory for the emitted current leaving a flat metal surface. They proposed that the
current is established from the probability of an electron successfully tunneling through
the potential barrier. Calculating the barrier transparency using the Wentzel-Kramers-
Brillouin (WKB) approximation [95] and incident electron flow, and then integrating,
allows for theoretical current density calculations. The Fowler and Nordheim theory
uses the following assumptions:
 the free electron model using Fermi-Dirac statistics is utilized by the
emitter in consideration
 the emitting material is atomically smooth and clean
 any and all potentials within the emitter are constant and are not affected
by the external electric fields; and the electric field is uniform in the
vacuum gap
 the temperature is 0 °K (field emission is weakly temperature dependent)
 the WKB approximation is used to determine the electron tunneling
probability.
If these conditions are met, the current density can be described by the following
equation:
∞
𝐽 = 𝑒 ∫0 𝑛(𝐸𝑥 )𝐷(𝐸𝑥 , 𝐹)𝑑𝐸𝑥 [6]
Here, J is the current density, e is the charge on the electron, Ex is the kinetic energy of
the electron, F is the electric field that is applied, and n(Ex) is the number of electrons
33
whose energy falls between Ex and Ex + dEx. Utilizing the aforementioned WKB
approximated barrier transparency, the classic F-N formula is derived with constants k1
and k2 (1.54 x 10-6 AV-2 eV and 6.83 x 107 eV-3/2Vcm-1 respectively) [96], J is the emission
current density (A/cm2), Φ is the work function of the surface from which the emission is
taking place (eV), and E is electric field between the anode and the emitting surface; or
V/d (V/cm):
3
𝐸2 Φ2
𝐽 = 𝑘1 exp⁡(−𝑘2 ) [7]
Φ 𝐸
From equation 7 we can see the exponential relationship between the emission current
and the applied electric field, with the work function also having a strong impact. It
should be clear that equation 7 is true in the case of a flat metal cathode, as was derived
by F-N. Since current is actually measured during field emission experiments, the
equation can be simply converted to current by multiplying through by an
approximation of the emission area.
Both theoretical and experimental validations of the F-N equation describing
electron field emission from cold cathodes of a flat surface have been reported [2, 86, 97].
However, fields greater than 3 x 108 V/m are required in order to generate field emission
from a typical flat metal surface. Therefore, early experiments sought to machine metal
emitters into sharp tips in order to take advantage of the concentrated fields that take
place on regions of high curvature. In other words, the local electric field at a tip will be
significantly larger due to the effect that gradients of electric field lines increase with
34
decreasing radius of curvature. Smaller applied voltages will result in much higher local
electric fields in the vicinity of the sharp tips; therefore smaller applied voltages are
needed to achieve field emission from the structure. This is known as field amplification
and is often represented by the field enhancement factor (β) using the following
equation:
𝛽𝑉
𝐸= [8]
𝑑
A consequence to using the sharp tip is that the electric field will be at its highest at the
apex of the tip, but it will decrease quickly moving off axis. Therefore, the traditional F-
N equation (Equation 7) cannot be precisely applied to obtain the emission current from
a sharp tip as it violates the assumption that there is a uniform electric field in the
vacuum gap region. However, modification of the F-N equation by replacing the
uniform electric field (E) with βV/d will allow for its use in calculating emission currents
from tips.
To further understand and represent experimental data, we can convert current
to current density, and use the localized electric field expression to derive an equation
that allows us to express the measured current:
3
(𝛽𝑉)2 Φ2
I = 𝑛𝛼𝑘1 exp⁡(−𝑘2 𝛽𝐸 ) [9]
Φ
35
where n represents the number of micro-tip emitters in a given field emitting array, and
α represents the emitting area per tip in cm2. It is common practice to reorganize
Equation 9 to present the equation in what is referred to as F-N coordinates:
3
𝐼 𝑘1 𝑛𝑎𝛽 2 𝑘2 Φ2
ln (𝐸2 ) = ln ( )− [10]
Φ 𝛽𝐸
This enables the creation of the F-N plot, which displays a linear relationship between
ln(I/V2) on the y-axis and the reciprocal of the extraction voltage 1/E on the x-axis. Figure
2.5 shows measured I-V characteristics and the calculated F-N plot for a carbon
nanotube field emitter as reported by [98]. The slope (m) of the linear relationship can be
calculated and used along with known information to calculate the field enhancement
factor using the following equation:
−𝑘2 Φ3/2
𝑚= [11]
𝛽
The F-N equation and F-N plot is widely used to validate electron field emission from
experimental data. Extraction of the field enhancement factor also provides a metric for
comparing field emitters to one another. Furthermore, a linear F-N plot verifies field
emission is taking place and not another emission process. A deviation from the linear
relationship described above can indicate another emission mechanisms is contributing.
Additionally, deviations can give insight into energy band structure and voltage-to-
barrier-field conversion factor of the emitting material [99].
36
Figure 2.5: CNT field emitter characterization as reported by [98]. Electron emission
current versus applied field characteristics for a CNT field emission sample (inset).
The F-N plot, as derived by equation 10, is shown.
2.3.2.1 Correction to the F-N Equation
While 2.3.2 introduced the work of Fowler and Nordheim as a means for
comprehending experimental field emission data, it is important to use care when
applying the F-N theory. Due to assumptions used in the theory, and intended
applications to flat surfaces, gross overestimates of parameters can be easily made. It is
possible for the assumptions in the F-N equations to lead to current density
approximations that are off by 3-8 orders of magnitude for modern nanostructure
emitters [100]. Many have worked to modify the F-N theory for use with nanostructures
such as carbon nanotubes [2, 97, 101]. Experts in the field, such as Forbes, have worked
to clarify and correct the misuse of the F-N equation. Additionally, they have reported
37
on improved conditional tests (Forbes orthodoxy test for example [100-103]) to validate
application of the theory to extract desired parameters. The modern versions of the F-N
equation add correction factors for several components of the equation, and while
important to the overall science, the detailed explanations are beyond the scope of this
work. It is important to note that modern F-N equations, as well as sophisticated
algorithms designed to follow and apply the work of Forbes and others, was utilized in
the work presented here.
2.3.3 Field Emission from CNTs
This section will focus on field emission from the type of structure utilized in this
work (i.e., metallic MWCNTs), and will not cover FE from semiconducting or SWCNTs
which has been reviewed in detailed elsewhere [96, 104]. As previously mentioned
briefly in chapter 1, carbon nanotubes encompass many of the attractive qualities of the
ideal field emitter including durability, low power operation, and acceptable current
densities. It is for these reasons CNTs have been recognized as one of the most
promising field emitters to date. Specific details on their field emission capabilities and
methods of emitter design from CNTs will be discussed in this section.
2.3.3.1 Unique FE Properties of CNTs
First reported as an electron field emitter in 1995 [18, 19, 105], CNT emission
properties have been well studied and have proven themselves to be a viable candidate
for electron sources in various applications [106, 107]. CNTs have several advantages as
38
FE electrodes. The most apparent advantage of CNT field emitters is their very large
aspect ratio and small radius of curvature at the tip. The diagram in Figure 2.6a shows
how the spatial distribution of the electric field potential is concentrated near a sharp tip;
this is especially true in CNTs. The large concentration at the tip equates to very large
field enhancement factors (i.e., lower applied voltages required). Figure 2.6b and Figure
2.6c provide SEM images of CNT field emitters and a standard tungsten filament used in
a field emission SEM.
Figure 2.6: (a) schematic showing the spatial distribution of an electric field potential
around a sharp tip, (b) SEM of high aspect ratio CNT emitters with tips shown in the
inset, (c) tungsten field emitter from a SEM reproduced from [108].
Figure 2.7 gives a potential-energy diagram for a CNT emitter (i.e. represented by a
micro-tip metal) illustrating the advantages to the micro-tip emitter in terms of
tunneling probability under an applied field. The solid green line represents the surface
potential barrier seen by the electrons in the CNT/metal. The solid blue line represents
39
an applied electric field; -eE(x). The electric field applied to a planar emitter will only
reduce the barrier slightly. The dashed blue line represents the “reduced” surface
potential barrier seen in the planar emitter case; V(x) = -e2/4x – eE(x). In the case of a
micro-tip emitter, the applied potential is multiplied by the enhancement factor; solid
red line –βeE(x). Therefore, the barrier is reduced dramatically increasing the tunneling
probability (i.e., tunneling current or emission current) significantly; represented by
V(x)= -e2 – βeE(x).
Figure 2.7: Potential-energy diagram illustrating the effect an applied electric field has
on the energy barrier of a planar emitter versus a micro-tip emitter.
Another advantage is the activation energy for surface migration of atoms on CNTs is
significantly larger (17 eV) than tungsten (3.2 eV) and rhenium (2.7 eV) (e.g. standard
materials used for commercial field and thermionic emitters) [106]. CNTs also possess a
high melting temperature when compared to refractory metals such as tungsten.

40
Additionally, CNTs have good conductance, extremely large Young’s modulus (high
stiffness), and high tensile strength (allowing the tip to withstand the extremely strong
fields (several V/nm) needed for FE) [106]. It is these characteristics that give CNT field
emitters their lower threshold fields when compared to conventional field emitters [109].
It has been shown that CNT field emitters can also endure large current densities [21,
110]; and Fursey et al. [2] has reported emission current densities approaching the free-
electron limit at a value of nearly 1011 A/cm2 at an area of 1013 cm2. While lifetimes of
various times from minutes to hours have been reported, a CNT emitter lifetime is
dependent on its application and several factors: temperature, ambient pressure,
surrounding gas species, CNT structure, and substrate [36, 38, 111]. Finally, it has been
shown that CNT field emitters can be described by the well-known F-N relationship,
given the inclusion of a few modifications, with acceptable accuracy [112, 113]. The afore
mentioned factors, as well as several others including CNT growth conditions,
alignment, inter-tube spacing, and CNT doping, have all been shown to affect the field
emission characteristics of CNTs. However, their study exceeds the scope of this work
and are only mentioned to offer a complete understanding. It is easily shown, however,
that the unique advantages provided by CNTs directly impacts their performance as a
field emitter. Table 1 provides a comparison of the threshold electric field required to
achieve an emission current of 10 mA/cm2 as reported by [98]. It is clear that CNT
41
emitters will provide comparable emission current at significantly less applied voltages
when compared to other traditional field emitter materials.
Table 1: Comparing threshold electric field requirements for different materials;

reproduced from [98].
Threshold Field (V/µm) for a

Cathode Material
current density of 10 mA/cm2
Mo tips 50 – 100
Si tips 50 -100
p-type diamond 160
Defective CVD diamond 30-120
Amorphic diamond 20-40
Cesium-coated diamond 20-30
Graphite powders 10-20
Nano-diamond 3-5 (unstable > 30 mA/cm2)
Assorted carbon nanotubes 1-2 (stable > 4,000 mA/cm2)
2.4 Field Emission Devices

A large challenge in the adoption of field emitter electron sources is the difficulty
that arises with integration and packaging. The growth of nanometer scale field emitter
arrays is typically dependent on specific substrates (e.g., silicon). Therefore, applications
are presented with engineering challenges to integrate the emitters to benefit from their
advantages in a way that will not impact the application parameters (i.e., reliability, cost,
etc.) negatively. Designing VMDs requires knowledge of the emitters themselves, the
platform on which they are grown on, as well as any integration challenges or system
level performance concerns that could come about from the integration of the field
emitter. To date, FE-VMDs have been utilized in a handful of applications with the most
42
prominent being flat low-voltage displays; several others are listed in Table 2. This
section will briefly introduce the more prevalent and modern VMDs under
development, the two primary operating modes (i.e., diode and triode), a brief
discussion of present VMD challenges and the motivation towards laterally oriented
devices, and finally specific background details related to previous work on the
Duke/RTI developed monolithic VMD platform.
Table 2: Primary FE Device Applications
FE Device Application
1.) Flat low-voltage displays of high brightness and high resolution
2.) Electron optics systems of super high resolution (e.g., SEM, TEM, electron
lithography, Auger electron spectrometer, tunnel microscopy)
3.) Active elements for integrated circuits (e.g., diodes, transistors, etc.)
4.) Employment in microwave devices
5.) Variety of pressure gauges, magnetic field gauges, and other sensors
6.) New types of ion sources
7.) Realization of new very efficient production technologies for microelectronics
2.4.1 FE Device Classifications
2.4.1.1 Spindt Cathode
It is well agreed upon in literature that Spindt and coworkers pioneered the field
emitter array in the late 1960’s using field emission cathodes now referred to as the
Spindt cathode [7]. The device leveraged present day microfabrication technology to
fabricate sharp molybdenum cone shaped field emitters inside a small etched cavity
through a Si wafer with an oxide layer on top. A counter electrode was deposited on top
surrounding the etched cavity to provide an extraction gate to generate field emission
43
from the Mo cone. Because of their small form factor, many Spindt tips, as they were
called, could be populated on the same substrate in close proximity to fabricate field
emitting arrays; an SEM of one Spindt-type emitter is given in Figure 2.8a. Spindt
cathodes do have drawbacks in the sense that the field emitters themselves, the metal
Mo cones, are subject to degradation during normal operation and high currents [114].
Sputtering of the tips is also possible which further degrades the tips [115]. Small
undesired deviations from the originally fabricated sharp tips lead to fast field
enhancement factor declines and ultimately lower emission and degraded efficiency.
The emitters are also subject to chemical reactions with ambient environment which
changes the electronic structure of the Mo [115, 116].
Figure 2.8: (a) Spindt-type field emitter. SEM of single emitter shown; reproduced
from [2]; (b) Deep reactive ion etched (DRIE) silicon field emitter arrays; reproduced
from [117].
2.4.1.2 Silicon Field Emitters
Silicon based VMDs, such as Si nanowires or pillars grown on substrates for
example, are another heavily studied type of FE-VMD. The devices are typically
44
developed by integrating the wafer based emitters with an arrangement of on or off chip
grids. Both bottom up (i.e., typically growth) and top down (i.e., etched using methods
like lithography and reactive ion etching) are used for fabricating the emitters.
Fabrication of the devices can involve many processing steps, but they can also achieve
sufficient current densities with low turn-on voltages. Failure of Si emitter based devices
has also been studied in detail [118-121]. Similarly to Spindt cathodes, thermal failure
and ion bombardment are two of the more common failure mechanisms due to the
nature of the emitting material (i.e., Si). It has also been shown that Si emitters are prone
to damage by a combination of joule heating and what is referred to as the Nottingham
effect, which is quantum-mechanical energy exchange process that contributes heavily
to thermal imbalances during field emission [2]. Failure of the emitter results in ultimate
failure of the VMD. High-current and uniform emitting capable silicon structures have
been reported [117]; Figure 2.8b shows an example of an array of Si emitters from the
Akinwande group.
2.4.1.3 Carbon Field Emitters
The last class of modern VMDs are based on carbon based emitters, either
diamond or CNTs. Carbon based FE cathodes and VMDs have been shown to be more
robust than both Spindt type cathodes and Si emitter based cathodes. This is mostly
attributed to the robustness of the emitters themselves as was discussed in section
2.3.3.1. Fabrication of VMDs based on CNT and diamond emitters has been
45
demonstrated in a variety of geometries; both vertical and lateral. VMDs that employ
nanodiamond emitters and are patterned in finger-like emitter structures have shown
strong performance in the realm of integrated circuit application via both suspended
and self-aligned anode designs [15, 122-126]. There are many similarities between the
two materials as emitters. The variation between the two is mostly realized through the
methods and geometries fashioned to create the VMDs. One advantage that both share
is the significantly reduced effects of sputtering and ion bombardment that is
experienced by the aforementioned VMDs based on Spindt and Si emitters. Present day
challenges with VMDs based on diamond and CNT are mostly related to lifetime and
integration [66, 127-129], and these two will be discussed in detail in section 2.4.3. Figure
2.9a gives an example of a microfabricated nanodiamond lateral FE diode as reported by
[15]. Figure 2.9b gives an example of a carbon nanotube field emitter array grown and
used in this work.
Figure 2.9: (a) SEM of a microfabricated nanodiamond lateral FE diode reproduced

from [15]; (b) SEM of a CNT emitter array utilized in this work.
46
2.4.2 VMD Operating Modes
The primary types of field emission devices were eluded to in the previous
section on modern VMDs. The bulk of research with VMDs fabricates either ungated
diode or gated triode structures; very similar to early vacuum tube development.
2.4.2.1 Vacuum Diodes
The field emission diode is the most basic field emission VMD. The emitters (and
whatever electrode that might be holding them) is referred to as the cathode, and an
anode is present to apply the necessary field to generate field emission. The anode also
acts as the primary collector of the emitted current. Typically the cathode is held at
ground, and the anode is set to a positive voltage. However, depending on application,
the cathode can be negatively biased and the anode held at ground or a small positive
voltage. Ideally the area of the anode is greater than the square of the distance between
the cathode and anode, allowing us to disregard any edge effects.
Figure 2.10: Schematic diagrams representing electrode type and placement in a

simple diode and triode configuration.
47
2.4.2.2 Vacuum Triodes
In a triode device, three electrodes are utilized for either amplification purposed,
or in the case of vacuum field emission devices, to achieve better control over emitted
electrons. In addition to the cathode and anode, a grid electrode is added in between in
order to modulate the electron current. This is typically the case in vacuum tubes where
small changes in the grid voltage allow for large changes in the anode current. This is
why the original triode vacuum tube was termed an amplifier circuit. In the case of
vacuum field emission devices, the grid in combination with the cathode establishes the
field needed for electron emission. In a vacuum field emission device, the electrons will
be emitted from the cathode and some will pass through the grid to continue towards a
positively biased anode. A triode design will result in lower current density reaching the
anode as majority of the electrons will be lost at the grid [130]. However, this is typically
offset by a larger field enhancement. Figure 2.10 shows a geometrical comparison
between the aforementioned diode and the triode.
2.4.3 Present VMD Challenges
There are several challenges in VMD development, and ultimately their path to
commercialization. Some of the main challenges are related to lifetime of the cathode
(i.e., the emitters), the ability to integrate the nano and micro scale emitters at a system
level (i.e., into an instrument), and the loss of electrons at a grid which correlates directly
to power loss and the need to run the devices at higher operating levels. Lifetime of
48
CNT field emitters is the largest challenge of the three. Improved lifetime of the emitters
will ultimately improve overall VMD development, has been investigated in great detail
[38, 65, 111, 128, 129], and even though much has been discovered on the failure
mechanisms, lifetime improvement has seen little progress. It is understood that several
factors play an important role in the failure of CNT emitters including: mechanical
stresses causing emitter loss and gradual degradation, ion bombardment (CNTs are
more resilient, but not immune), and CNT shortening which ultimately increases the
applied voltage to maintain the required field for emission. Additionally, it has reported
that high temperatures caused by the large flow of current are also failure mechanisms
[34, 93, 131, 132]. In regards to electron loss, it is apparent that any improvement in
reducing the number of electrons that are lost at the grid and are able to make their way
to the anode is an improvement to a VMD. This is because in almost all VMD
development, the current at the anode is the desired signal. These three challenges are
all addressed in this work. Improvement to the lifetime of CNT emitters is discussed in
chapters 3 and 4, the transmission of electrons in a VMD is discussed in chapter 5, and
novel packaging methods are discussed in chapters 3 and 6.
2.4.4 Duke/RTI MEMS VMD
This section will briefly introduce the two primary geometrical layouts utilized
in VMD development. This will serve as a passage to introduce the platform developed
49
by our current research team over the past ten years. This platform served as the
foundation for which the work outlined in chapters 5 and 6 were built upon.
2.4.4.1 Vertical and Lateral VMDs
The orientation chosen for device development impacts a variety of factors.
Primarily there have been two orientations explored due to practical application
potential of both in vacuum micro/nanoelectronic devices. Devices can be developed in a
vertical orientation where the cathode, grid(s), anode, and supporting structures are
stacked vertically in some respect; the Spindt cathode is one such example. Other
devices are developed laterally, where the elements are all fabricated in the same plane
along the substrate. It has been shown that laterally developed devices offer many
advantages, specifically related to high-frequency and high-speed applications [133-144].
Lateral devices still maintain a short electron path length as microfabrication allows for
precision placement of all electrodes; this ultimately improves speed. Additionally, one
of the more detrimental factors to a devices speed is the capacitance experienced
between the electrodes and the substrate. A laterally constructed device reduces
capacitance due to the small amount of overlapping area that exists.
2.4.4.2 History and Previous Work
In 2002, the research team consisting of Duke University and RTI International
proposed a micromachined vacuum triode fabricated using a microelectromechanical
systems (MEMS) platform and integrated carbon nanotube cold cathodes [145, 146]. The
50
device was the first demonstration of a MEMS and carbon nanotube based technology
designed for on-chip power-amplifying vacuum devices. The fully integrated on-chip
vacuum microtriode combined solid-state fabrication technology with high-performance
nanomaterials to offer respectable current densities, transconductance values, and low
power requirements. The triode structure provided a means to parameterize
characterization and establish insight into the performance and design fundamentals of
the device before more sophisticated devices were explored. Figure 2.11a shows the
originally developed MEMS CNT FE-VMD. In 2007 - 2010, the utilization of the
microtriode device as an ion source was explored [147-150]. The MEMS fabrication
provided an easily amendable platform that allowed for the inclusion of additional
panels to serve as ion collector electrodes on-chip. The CNT emitters provided an
electron source that could be used for electron ionization (EI) of an analyte. Ion
collection was achieved on the added electrodes. The ion collection efficiency of the
device established its potential to perform as a miniature ion source that benefits from
reduced size and cost, while still maintaining core ion source requirements. Figure 2.11b
shows the MEMS CNT FE-VMD operated as an ion source with the ion collector on chip.
And in 2011 the device was investigated for its ability to expand beyond single-charge
carrier operation [151]. Utilizing both electrons and ions as charge carriers, the device
was able to demonstrate the first microelectronic device able to utilize both positive and
negative charge states similar to how a complimentary metal-oxide-semiconductor can
51
be configured as a p-channel or n-channel device. The second charge state leads to the
realization of additional circuit applications, in particular digital logic. Figure 2.11c
shows the MEMS CNT FE-VMD operating as a bipolar vacuum microelectronic device.
The two lateral panels orthogonal to the cathode are the bipolar collectors.
Figure 2.11: SEM’s showing evolving development of the Duke/RTI VMD platform;
(a) original concept as fabricated with MEMS platform and CNT emitters, (b)
adoption of CNT FE-VMD as an ion source with ion collection on chip laterally, (c)
adoption of the CNT FE-VMD for dual-charge carrier operation; reproduced from
[145, 146, 148, 151].
2.4.4.3 Microelectromechanical Systems (MEMS)
MEMS is a technology that allows for the development of miniaturized
mechanical and electro-mechanical elements using microfabrication techniques similar
to modern day IC processing. Using MEMS, the field of miniaturized sensors, actuators,
and VMDs has grown significantly. The MEMS devices in this work have been
developed using Multi-User MEMS Processes (or MUMPs®) which is a well-established
commercial program that allows for “cost-effective access to MEMS prototyping and a
streamless transition into volume manufacturing” [152]. The PolyMUMPs process
52
integrates consecutive layers of polysilicon and sacrificial oxides, 7 physical layers total,
with masking and etching steps to create 3D structures out of conductive polysilicon.
2.4.4.4 Device Assembly
The details of the microtriode fabrication process have been outlined in detail
previously [145-147]. Briefly, MEMS devices received from the foundry are released
from their sacrificial oxide using an acetone, isopropyl alcohol, hydrofluoric acid, DI
water, and methanol process. Devices are then transported to a critical point CO2 dryer
to ensure a stiction-free surface. Devices are then masked for Fe catalyst deposition
using integrated MEMS masks that contain an array of patterned holes. MEMS masks
are manually flipped over and secured on top of each device using optical
adhesive/epoxy that is then cured with UV exposure. Devices are secured onto 4”
stainless steel discs with laser etched metal masks placed over the MEMS mask where
the array is located. 50 Å of Fe catalyst is deposited using electron-beam deposition.
CNTs are then grown following a similar process as described in [56]. Finally, devices
are masked again using metal masks that expose the MEMS contact pads and electron-
beam deposition is used to deposit 1500/5000 Å Ti/Au to be used for wire bonding.
Devices are then assembled using a probe station and micropipettes attached to the
micromanipulator arms. MEMS latches are lifted up with one micropipette while the
electrode panels are flipped with the other. All electrodes are locked in using this
process. Finally, devices are mounted to a PCB test board using carbon tape and wire
53
bonds are secured. Figure 2.12a contains a process flow graphic illustrating the steps
involved in device prep, and Figure 2.12b shows a device mounted on a test board.
Figure 2.12: (a) PolyMUMPS process flow with assembly; (b) device on test board.
2.4.4.5 Device Testing
Devices were tested in a custom built UHV chamber equipped with 12 electrical
feedthroughs and a base pressure of 1 x 10-7 Torr. Figure 2.13 provides a picture of the
test setup. Keithley model 4200-SCS Parameter Analyzer (hereinafter referred to as
Keithley 4200) equipped with six internal source measure units (SMU) was used to
electrically characterize the performance of the field emission microtriode. When
additional configuration options were needed, developed LabVIEW code was used to
integrate the Keithley 4200 with up to seven Keithley model 2410 SMUs. Developed
LabVIEW code is available in Appendix A; programs to perform I-V and lifetime
characterization are included. The Keithley 4200 provided sourcing voltages up to ± 210
V with low current measurement options. The accuracy of the current measurements
54
was 10-5 times the current range measured which was typically 1-10 µA, providing an
accuracy of 0.1 nA. Parallel channel measurements was possible using the six source-
measure units (SMU) available, which included one high accuracy preamplifier
equipped SMU capable of fA accuracy. Device test protocols were developed to collect
transfer and output curves from the devices.
Figure 2.13: UHV test system used for field emission device testing.
2.5 Mass Spectrometry (MS)

Chapters 3 and 6 focus on the utilization of carbon nanotube field emission based
devices as the electron source for use in mass spectrometry applications. Therefore, this
section will provide a brief introduction to the fundamentals of mass spectrometry.
55
2.5.1 Introduction to Basic Concepts
MS is an analytical technique that produces spectra of the masses of the atoms or
molecules comprising a sample of material. The spectra are used to determine the
molecular, elemental, or isotopic signature of a sample, the masses of particles and of
molecules, and to elucidate the chemical compositions of molecules, such as peptides
and other chemical compounds. MS works by ionizing chemical compounds to generate
charged molecules or molecule fragments and measuring their mass-to-charge ratios
[153]. It is the role of the ion source to convert a portion of the sample into ions.
Extracted ions of varying mass are moved through a mass analyzer, sorted by their
mass-to-charge ratio, and carried forward to make contact with a detector. There are
several types of ion sources that are used in mass spectrometry ranging from thermionic
and field emitters, to radioactive sources [153, 154]. Mass analyzers can also vary;
examples include single and double focusing magnetic sectors which separate ions by
mass and time of flight (TOF) mass analyzers which separate ions by time [153-156]. A
simple schematic of the three main system components, ion source, mass filter, and
detector, is shown in Figure 2.14.
56
Figure 2.14: Schematic diagram of a mass spectrometer.
2.5.2 Ionization Processes
“Ionization is the process by which an atom or a molecule acquires a negative or
positive charge by gaining or losing electrons to form ions, often in conjunction with
other chemical changes [157].” There are several ionization processes used in modern
day mass spectrometry [153, 155]. The fundamentals of the two utilized in this work are
briefly provided here.
2.5.2.1 Electron Ionization
In electron ionization MS (EI-MS), samples are introduced in the vapor state and
are bombarded by energetic electrons moving quickly across an ionization region. A
rapidly moving electron will not be captured by a molecule, instead however, they
impact the molecule and knock away one of its electrons. The molecule will lose one of
its least tightly bonded electrons, i.e. one of the electrons located in the highest occupied
57
molecular orbit (HOMO) [158]. The typical order electrons are lost upon EI is the lone
pair first, then the π-bonded pair, then the s-bonded pair. EI is a relatively harsh
technique due to the excess amount of energy typically delivered to the molecule. While
the specific energy required for removal of an electron is dependent on what orbital it
was occupying, the approximate energy required is 7 eV. The excess energy can be
delivered to the molecule, causing excess vibrational energy, and results in breaking up
of the molecule, also known as fragmentation [158]. Fragment ions, those formed from
decomposed molecular ions, are abundant in EI which can mean significantly less
intense molecular ion peaks [153, 155].
2.5.2.2 Chemical Ionization
In chemical ionization (CI), ions are formed by a process called ion-molecule
reaction. These reactions take place when a reagent gas, typically ammonia or methane,
is ionized by EI and then undergoes a chemical reaction with an introduced sample
molecule. In the process an electron, proton, or another charged species is transferred
between the ionized reagent gas and the sample [159]. Because samples are ionized by
protonation, the results are typically the production of [M+1]+ ions ,where M is the
analyte introduced. There is little excess energy in that process which results in much
less fragmentation. In the CI process both positive and negative ions can be formed and
analyzed providing improved identification of the sample. Schematic diagrams
58
illustrating the ionization process in both electron ionization and chemical ionization are
shown in Figure 2.15.
Figure 2.15: Schematic diagrams showing the ionization process in both, (a) electron
ionization, (b) and chemical ionization.
2.5.2.3 CNT Emitters for Mass Spectrometry
For the work in chapters 3 and 6, CNT field emitters as ionization sources in
mass spectrometry (MS) applications, there are additional benefits contributing to the
use of CNT field emitters over conventional emitters. During MS operation ions impact
electron sources, thereby sputtering the electrode and decreasing its lifetime [160].
CNTs are composed of carbon, which has a low sputter coefficient [161], making them
robust field emitters for applications involving ion creation (e.g. MS). Many groups have
shown that CNT field emitters are capable of emission current exceeding 4 A/cm2 [21,
59
162, 163], demonstrating they can provide sufficient electron emission current for
applications such as MS, which usually require current levels in the 1-2 mA/cm2 range
(10s to 100s of µA emitted from a point on the filament). Finally, the low turn-on fields
for CNT field emitters discussed earlier provide benefits in not only enabling low power
operation, but also allowing for control of the ionization energy and, in turn, an increase
in the ionization rate, i.e. the ionization probability in unit time.
60
3. Chemical Ionization Mass Spectrometry Using Carbon
Nanotube Field Emission Electron Sources
In the last five years, extensive investments have been made by the Department of
Homeland Security (DHS) into improving national security [164]. One of the eight key
Security Technologies receiving these investments is in the area of explosives trace
detection (ETD) [164]. In 2011 alone, DHS awarded $15 million for the purchase of 400
fixed ETD units, and an additional $39 million to purchase 800 portable ETD machines
[164]. Quoting TSA acting administrator, Gale Rossides, “Explosive Trace Detection
technology is a critical tool in our ability to stay ahead of evolving threats to aviation
security……Expanding the use of this technology at checkpoints and at departure gates
greatly enhances security to keep the traveling public safe [165].” As a result to this
demand, the need for robust, reliable, affordable, and technologically capable
instrumentation (e.g. ETD’s) is essential to the field. Mass spectrometry (MS) is a
standard laboratory technology for identifying trace levels of chemical compounds in
complex environments. The selectivity and specificity of chemical identification via MS
across a wide range of species exceeds that of other more commonly fielded
instruments, such as Raman spectroscopy and FTIR. Because the rapid and accurate
identification of trace explosives is so important, mass spectrometry is of great interest
in the realm of early threat detection
This chapter investigates the development of a novel packaged CNT field
emission electron source for use in a commercially available mass spectrometer

61
instrument. The source was designed to integrate nanostructures with straightforward
and functional packaging options to enable the efficiency of nanostructures to be
realized in field deployable and desktop instrumentation. CNT emitters were grown
directly on a readily available substrates and integrated into scalable packages to
achieve the required emission geometries. The electron source was fully characterized
and methods to improve the lifetime of the CNT emitters was also explored. The
packaged source aimed at improving explosives trace detection instrumentation in
homeland security circumstances (e.g. security screening for the Transportation Security
Administration, TSA). The source was designed to replace the current electron source,
i.e., a filament thermionic emitter, in a commercially available instrument, i.e., a FLIR
Systems, Inc. ETD mass spectrometer. The instrument primarily operates as a chemical
ionization mass spectrometer (CI-MS) due to the benefits of using CI-MS’s in explosive
trace detection. The developed CNT field emission CI-MS source was evaluated by
doing a direct comparison to a standard filament thermionic electron source in the same
system under the same operating conditions.
The research aims to optimize device parameters including electrical
performance, lifetime at operating pressure, power requirements, and the collection of
mass spectra and its related parameters including resolution, collision energy, and
selectivity. The research demonstrates the first reported use of a CNT-based ion source
capable of collecting chemical ionization mass spectra in both positive and negative
62
modes; furthermore, design validation is achieved through mass spectra collection of a
standard MS calibration compound (PFTBA) as well as trace explosives pertinent to
homeland security applications (i.e. TNT, RDX, and PETN).
3.1 Introduction
Mass spectrometry is a standard laboratory technology for identifying trace
levels of chemical compounds in complex environments. The selectivity and specificity
of chemical identification via MS across a wide range of species arguably exceeds that of
other more commonly fielded instruments, such as Raman spectroscopy and Fourier
transform infrared spectroscopy (FTIR). For example, the accurate and rapid
identification of trace explosives by MS is of great interest in the realm of early threat
detection for homeland security and defense [166, 167]. The purpose of the work
reported here was to evaluate the use of carbon nanotube field emitters as the electron
source in a mass spectrometer designed for security checkpoint screening and reports
the first utilization of a CNT field emission source for chemical ionization mass
spectrometry.
Ionization of the analyte of interest is a critical step in the identification process
during mass spectrometry [153]. Electron ionization and chemical ionization are both
used when identifying chemical threats with MS. CI-MS is advantageous for the
selective identification of explosives as they can be negatively ionized more easily than
most interferents due to the strong electron affinity of the nitro group of these
63
compounds [168]. However, gas requirements, power consumption, and inadequate
lifetime are often limiting factors for the use of conventional ion sources in portable
mass spectrometers. Thus, the development of a low cost, replaceable CI mass
spectrometer field emission electron source would be beneficial for use in mass
spectrometers for portable applications, such as security checkpoint screening.
Field emission electron sources have several advantages for portable applications
such as very small size, low power consumption, and minimized thermal degradation of
the materials. Since first being reported as an electron field emitter in 1995 [18, 19, 105]
carbon nanotubes have proven themselves to be a viable candidate for electron sources
in various applications [106, 107]. CNTs have a high aspect ratio, small tip radius of
curvature, good conductance, extremely large Young’s modulus (high stiffness), and
high tensile strength allowing the tip to withstand the extremely strong fields (several
V/nm) needed for field emission [106]. Mass spectrometers usually require current levels
in the 1-2 mA/cm2 range (10s to 100s of A emitted from a filament). Many groups have
shown that CNT field emitters are capable of emission current exceeding 10 mA/cm2 [21,
162, 163], demonstrating they can provide sufficient electron emission current for MS.
Turn-on fields for CNT field emitters are also very low, enabling low power operation.
Wang et al. reported turn-on fields as low as 0.64 V/µm at a current density of 10 µA/cm2
from functionalized CNT structures [169]. Furthermore, the highly ordered covalently
bonded crystalline structure of the CNTs provide increased stability when compared to
64
other metal field emitters commonly used such as tungsten and rhenium. The activation
energy for surface migration of atoms on CNTs is significantly larger (17 eV) than
tungsten (3.2 eV) and rhenium (2.7 eV), thus CNTs are less sensitive to surface migration
[106]. CNTs also possess a high melting temperature when compared to refractory
metals such as tungsten. Additionally, ions impact electron sources during MS
operation, thereby sputtering the electrode and decreasing its lifetime. CNTs are
composed of carbon, which has a low sputter coefficient [161], making them robust field
emitters for mass spectrometry. With so many benefits, it is not surprising that the
number of CNT field emitter applications have increased in the last decade. However,
while CNTs have been used as field emission sources in numerous applications [170],
including EI-MS [147, 171-173], there are to the authors’ knowledge no reports that have
examined CI using a CNT field emission electron source.
In this research, we evaluate a custom packaged CNT field emission electron
source that allows for direct replacement of an existing filament thermionic emission
electron source in a FLIR Systems, Inc. (“FLIR”) explosives trace detection desktop mass
spectrometer for use in CI-MS mode. To the authors’ knowledge, the present research
demonstrates the first use of a CNT field emission electron source for CI-MS. Electrical
characteristics, power requirements, and lifetime for these devices have been evaluated.
Both negative and positive chemical ionization (NCI and PCI, respectively) are
65
examined. Mass spectra for MS calibrants and trace explosives have been obtained with
this novel CI source.
3.2 Experimental Methods

Fabrication of the CNT field emission electron source involved a two-step
process: CNTs were grown on prepared substrates and then mounted onto a specially
designed printed circuit board (PCB) field emission platform. CNT substrates were
prepared by performing a 250 µm shallow cut (or trench) with a dicing saw into 500 µm
thick conductive silicon wafers to define 3.6 mm2 die sizes. The trench allowed for
separation after growth of the CNT emitters by carefully snapping the wafer along this
trench. A 50 Å film of iron was deposited onto the substrates by electron beam
evaporation to serve as a CNT catalyst. CNTs were prepared using microwave plasma-
enhanced chemical vapor deposition (MPECVD) as previously reported [56]. Briefly, the
substrates were loaded into the growth chamber and treated with a 100 sccm (standard
cubic centimeters per minute) ammonia heat-up cycle for 120 s to reach pretreatment
conditions of 850 °C, 21 Torr, and 2.15 kW. Next, a pretreatment step consisting of 100
sccm of ammonia for 360 s de-wet the iron film into catalyst nanoparticle templates with
diameters of 50-100 nm. Vertically aligned multiwalled nanotubes (VA-MWCNTs,
hereafter CNTs) approximately 30 µm in height were grown using a 3:1 gas ratio of 150
sccm methane and 50 sccm ammonia for an additional 360 s. After growth, the 3.6 mm2
66
dies were separated by snapping along the trenches for mounting and testing. A
scanning electron microscope (SEM) image of the CNT forest is shown in Figure 3.1a.
A custom PCB platform (Figure 3.1b) was designed to allow for direct fit and
replacement of the existing filament thermionic emission source installed in the
prototype desktop mass spectrometer. A single die with CNTs was mounted with
conductive silver paste to the center electrode; the thickness of the paste is
approximately 20 µm. A surrounding square electrode was then fitted with a custom 750
µm thick copper standoff fabricated by photochemical machining (Fotofab, Inc.). An
extraction grid of tungsten woven wire mesh with 36% open area was attached to the
top of the copper standoff, providing an extraction grid for electron field emission.
Thinner meshes were investigated, but did not provide sufficient mechanical stability.
Figure 3.1c shows devices with and without the extraction mesh above the CNT die. The
CNT tip to mesh distance was in the range of 195 µm to 205 µm with an average of 200
µm due to the thickness of the conductive silver paste.
Prior to testing in the mass spectrometer, the fabricated devices were
characterized in a test bed using two Keithley 2410 source-measure units and a custom
LabVIEW program. This test bed provided a controlled environment and geometry for
device characterization prior to mounting in the desktop mass spectrometer. The test
bed also allowed for failure analysis and examination of the effects of controlled
pressure variation. Current-Voltage (I-V) curves were measured to determine basic
67
device parameters and model the electrical behavior (hereafter referred to as ex-situ
characterization to distinguish it from the data taken while in the mass spectrometer). I-
V curves were taken at two pressures, a low vacuum level of approximately 1x10-4 Pa
(1x10-6 Torr) to verify device operation, and 1x10-2 Pa (1x10-4 Torr) of room air, the
approximate operating pressure and reagent gas used in the explosives trace detection
desktop mass spectrometer during CI mode.
Figure 3.1 Images of the CNT electron source components (a) SEM image of CNT field
emitters as grown on the substrate, (b) photograph of the Duke/FLIR CNT electron
source platform set inside its wiring harness mount, (c) photograph of CNT field
emitters mounted into the platform. The source is shown before and after placement
of extraction mesh.
During the ex-situ characterization, the turn-on voltage (Vto) and threshold
voltage (Vth) were measured for all devices. Vto is defined as the applied voltage when
the emitted current reaches 1 nA, and Vth is defined as the voltage required to emit 1 µA
of electron current. Devices were then subjected to lifetime testing at a pressure of 1x10-2
Pa of lab air until failure. Emitter current was held constant by using a feedback control
loop to vary the bias applied to the extraction grid to maintain 5 µA. I-V measurements
from the electrodes were collected every second. Devices that were used in the desktop
68
mass spectrometer tests underwent one hour of burn-in [98] at 1x10-2 Pa to condition the
CNT emitters before installing them into the mass spectrometer. Initial testing of the
sources in the mass spectrometer was performed by operating the instrument with the
ion source outlet flow restrictors removed so that the source was effectively performing
electron ionization rather than CI. Once device performance was confirmed, flow out of
the ion volume was again restricted to achieve source pressures suitable for CI.
The ion source conditions were identical when using either the CNT field
emission electron source or the filament thermionic emission source. A short capillary
restrictor admits the sample into an ion region heated to 180 °C with a volume of about 1
cm3. Two small orifices communicate with the bulk vacuum chamber of the mass
spectrometer. A 200 µm diameter orifice in a 6 mm diameter stainless steel plate serves
to admit electrons from either the filament or the CNT source. A 400 µm diameter orifice
in another plate allows ions created in the ion source to enter into electrostatic lenses
that focus the ion beam into the mass analyzer. The pressure in the ion source, while not
measured directly in these experiments, can be calculated in the 13 to 133 Pa (0.1 to 1
Torr) range based on the conductance’s of the inlet capillary and the orifices that let gas
out of the ion volume into the main vacuum chamber. This pressure range is consistent
with most CI source pressures. The only gas admitted into the ion volume was lab air
from directly above the sample ticket that also contains the analytes in the gas phase;
therefore the “chemical ionization gas” consisted primarily of nitrogen and oxygen.
69
Mass spectra were acquired over the m/z range of 40 to 700 for the standard MS
calibration compound perfluorotributylamine (PFTBA). Headspace vapor was leaked
into the vacuum system under control of a flow restrictor and solenoid valve. Spectra for
trace explosives were acquired by dosing aliquots of a solution containing the explosive
in an organic solvent (typically methanol) onto a surface-sampling ticket, allowing the
solvent to dry, and then analyzing the ticket via thermal desorption and transport of the
explosive analyte into the CI volume. Mass analysis was performed with an ion trap
analyzer coupled to the CI volume with electrostatic lenses for ion transport. Ion
detection was via a conversion dynode/electron multiplier assembly.
3.3 Results and Discussion

3.3.1 Ex-Situ Characterization
Figure 3.2a displays typical ex-situ I-V characteristics for the CNT field emission
electron source. The I-V curve provides both a turn-on voltage and operating bias for
desired emission current levels. This information is essential to choosing operating
conditions for the explosives trace detection mass spectrometer during testing. The three
I-V plots shown in Figure 3.2a were obtained with an increasing sweep voltage applied
between the CNTs and the extraction grid electrode. The devices maintained reliable
emission current throughout an operating range of 1 nA to a saturation level of
approximately 500 µA. The saturation level is 14 mA/cm2, which is more than sufficient.
70
Figure 3.2 Electrical characteristics of the carbon nanotube electron source (a) I-V
characteristics showing three consecutive and increasing voltage sweeps, (b) Fowler-
Nordheim plot of I-V curve #3 with nonlinearity of the slope attributed to a nonlinear
field enhancement factor, (c) Lifetime analysis operating at a pressure of 1x10-2 Pa
(1x10-4 Torr) of room air and a fixed 5 µA CNT emission current.
The Fowler-Nordheim (FN) plot shown in Figure 3.2b was generated from the 0
V to 450 V I-V curve of sweep #3 in Figure 3.2a. To create this plot, the FN equation was
re-written in FN coordinate form (equation 1) where J denotes the emission current
density, ϕ is the work function of the CNT emitters, E is the applied electric field, 𝛽 is
the field enhancement factor, and the parameters a and b are universal constants defined
in literature, 1.54 x10-6 AeVV-2 and 6.83 x103 eV-3/2 Vµm-1 respectively [174]:
J 2  3/2
ln( )  ln( a )  b [12]
E2  E
71
The slopes of the generated FN plots indicate that our CNT field emission
electron sources exhibit the non-linearity that is characteristic of CNT field emitters
[174]. This non-linear phenomenon is not clearly understood. Researchers have
attributed it to space charge effects and varying electron transport tunneling
mechanisms, with the transition point represented by the “knee” in the F-N plot [175-
177]. The device characterized in Figure 3.2 has a knee between the low and high field
behavior at a field of 1.575 V/µm, which closely matches values reported in literature
[178]. Using the FN plot, slope coefficients were extracted and field enhancement factors
(β1 and β2) were calculated for both regions using the following equation:
 3/2
  b [13]
slope
For the device whose data is shown in Figure 3.2, and using a typical MWCNT
value of 4.8 eV for ϕ, we observed slope coefficients of -16.67 and -33.49 for the high and
low regions respectively, which yielded β values of 4309 and 2144 respectively. We
observed that the computed β can diverge from the reported values by +/- 18%. This is
due to the variation of the distance from the CNTs to the extraction mesh caused by the
silver paste thickness. The reported β values, inclusive of the variation range, also
closely coincide with literature as expected [98].
Figure 3.2c shows the ex-situ emission lifetime measurements of a device at a
steady state pressure of 1x10-2 Pa (1x10-4 Torr). The device functioned for more than 320
hours of continuous operation. Assuming 10 hours of continuous operation per day, this
72
indicates a required emitter replacement period of approximately once per month.
However, assuming a reasonable duty cycle that accounts for the sample collection and
traveler interactions that would occur at a security checkpoint as 25% on-time, then this
320 hour lifetime would equate to 4 months of service. Another benefit of using the
CNTs is the ability to cycle the emitter on and off with minimal degradation. A standard
tungsten filament could not be cycled quickly without dramatically shortening its
lifetime. Cold field emission cathodes, including these CNT field emitters, can be
quickly cycled between on and off states to conserve power without affecting emitter
lifetime [179]. We found that a 10 s on/off cycle had little effect on CNT cathode
performance or lifetime in the test bed. Specifics of pulsing performance will be the
focus of a future publication. It should be noted that an air jet directed at the CNTs
during CI operation in the explosives trace detection mass spectrometer can reduce on-
time, however modifications could be made to the system to correct for this.
Nevertheless, the ability to power cycle without a lifetime penalty, coupled with its low
power and low temperature characteristics, make the CNT field emitters attractive
options for further study and a viable candidate for CI and EI ion sources.
The increase in the voltage required to maintain 5 µA emission over time
suggests gradual CNT field emitter degradation (Figure 3.2c). This degradation effect
has been reported previously [132, 160, 180-182] and was related to several distinct
causes, including shortening of the CNTs from ion bombardment and damage to the
73
sidewalls from joule heating at the CNT tip during electron field emission. The voltage
spikes observed in Figure 3.2c can be attributed to sudden changes in emission current
forcing fast instrument correction to maintain the set current. These sudden changes in
emission current could be explained by CNTs undergoing deflection during the emitting
process. It has been reported [182] transients in emission current can be caused by
electrodynamic interactions between field emitting CNTs. Deflected CNTs experiencing
these interactions can undergo an abrupt pull, resulting in the sudden current changes.
3.3.2 Integration into the Desktop Mass Spectrometer
The fabricated CNT field emission electron sources were incorporated into the
explosives trace detection mass spectrometer. The schematic in Figure 3.3a illustrates the
position of the device with respect to the ionization region, repeller electrode, sample
inlet capillary, and the aperture leading to the mass analyzer. As described above, CNTs
were grown on a 3.6 mm2 die, which was then mounted to the PCB with conductive
silver paste. This PCB was designed to be the same size and have the same electrical
connections as the filament assembly used in the desktop mass spectrometer, allowing
the CNT field emission electron source to be a drop-in replacement. Figure 3.3b shows a
wide view image of the explosive trace detection desktop mass spectrometer with the
device installed; the wiring harness mount protrudes from the top for electrical
connection. Figure 3.3c shows the CNT field emission electron source integrated into the
74
system just above the ionization region with electrical extensions from the harness board
extending down to it.
Power requirements of the CNT field emission electron source installed in the
mass spectrometer were minimal. Operating voltages varied between 500 to 1500 V with
5 to 50 µA of emission current, equating to a maximum source power requirement of 75
mW. The mass spectrometer allowed 10 ms between the time the voltage was applied to
the source and the time ions were accepted from the source by the mass analyzer for
emission of electrons to begin. The minimum response time of the CNT source was not
interrogated, but in all cases emission was observed after this 10 ms period in the form
of ion signal. Thus 10 ms serves as a maximum bound for the turn-on time. The kinetic
energies of electrons emitted from the CNT field emission electron source was not
directly measured, but are initially expected to be similar to the bias voltage applied
before being cooled by the gas in the source.
Figure 3.3 Integration of the carbon nanotube electron source into the explosive trace
detection mass spectrometer. (a) Schematic of the ionization region showing source
location, (b) photograph of the desktop mass spectrometer, (c) a magnified
photograph of the ionization region showing the CNT field emission electron source
installed.
75
3.3.3 Evidence for Chemical Ionization
The chemical ionization conditions for this work differ from more traditional CI
investigations. The technique is normally performed using methane, isobutane, or
ammonia as the CI gas [183-185]. In those cases, protonated molecules and molecular
fragments tend to dominate the positive ion chemical ionization mass spectra. For the
data presented here, the chemical ionization gas (lab air) does not donate a proton, but
rather the following simplified mechanism dominates, according to Hunt and Crow
[186].
N 2  e   70 eV   N 2   2e  [14]
N2  M  M   N 2 [15]
Mass spectra collection was conducted with the filament thermionic emission
source operating at its standard setting of 200 µA and the CNT field emission source at
50 µA. The latter was limited by the dimensions of the CNT source and the instrument
capabilities. Nonetheless, the lower current is beneficial for mobile instruments for
portable operation due to its contribution to lower power. The differences in electron
current could have an effect on the intensity of the mass spectral signal if the electrons
are the limiting reagent in the ionization reaction. Thus, this work makes no assertion
about the MS signal intensity resulting from the CNT vs the filament source. However,
the current is not expected to affect the peaks that appear for each analyte nor their
relative abundance. Thus, the nearly identical peak structure of the resulting mass
76
spectra indicate that the effect of the electrons from the CNT array, once emitted and
cooled by the CI gas, are essentially identical to the effect of the electrons emitted by the
filament.
Prior to collection and examination of mass spectra for explosive analytes, the
instrument was calibrated using a standard MS calibration gas (PFTBA) in EI mode, as
well as both positive and negative chemical ionization modes. Analysis and brief
discussion of the PFTBA spectra can be found in Appendix B and provides further
evidence for chemical ionization resulting from each source. After spectra were collected
using the calibration gas, amounts consistent with trace standards in the security field of
trinitrotoluene (TNT), Research Department explosive (RDX), and pentaerythritol
tetranitrate (PETN) were examined. Identical amounts of trace explosives were
introduced during spectra collection for each source. The same emission currents used
for PFTBA spectra collection were also used with the trace explosives (50µA for the CNT
field emission source and 200 µA for the filament thermionic source).
The normalized mass spectra for TNT collected using the CNT field emission
source and filament thermionic emission source are shown in Figure 3.4a and Figure
3.4d, respectively, and correlate well with each other as well as literature spectra
collected with filament thermionic emitters [185, 187]. Gas molecules in relatively high
pressure ion sources can collisionally cool electrons to kinetic energies near 0 eV. These
energies are low enough for attachment to molecules of compounds that have positive
77
electron affinities while causing little bond breakage, forming molecular anions. In the
case of TNT, the process is accurately referred to as electron capture (EC). However, the
EC process in a gas that has been intentionally added to collisionally cool electrons is
often referred to as negative chemical ionization (NCI) in the literature [188]. This latter
convention will be utilized in the present manuscript. The mass locations and
assignments for the fragments of TNT include m/z = 197 [(TNT-NO)-], m/z = 210 [(TNT-
OH)-], and an intense peak appearing at m/z = 227, as expected for NCI. The presence of
the molecular anion is strong evidence of chemical ionization. Electron transfer from the
reagent ions and electron capture can both result in molecular ions [187].
The normalized mass spectra for RDX collected using the CNT field emission
source and filament thermionic emission source are shown in Figure 3.4b and Figure
3.4e. The data shows adduct ions that are clearly the result of ion-molecule reactions. For
example, m/z 268, observed in both the CNT and filament source data, seems likely to be
the result of the reaction:
 RDX  NO2 

RDX  NO2   [16]
If EI dominated the ionization mechanism, one would expect no significant
signal beyond m/z 222, which corresponds to the molecular ion of RDX. The source of
the NO2- is likely RDX itself, although some NOx production in an ion source that
contains both N2 and O2 may be reasonably expected. The mass locations and
assignments for additional fragmentations include m/z = 102 [(C2H4N3O2)-], m/z = 129
78
[(C3H5N4O2)-], and m/z = 324 [(RDX+102)-]. The above peaks are consistent between the
two sources as well as those observed with NCI literature spectra using filament
thermionic emitters [185, 187, 189]. Finally, the small peak at m/z 176 could be attributed
to [(RDX-NO2)-] [C3H6N5O4]- [185].
The normalized mass spectra for PETN collected using the CNT field emission
source and filament thermionic emission source are shown in Figure 3.4c and Figure
3.4f. Similar to RDX, the ion signal for PETN at m/z 378 probably results from the
following reaction:
 PETN  NO2 

PETN  NO3  [17]
as the molecular weight of PETN is 316 g/mol, so a peak at m/z 378 cannot be the result
of electron ionization and must be the product of an ion-molecule reaction. Both of these
product ions are clearly shown in previously published, more traditionally generated CI
spectra [185]. The mass locations and assignments for additional fragments include m/z
= 62 [(NO3)-], m/z = 315 and 317 [(PETN-H)- and (PETN+H)-], and m/z = 333
[(PETN+OH)-]. The peaks are consistent between the two sources and with those in
literature using filament thermionic emitters [185, 190]. The calibration curves were
generally linear as well. In the case of TNT, the linear plot (which is included in
supplemental information for reference) had a slope of 991, a y-intercept of -4,518, and a
R2 of 0.963. The CNT field emission electron sources show similar overall sensitivity to
the standard system using filament thermionic emission.
79
Figure 3.4: Trace explosive chemical ionization spectra collected using both the CNT
field emission (left column) and the filament thermionic emission (right column)
sources in the explosive trace detection desktop MS. The spectra for TNT are shown in
(a) and (d), the spectra for RDX are shown in (b) and (e), and the spectra for PETN are
shown in (c) and (f).
3.4 Conclusion
A custom designed, fully packaged CNT field emission device has been
developed and used in a prototype commercial mass spectrometer as an electron source
80
to obtain chemical ionization mass spectra in both positive and negative modes.
Although further study is needed, this source is a candidate for CI and EI mass
spectrometry applications. The CNT field emission source demonstrated low power, low
temperature, and attractive lifetime. A constant-on lifetime of 320 hours was
demonstrated for the CNT devices. This lifetime equates to 4 months of operation,
assuming a 25% on-time in real-time security checkpoint deployment. The CNT emitters
also demonstrated the ability to cycle and thus avoid continuous-on operation, the
details of which will be the subject of future publication. Spectra were collected for a
standard MS calibration material (PFTBA) as well as trace amounts of explosives (TNT,
RDX, and PETN). The spectra collected showed similar peaks for both the CNT field
emission source and a traditional filament thermionic emission electron source in the
same system. Furthermore, the EI and CI spectra collected with the CNT field emission
source closely matched those observed in literature that were produced with traditional
filament thermionic emission sources. Sensitivities for the CNT field emission source
were similar to filament thermionic emitters used in the same mass spectrometer.
81
4. Integrating Carbon Nanotube Forests into Polysilicon
MEMS: Growth Kinetics, Mechanisms, and Adhesion
Chapters five and six of this work discuss development of next-generation vacuum
microelectronic devices for integrated circuit and micron scale mass spectrometer ion
source applications. Both technologies are built upon a previously investigated platform
that encompasses two proven technologies: Micro-Electro-Mechanical Systems (MEMS)
platforms and CNT field emitters. Where the research focuses on both functionality and
performance improvement, as well as additional operation modes, a core fundamental
concern has yet to be investigated. The electrodes fabricated within the MEMS platform
are fabricated explicitly from polycrystalline silicon (poly-Si); and the carbon nanotube
emitters are grown directly on the poly-Si electrodes. While growth of carbon nanotubes
on single crystalline silicon has been well studied, the growth of CNTs and CNT field
emitters on poly-Si has not been explored. More specifically, a general understanding of
the growth mechanisms and the kinetics involved with CNT growth on poly-Si has not
been investigated.
Fundamentally, it is important to have a good understanding of all material
interfaces and interactions in a system. This will reduce undesired effects at a systems
level. On a device performance concern, it is very important to be able to control specific
properties of the CNT emitters on the device. Two important CNT emitter characteristics
for device performance are the length of the emitters and the uniformity of the CNT
diameters. The benefits of scaling down VMDs, specifically the ability to place the
82
cathode and the grid near each other, are easily lost if the length of the CNT emitters
cannot be controlled. Too short and the required voltages are too large for reasonable
performance. Too long and the CNT emitters will short the electrodes, resulting in
complete device failure. Because field emission from CNTs is directly related to the field
enhancement factor, and the field enhancement factor is directly related to the
geometrical properties of the emitter, having control over the CNT diameter is also of
great important. Additionally, the CNT emitters have a specific adhesion strength when
grown on poly-Si. Adhesion is also critical to device performance. Poor attachment of
the CNT emitter under the high potentials needed for field emission can result in
extraction of the emitter and lead to shorting of the electrodes and device failure.
This chapter will focus on the growth of CNTs on poly-Si. The growth
mechanisms, kinetics, and adhesion of the CNTs on poly-Si will be discussed and
contrasted with single crystalline silicon (Si). We have shown that the lifetime and
operation characteristics of devices based on those CNT emitters, are influenced by the
substrate variation. These results are not only important for improving VMD designs
that incorporate CNT emitters, but also for the general scientific community and all
applications involving interaction between MEMS and CNTs. The results have
improved the general understanding of the integration of these two enabling
technologies. More specifically, the results have led us to improved development of the
next generation VMD devices which will allow expansion in application.
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4.1 Introduction
Vacuum microelectronic devices (VMDs) and sensors [7, 191-195] present an
attractive alternative to solid-state technology in applications where solid-state devices
are unreliable or do not provide adequate performance. Situations that require high
frequency and high power device performance, or operation in harsh environments such
as high temperature or radiation, are ideal for vacuum microelectronics. While charges
flowing through semiconducting channels tend to scatter, resulting in a loss of power
and signal quality, electrons in a vacuum tube are unaffected by scattering loss [195].
Despite the performance advantages in certain applications, the use of vacuum
electronics has been limited due to inadequate development of a suitable cathode that
can be integrated into the common vacuum microelectromechanical systems (MEMS)
platform. MEMS devices are fabricated by silicon based microfabrication techniques
[196], are constructed from almost entirely polycrystalline silicon (polysilicon or poly-Si)
to achieve conductive structures, and can be micromachined into desired architectures.
MEMS, a technology presently used as a platform for many types of navigation,
automotive, and consumer microelectronic devices, offers a versatile and reliable
microscale platform that can allow for integration of a large number of vacuum circuit
elements on a single substrate.
Carbon nanotube (CNT) cold-cathode field emitters have been shown to be
excellent candidates for integration with MEMS [197-199] owing to their outstanding
84
electrical and mechanical properties, allowing for the design and fabrication of complex
and innovative integrated VMDs. To date, however, the factors involved with
integrating CNTs as field emitters, specifically in situ growth of CNTs on polysilicon
substrates, have not been well studied. A scalable and reliable technology requires
precise control over all components and conjoined materials. For CNT field emitters,
precise control of the distance between the cathode and extraction electrode is critical to
controlling power requirements and to avoid electrode shorting and device failure.
Understanding CNT growth mechanisms, kinetics, and adhesion on MEMS substrate
materials will enable seamless integration of CNT technology with existing standard
MEMS processing techniques. CNT diameter, forest density, and length all influence
field emission characteristics. Here, we will focus on the growth kinetics as a means to
developing fine control over these parameters.
While no studies have been performed on the kinetics and mechanisms of CNT
growth on polysilicon to our knowledge, significant research has been performed
studying growth kinetics and mechanisms for CNTs grown on monocrystalline silicon
by both thermal and plasma-enhanced chemical vapor deposition (CVD). In early
experiments by Baker et al. [200] on thermal growth of carbon nanofibers with catalyst
particles fixed at the tips (tip-growth mode), bulk carbon diffusion through the catalyst
was identified as the rate-limiting step due to the similarity of the growth activation
energy with carbon diffusion. Similarly, Chhowalla et al. [201] reported a bulk-
85
diffusion-limited growth process in tip-growth by plasma-enhanced (PE) CVD, finding
an activation energy of 1.4 eV and a growth rate that varied inversely with catalyst
nanoparticle diameter [202]. Several other groups have reported activation energies in
the range of 1.3 – 1.6 eV [203-205], and others have found the energy barrier to CNT
growth closer to 2.2 – 2.4 eV [206-208]. Conversely, in the low-temperature regime (T =
150 – 500 °C), Hofmann et al. [209] reported a very low activation energy of 0.25 eV for
tip-mode PECVD growth, attributing the low value to surface diffusion of plasma-
dissociated precursors across the catalyst particle. As such, bulk diffusion through the
catalyst is not required for successful CNT growth. While most growth trends are
nearly linear, especially for tip-mode thermal CVD deposition techniques, parabolic
growth trends have been observed as well by several groups [210-213] in thermal CVD.
This effect was attributed to gas phase diffusion-limited deposition. Wirth et al. found a
0.6
pressure dependence of p and activation energy < 1 eV for tip-growth thermal CVD
[214], attributing observations to both dissociation of acetylene on the catalyst surface
and a rate-limiting step of diffusion in the catalyst. Surface-diffusion-based growth
mechanisms have been described theoretically by Louchev et al. [215, 216] involving
carbon precursor species traveling along the length of growing CNT forests. In addition
to a lack of literature addressing CNT growth kinetics on polysilicon substrates, there is
a lack of existing research studying higher temperature (800 – 900 °C) PECVD base-
growth kinetics and mechanisms, especially considering a mechanism involving a rate-
86
limiting step of surface diffusion along the length of the growing CNT forest to the
catalyst.
Despite significant efforts to understand CNT growth kinetics on
monocrystalline Si, little is known about growth details on poly-Si substrates. Therefore,
we study base-growth of CNTs by PECVD (catalyst particles fixed at the substrate
surface) on Si (100) and polysilicon substrates, designed identically to those fabricated in
the industry-standard Polysilicon Multi-User MEMS Process, or PolyMUMPs, with the
goal of modeling the same type of growth that occurs on MEMS devices. We observe a
parabolic growth trend between CNT forest height and deposition time, separate
activation energies corresponding to different phases of growth, and present evidence in
favor of a growth mechanism dominated by surface diffusion of carbon precursor along
the outer surface of the CNTs, along the length to the catalyst fixed at the base of the
forest. Data is then presented to explain the causes of growth differences between CNTs
deposited on Si (100) and CNTs deposited on poly-Si. Finally, we engineered thin film
interlayers between the catalyst and the polysilicon substrate to improve the adhesion of
CNT field emitters to the substrate.
4.2 Experimental
4.2.1 Substrate Preparation
The monocrystalline silicon substrates used for the growth of CNTs in this study
were N-type conductive (100) silicon. The polycrystalline silicon wafers were likewise
87
fabricated at RTI International using a similar process to the standard PolyMUMPs to
replicate the substrate conditions for CNT growth on a MEMS device. A 1 µm-thick
polysilicon film was deposited on a 500-µm thick N-type (100) silicon wafers via low-
pressure CVD (LPCVD) followed by a 200 nm thick sacrificial layer of phosphosilicate
glass (PSG) to serve as a phosphorus dopant source. The wafer was then annealed at
1050 °C for 1 hour in argon to N-dope the polysilicon as well as release stress in the
polysilicon film formed during the LPCVD process. Next, the substrates were cleaned in
a buffered oxide etch (BOE), rinsed with DI water, and dried with N2 gas. All CNT
growth substrates were coated with an iron catalyst layer 5 nm in thickness at RTI
International using a CHA electron beam evaporation system.
Improvements in CNT adhesion to polysilicon substrates were made
possible through the use of 2.5 nm thick metallic layers introduced between the
polysilicon substrates (prepared as described in Section 2.1) and the thin film CNT
catalyst. It has also been shown [217-219] that these interlayers can result in better
control of the final CNT film morphology by reducing catalyst diffusion into the poly-Si
substrate during growth, but this was not directly investigated in this study. In order to
compare the adhesion between CNT films with and without a metallic interlayer,
samples of identical dimensions were fabricated for each of the interlayers, as well as a
control sample that contained no interlayer. A dicing saw was used to precisely define
6.25 mm2 substrates. Next, a brief BOE rinse was performed to remove any residue and
88
then the substrate was loaded into an electron beam evaporator to deposit the refractory
metal layers and iron catalyst.
4.2.2 Carbon Nanotube Growth
Microwave PECVD was employed for the growth of CNT forests on each type of
substrate, which has been described in detail in previous publications [220-225]. In brief,
the process occurs during two steps: heat up and growth. The heat up step involves
raising the substrates to the desired deposition temperature, which is regulated by a
thermocouple located directly under the quartz sample stage, followed by igniting and
tuning a reducing plasma. The plasma is struck under a 100 sccm flow of NH3 at the
base reactor pressure, and tuned to approximately 2.1 kW microwave power as the
pressure in the reactor rises to 21 torr. During this initial temperature and plasma ramp,
the iron film dewets into catalyst nanoparticles. Following pretreatment, CH4 is
introduced as the carbon-containing precursor at 150 sccm flow rate, and the NH3 flow is
decreased to 50 sccm.
CNTs were grown for different time intervals (1, 2, 3, 4, and 5 minutes) at
temperatures of 825, 850, and 875 °C on both Si (100) and polysilicon for the purpose of
identifying activation energies associated with different stages of growth. An extended
range of deposition times was performed on each substrate at 850 °C in order to identify
the diffusivity values of carbon feedstock through the growing CNT film. CNTs grown
on each substrate possess bamboo-type inner walls as seen in Figure 4.1, grow by the
89
base-growth mode, and CNTs grown on polysilicon substrates frequently display a
region of lower density, smaller diameter CNTs past the tips of the bulk CNT film.
Figure 4.1 Morphology of carbon nanotubes simultaneously grown on a) Si (100) and

b) polysilicon imaged by SEM. c) TEM micrograph of a CNT with bamboo-type inner
walls, with inset depicting a catalyst iron nanoparticle embedded within the CNT
base; d) schematic of field emission test chamber to determine poor CNT adhesion.
4.2.3 Characterization Techniques
Scanning electron microscopy (SEM) was performed with a FEI XL30 SEM-FEG
microscope to measure the CNT film thickness, and a Tecnai G2 Twin instrument was
used to collect transmission electron microscopy (TEM) images. Raman spectra were
90
measured using a Horiba Jobin Yvon LabRam ARAMIS Raman microscope with a 633
nm HeNe laser. Adhesion tests were performed using reflectance mode of a Shimadzu
UV-3600 UV-Vis-NIR Spectrophotometer. Field emission testing to determine poor
adhesion was performed in a custom UHV test chamber with Keithley 2410 SMU’s.
4.2.4 Adhesion Testing
Adhesion of the CNT emitters to the substrate was examined using the standard
American Society for Testing and Materials (ASTM) test methods for measuring
adhesion of thin films [226], which assesses the adhesion of films to substrates by
applying and removing pressure-sensitive tape over the film (3M Magic Tape 810D).
This procedure was combined with spectrophotometer measurements performed
iteratively after each tape test in order to measure the reflectance from the underlying
sample. More than ten samples from each interlayer set were tested with 50-60
spectrophotometer measurements performed on each sample for statistical relevance.
The reflectance correlated directly to the CNT density remaining on the sample after
each adhesion test, which provided quantitative measurements of the degree of
adhesion of the CNT film to the substrate. Each sample was mounted onto a custom 3D-
printed sample holder that was designed to be compatible with the spectrophotometer.
The instrument was operated in reflectance mode, scanning wavelengths between 200
and 700 nm. After the baseline measurements, the sample holder was removed from the
instrument and the first tape test was performed. Constant pressure was applied using
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fixed weights that were moved uniformly across the film surface, and tape removal
speed was carefully monitored; however, it has been shown [227] that variability in the
speed at which the tape is removed, as well as the variability in applied pressure, do not
strongly impact adhesion evaluation. After the tape was removed, the sample was
loaded back into the spectrophotometer for another set of reflectance measurements.
This process was repeated until the reflectance measurements saturated, indicating that
all possible CNTs were removed.

4.3.1 CNT Growth Kinetics and Activation Energies
In order to understand the differences between CNT growth on crystalline
silicon substrates using PECVD and the corresponding growth on a polysilicon
substrate, modeling was performed of the growth kinetics on each substrate. A model
based on Fick’s first law for a thin membrane [228] was used in a similar way to the Deal
and Grove model of thermal oxidation of silicon [212, 213, 229]. In short, the flux of
carbon species through the boundary consisting of the tip of the CNT forest is given by
Fick’s first law, and the diffusion constant for carbon through this boundary layer as
well as the thickness of the boundary are assumed constant in space and time. The
steady-state assumption is also in effect, whereby the flux of carbon species impinging
upon the growing CNT array is assumed equal to the flux of carbon species through the
CNT array, and also equal to the flux through the catalyst particle [230]. If N is the
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number of carbon species that diffuse into the iron catalyst and are subsequently
incorporated into the CNT film and F is the overall flux, the growth rate of the forest
may be expressed as
dL dt = F N (18)
The general solution to this expression takes the form
B(t gr )  AL  L2 (19)
where A and B may be expressed in terms of the diffusivity D, which is proportional to
exp(-Ea/kBT), kB is Boltzmann’s constant, T is the growth temperature, and tgr is the
growth time [229, 230]. For short growth times, hereafter referred to as the “linear”
region, equation (2) may be approximated as 𝐵(𝑡𝑔𝑟 ) ≈ 𝐴𝐿, and thus the linear rate
constant is B/A. For longer growth times, equation (2) may be approximated as
𝐵(𝑡𝑔𝑟 ) = 𝐿2 which will be referred to as the “parabolic” growth regime. From the
relationship between the linear rate constant and the activation energy associated with
the physical process that occurs during this period (i.e. nucleation of CNTs), the
activation energy may be calculated via the slope of the corresponding Arrhenius plot.
Likewise, the activation energy corresponding to the physical process occurring during
the parabolic region (i.e. the diffusion of carbon feedstock from the gas phase to the
catalyst through the growing nanotube forest) may be determined in the same way
using the parabolic rate constant B [230]. The termination growth regime, existing for
growth times exceeding the time steps considered for the parabolic region, is not
93
discussed here, although reports of CNT growth termination mechanisms may be found
in the literature [231-234].
As discussed in the Experimental Section, to determine the activation energies
for each phase of growth, growth temperatures of 825, 850, and 875 °C were used for
deposition times of 1, 2, 3, 4, and 5 minutes. As such, each point in Figure 4.2 is a
composite of five growth data points. During each growth experiment, Si (100) and
polysilicon substrates were loaded simultaneously in the PECVD reactor, and the film
thickness for each was measured by SEM. Figure 4.2 is the Arrhenius plot displaying
the natural logarithm of both the linear and parabolic rate constants as a function of
inverse temperature. The slope (m) of the Arrhenius curve is related to activation energy
by 𝐸𝑎 = −𝑘𝑏 𝑚. The results of this analysis indicate activation energies during nucleation
𝑆𝑖
corresponding to diffusion of carbon feedstock into the catalyst of EaSi,lin EaSi,lin 𝐸𝑎,𝑙𝑖𝑛 =
𝑝𝑜𝑙𝑦−𝑆𝑖
1.61⁡𝑒𝑉 on the Si (100) substrates, and 𝐸𝑎,𝑙𝑖𝑛 = 1.54⁡𝑒𝑉 on polysilicon substrates.
These values closely match the literature values for bulk diffusion of carbon into γ-Fe,
which have been reported in the range of 1.54-1.6 eV [235]. While γ-Fe typically does
not form below a temperature of 912 °C [236], the existence of residual carbon in the
PECVD reaction chamber could allow for the formation of γ-Fe rather than α-Fe or a
mixed phase. On the other hand, activation energies from the parabolic growth regime
𝑆𝑖 𝑝𝑜𝑙𝑦−𝑆𝑖
were found to be 𝐸𝑎,𝑝𝑎𝑟𝑎 = 1.90⁡𝑒𝑉 and 𝐸𝑎,𝑝𝑎𝑟𝑎 = 3.69⁡𝑒𝑉 for CNTs grown on Si (100)
and polysilicon substrates respectively.
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Figure 4.2: Arrhenius plot used to determine activation energies corresponding to the
linear and parabolic regions of CNT growth. The slope of the linear region for both
substrates is quite similar and corresponds to bulk diffusion of carbon precursor into
the γ-Fe catalyst nanoparticles. The slope in the parabolic region differs between
CNTs on Si (100) and polysilicon, leading to different activation energies for the
diffusion-limited phase of growth.
To understand the physical processes responsible for the increased energy
barrier during CNT growth compared with bulk diffusion occurring during nucleation,
as well as to understand parabolic activation energy differences between growth on each
substrate, the theory of diffusion developed by Deal and Grove [229] was again
employed. The overall growth rate expression used to fit growth rate data is
 4 B(t gr ) 
R(t )  0.5 A  1   1 (20)
 A2 
 
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where R is the height of the CNT forest, tgr is the growth time, and A and B are
composite terms previously discussed, and defined as
A  2D k , B  2Dn0 ns (21)
D is the diffusivity, k is the effective rate constant for the conversion of feedstock into
nanotubes, n0 is the concentration of feedstock at the tips of the CNTs as estimated by
the ideal gas law [237], and ns is the density of the deposited nanotubes (~0.02 g cm-3)
[212].
A more robust data set was needed to effectively fit equation (3), and thus
another growth series was performed at 850 °C with growth times of 20, 30, 40, 50, 60,
120, 240, and 480 s. Equation (3) was fit to the above set of data treating A and B as
constants to determine through the fit. The Levenberg-Marquardt nonlinear least
squares algorithm was used to calculate values of A and B, which were subsequently
used to extract diffusivity values (Figure 4.3). The diffusivity values calculated by this
method were 3.5 x 10-4 cm2/s and 7.9 x 10-5 cm2/s for CNT growth on Si (100) and
polysilicon substrates, respectively.
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Figure 4.3: CNT forest height kinetics at 850 °C. The solid curves correspond to the fit
to the Deal and Grove expression, with A and B values listed.
To determine the degree to which the growth process is diffusion-limited, a
quantity referred to as the diffusion-limiting factor α was calculated in a similar fashion
to Puretzky et al. [212]. The time-dependent term found under the radical in equation (3)
clearly plays a crucial role in the curvature of the length vs. deposition time curve for a
CNT growth reaction, and is defined as
 (t gr )  4 Bt gr A2  2n0 k 2t gr Dns (22)
Based on our fit of the Deal and Grove expression, the corresponding values of the
diffusion-limiting factor as a function of growth time are 𝛼𝑆𝑖 = 0.012𝑡𝑔𝑟 and 𝛼𝑝𝑜𝑙𝑦−𝑆𝑖 =
0.834𝑡𝑔𝑟 ⁡for growth at 850 °C. In order for the process to be considered diffusion-
97
limited, 𝛼 ≫ 1⁡[212]. Therefore, it is clear that growth of CNTs on polysilicon becomes
diffusion-limited about 10 times faster compared with CNTs grown on Si (100), resulting
in a CNT growth rate reduction earlier in the growth process on poly-Si compared to Si
(100).
4.3.2 Diffusion Mechanisms
Considering the above description of CNT growth kinetics on Si (100) and
polysilicon substrates, two closely related issues have arisen. First, the activation energy
for the parabolic region of growth is higher than the bulk activation energy calculated
for the linear region associated with nucleation, and the activation energy found for the
parabolic region of growth on polysilicon is significantly larger than the equivalent
energy barrier for growth on Si (100). Second, the diffusivity for growth on polysilicon
is significantly lower than the diffusivity for growth on Si (100). To understand the
factors giving rise to these observations, we must first consider the physical diffusion
mechanisms of the growth process under our PECVD growth conditions.
The first potential mechanism to consider is that of precursor transport through
the channels in between adjacent CNTs in the growing forest, or Knudsen diffusion.
The Knudsen number, the figure of merit determining whether transport is governed by
Knudsen diffusion, is the ratio of the pore size (r) to the mean free path of the carbon-
containing precursor (λMFP). Namely, if this ratio is less than 0.1, Knudsen diffusion may
occur [213, 238, 239]. Mean free path may be calculated as [240]
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MFP  RT 2 d 2 N A p (23)
where R is the ideal gas constant, T is the temperature, d is the molecular diameter, NA is
Avogadro’s number, and p is the chamber pressure. Considering methane as the
carbon-carrying species and the growth parameters enumerated in the Experimental
Section, 𝜆𝑀𝐹𝑃 ≈ 7.8⁡𝜇𝑚. If the inter-CNT pore size is on the order of tens of nanometers,
then the above ratio is much less than 0.1. Therefore, it is possible that some Knudsen
diffusion may occur during growth. It seems unlikely, however, that this is the primary
diffusion mechanism, as most carbon-containing species exist in the form of reactive
radicals due to the presence of the plasma. Additionally, the CNTs possess a high defect
density due to ion bombardment, which may serve as adhesion sites for reactive radicals
and hinder Knudsen diffusion.
There are several pieces of supporting evidence that favor surface diffusion along
the length of the CNTs as the primary diffusion-limiting mechanism during steady
growth. In the case of iron-catalyzed growth in this PECVD reactor, the growth
proceeds from the iron catalyst nanoparticles, which remain anchored at the substrate-
nanotube interface. A growth mechanism dominated by surface diffusion must allow
for diffusion of carbon species from the gas-nanotube interface to the catalyst particle at
the substrate surface, so surface diffusion must occur along the length of the CNTs.
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Figure 4.4: CNT forest height as a function of growth temperature on polysilicon
MEMS devices. All CNT forests were grown for 150 s.
Across a wider temperature range (700 – 900 °C), we observe a general inverse
relationship between CNT forest height and growth temperature on MEMS devices
(Figure 4.4). This is also reflected in the results of several other mechanistic studies [56,
201, 216, 241], and we initially attributed this effect to diffusion of the catalyst into the
polysilicon substrate; however, it is unlikely that a significant amount of iron silicide
exists in the catalyst nanoparticles, at least during the linear phase of growth, due to the
earlier conclusion that the nanoparticles are austenite, which does not form readily if a
significant amount of silicon has become incorporated into the nanoparticle [242].
Another explanation of the trend of decreasing CNT length as a function of
temperature could stem from the assumption that the majority of the diffusion of carbon
100
species from the gas phase to the catalyst particle occurs by the surface diffusion
mechanism along the CNT sidewalls. The average distance that a carbon species may
travel along the length of a CNT is given by [216]
SD  a0 exp  Eads  ESD  2 K BT  (24)
where a0 is the distance between adsorption sites on the CNT surface, Eads is the energy
barrier to adsorption, and ESD is the activation energy of surface diffusion along the
length of the CNT. Under these experimental conditions and using literature values to
approximate the different energy barriers, 𝜆𝑆𝐷 is on the order of tens of micrometers, and
this characteristic length is reduced strongly with increasing temperature. Therefore, it
is possible that the reduction in CNT length with increasing temperature on polysilicon
MEMS devices is primarily due to the limitation in surface diffusion length.
In order to elucidate the surface diffusion mechanism as well as understand the
large activation energy for the parabolic growth region on polysilicon substrates, Raman
spectroscopy was used to measure the mean distance between defect sites on CNTs
grown on each substrate. Through the Tuinstra-Koenig relationship [243], it is possible
to calculate the mean crystallite size (La) of CNTs by studying the relative intensities of
the D and G Raman bands. This expression was modified by Matthews et al. to take into
account the wavelength of the incident laser [244]. As seen in Figure 4.5, there is a
significant difference in La between CNTs grown on Si (100) and polysilicon, which were
found to be 66 and 201 Å respectively. This difference in La may arise from the presence
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of smaller catalyst nanoparticles on poly-Si substrates, discussed below in Section 4.3.3,
which could produce smaller diameter and more crystalline CNTs. If it is assumed that
La is a good approximation to a0 in equation (7), the distance between adsorption sites
that act as a pathway to surface diffusion along the length of the CNTs is larger for
CNTs grown on polysilicon. This may explain the large Ea for the parabolic region of
growth on polysilicon (3.69 eV) compared to CNTs grown on Si (100) (1.90 eV), as the
energy barrier for transport between adsorption sites should increase with increasing
distance between adsorption sites. In addition, the parabolic activation energy for CNTs
grown on Si (100) is close to the reported value for carbon adsorption on CNT sidewalls
[216, 245].
Figure 4.5: Raman spectra of CNTs grown on Si (100) and polysilicon substrates. The
crystallite size is 66 Å for CNT on Si (100) and 201 Å for CNTs on polysilicon.
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More support of surface diffusion as the primary diffusion mechanism in this
system comes from a hybrid carbon nanostructure consisting of few-layered graphene
covalently bonded to the sidewalls of CNTs referred to as graphenated carbon
nanotubes (g-CNTs). As reported elsewhere [220-224, 246], this hybrid nanostructure
(Figure 4.6) usually requires an elevated temperature (~1050 °C) in order to form the
leaves of few-layered graphene, referred to as “foliates.” The growth mechanism of
these foliates has been proposed as either a stress-buckling mechanism [221] where
varying growth rates between concentric nanotube walls causes buckling and fracture,
allowing growth of the foliate at the fracture site, or an ion bombardment mechanism
[222] where energetic ions from the plasma environment cause defects in the outer
nanotube walls, allowing foliates to nucleate and grow. In either case, defect sites in the
outer walls of the CNTs exist at high spatial frequency, which is also the pathway by
which surface diffusion-driven growth occurs. However, at the elevated temperatures
used to grow g-CNTs, growth typically terminates at about 10 μm, after which point
growth of foliates begins [221, 222]. This lower terminal length is in agreement with a
surface diffusion mechanism that limits the maximum forest length as temperature is
increased. If the temperature during growth remains lower (~850 °C), these g-CNT
structures may also form, but only when the growth time is much longer [223]. These
lower temperature g-CNTs also form foliates only after the termination length of the
forest is reached, which is typically about 40-50 μm at 850 °C.
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Figure 4.6: Plan view SEM micrograph of graphenated CNTs and b) higher
magnification image of a g-CNT. Inset: TEM micrograph of a few-layered graphene
foliate terminating in 3-5 graphene layers.
There are two heat sources during the growth reaction: the first is the substrate
heater underneath the growth substrate, and the second is the plasma above the
growing CNT array. The heat generated in the CNT film by ion- and reactive radical-
bombardment from the plasma, powered by 2.1 kW microwave power, should be higher
than that of the substrate heater, so a thermal gradient exists in the downward direction.
As a result, the CNT tips are the hottest regions of the film. After growth terminates due
to the limitation in surface diffusion length, the tips continue to experience reactive
carbon-containing radicals impinging upon them. As the tips are at a higher
temperature than the lower regions of the CNTs due to the aforementioned thermal
gradient as well as heat loss occurring from conductive losses along the length of the
tube and convective loss from gas molecules in the region between CNTs (due to some
limited Knudsen diffusion), the surface diffusion length is smallest for this region. As
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carbon species adsorb onto the CNT tips, surface diffusion may occur over a very small
length scale, especially at higher growth temperatures, and nucleate foliates at the defect
site where it comes to rest. In this way, surface diffusion seems the most likely
mechanism in light of the evidence presented for this hybrid nanostructure.
As a final point on the diffusion mechanism, it has been observed that when the
temperature is increased further (1100 °C or higher), CNTs or g-CNTs are no longer
present in the resultant film. Instead, vertically oriented sheets of few-layered graphene
are deposited on the substrate without any nanotube structure present [222]. As the
CNTs grown by this PECVD reaction have bamboo-type inner CNT walls, it is possible
that the surface diffusion length is even smaller for these conditions than the length of a
single bamboo segment, preventing the growth of nanotubes. Bamboo-type growth has
also been associated with a surface diffusion mechanism [215].
4.3.3 Causes of Reduced Diffusivity for CNTs grown on Polysilicon
Thus far, we have discussed the kinetics of CNT growth on polysilicon as
compared to growth on Si (100), examined the physical interpretation of the associated
activation energies, and considered diffusion mechanisms. Here, we hope to
understand the reason why growth on polysilicon has lower diffusivity and becomes
diffusion-limited earlier in the growth process compared with CNTs grown on Si (100).
It is well known that the diameter of the catalyst nanoparticles is closely related
to the diameter and growth rate of the resultant CNT [201, 247, 248]. Catalyst
105
nanoparticle diameter and CNT diameter are directly proportional, and CNT diameter
and CNT growth rate are inversely proportional. It is therefore important to examine
the way in which the iron catalyst film dewets on polysilicon in relation to Si (100).
Figure 4.7 shows SEM micrographs of catalyst nanoparticles forming on each substrate
at 850 °C, prepared by terminating the CNT growth process before introduction of the
carbon precursor. From Figure 4.7, it is clear that nanoparticles that dewet on
polysilicon are less uniform, with the highest frequency nanoparticle diameter between
20 and 30 nm, and form a bimodal distribution. In contrast, the nanoparticles that form
on Si (100) substrates possess more uniform diameters and are larger on average.
Additionally, the nanoparticles that form on top of the grains on polysilicon substrates
tend to be larger (~60-70 nm) and smaller particles aggregate near the grain boundaries.
The lower mode in our bimodal distribution is attributed to particles formed around the
grain boundaries, where the crystal facets are expected to vary. This is in agreement
with literature [249], in which smaller particles form on the Si (111) crystal face (25-35
nm) and larger particles (55-65 nm) form on Si (100) due to differences in surface energy.
While catalyst thickness and pretreatment time impact the resultant nanoparticle
dimensions [250, 251], these parameters were very similar in the referenced study
compared to the present experimental conditions.
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Figure 4.7: Catalyst nanoparticle arrays produced by dewetting at 850 °C in an
ammonia plasma environment on a) Si(100) and b) polysilicon. A typical particle size
of 65 nm was observed on Si (100) and at the top of polysilicon grains, and smaller
nanoparticles of approximately 25 nm diameter were observed at the polysilicon grain
boundaries.
As mentioned above, the catalyst nanoparticle diameter influences the resultant
CNT diameter as well as growth rate. Since the nanoparticle diameters are dispersed
across a range of values more so on polysilicon compared to Si (100) substrates, there is
also a dispersion of growth rate of the nanotubes catalyzed by these particles. Due to
the close proximity of CNTs to one another during the growth process, van der Waals
forces [252, 253] may cause neighboring CNTs with differing growth rates to collectively
bend and become tortuous. Since the dispersion of nanoparticle diameters is higher for
CNTs grown on polysilicon due to the variety of surface energies displayed by the
various exposed crystal faces, the tortuosity of these films is expected to be higher. CNT
films with a higher degree of tortuosity have a lower apparent film thickness, assuming
equal CNT length, due to the compression of CNT length along the vertical direction
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[254]. Therefore, an increase in tortuosity would lead to a reduction in apparent growth
rate and a reduction in diffusivity, as is observed for CNT growth on polysilicon
compared to growth on Si (100). This discrepancy would be eliminated if real CNT
length were used for kinetics calculations rather than film thickness. Additionally, from
SEM analysis (Figure 4.8), CNTs grown on polysilicon possess a much higher degree of
tortuosity compared with CNTs grown on Si (100). This may also help to explain why
the diffusivity is markedly lower for growth on polysilicon and the parabolic activation
energy is larger, as the effective growth rate disparity is reduced when taking tortuosity
into account.
Figure 4.8: (a) Si (100) and (b) poly-Si. The CNTs on poly-Si appear to display a
higher degree of tortuosity, which could explain why the diffusivity is markedly
lower for growth on polysilicon and the parabolic activation energy is larger.
4.3.4 Improving CNT Adhesion to Polysilicon
A practical requirement for the industrial viability of a packaged carbon
nanotube field emission vacuum microelectronic device (CNT FE-VMD) is the ability to
integrate a VMD platform with cathodes that can provide high current density and long
108
lifetime. There have been numerous studies [38, 255, 256] on the failure mechanisms of
stand-alone CNT field emitters, and there are several possible causes of failure.
Examples include shortening of the CNT emitter length during operation over time due
to enhanced oxidative ablation of the tube caused by local resistive heating (i.e. thermo-
mechanically activated fracture) [255, 257], degradation due to ion
irradiation/bombardment and the concurrent degradation of the CNT [160, 258], and
extraction of the CNT from the substrate due to either electrodynamic force-activated
failure or increased resistive heating at the substrate-CNT interface [255, 256]. In the
case of CNT emitters grown on MEMS polysilicon-based substrates, poor adhesion
between the CNT emitter and its substrate is the primary limiting factor for overall
device lifetime. A loss in adhesion between the emitter and the substrate will not only
render the emitter unable to contribute to the total emission current density, but it could
lead to catastrophic device failure if that emitter bridges electrically isolated components
(e.g. the cathode and the extraction grid). A common method to improve adhesion of
thin films is to use an adhesion layer between the substrate and the film, and because
CNTs nucleate from a thin film catalyst, we investigated the integration of an adhesion
layer between the polysilicon substrate and catalyst to improve adhesion of the CNT
film. Many groups have explored adhesion layers for CNT films on crystalline silicon
and metallic substrates [259-261]. Titanium and molybdenum adhesion layers were
specifically chosen based on the best literature results on crystalline silicon, and we
109
compared them to a control sample without an adhesion layer. The titanium interlayer
produced the best adhesion compared to the control and the molybdenum interlayer
samples (Fig. 9). The reflectance for the as-prepared films and the average reflectance
after each subsequent tape pull were directly compared to the other interlayer samples
by measuring against control samples for each metal interlayer without a CNT forest.
The titanium interlayer samples required approximately 2.5 times more adhesion tests to
reach saturation when compared to the control sample, whereas the molybdenum
showed only a small improvement of approximately 1.3 times more than the control
sample. It was also seen throughout all the samples tested that the titanium interlayer
samples had a final reflectance saturation point of approximately 35%, whereas the
control and molybdenum samples averaged approximately 40%. This could indicate
that more CNT emitters remain permanently adhered (i.e. have an adherence strength
larger than the removal force of the tape) after all adhesion tests were performed when
compared to the control and molybdenum samples. This data indicates that using a
titanium interlayer for CNT emitter growth on MEMS structures can offer improved
adhesion properties, which could correspond to improved device lifetime. Furthermore,
additional interactions could exist at the interface between the CNT emitter and the
polycrystalline substrate that could reduce contact resistance and improve field emission
properties of the emitter, while also reducing resistive heating at the substrate-CNT
110
interface during operation of the emitter. These interactions will be the subject of future
research.
Figure 4.9: Average reflectance from the underlying substrate as measured by

spectrophotometer for CNTs grown using various metallic interlayers. The error bars
represent standard deviation. An adhesion improvement of approximately 1.3x was
observed for Mo interlayers, and approximately 2.5x for Ti interlayers compared with
the control sample of CNTs grown on Fe-coated poly-Si.
4.4 Conclusions
Growth of CNTs on polycrystalline silicon substrates has been studied to
improve understanding of growth mechanics for applications in MEMS technology. The
kinetics of CNT growth on polysilicon was elucidated using the model of Deal and
Grove [229] to understand the activation energies and mechanisms for base-mediated
111
growth using microwave PECVD. These results were compared to CNT growth on
crystalline (100) silicon substrates, finding nucleation-stage activation energies that
match literature values for bulk carbon diffusion into austenite catalyst nanoparticles.
Parabolic diffusion-limited growth was observed on each substrate, with activation
energies for the diffusion-limited growth phase of 1.90 and 3.69 eV for growth on Si
(100) and polysilicon, respectively, in the temperature range of 825 – 875 °C. A
difference in overall diffusivity of carbon species through the growing CNT network
was found, with values of 3.5 x 10-4 cm2/s for growth on Si (100) and 7.9 x 10-5 cm2/s for
growth on polysilicon at 850 °C. In addition, deposition became diffusion limited earlier
in the growth process using polysilicon substrates. Evidence was presented in favor of a
growth mechanism involving surface diffusion of carbon species along the length of the
growing CNTs from the gas phase to the catalyst at the base of the CNT forest, but some
limited Knudsen diffusion may also occur. Possible reasons for this difference in
diffusivity and the activation energy differences were explored through analysis of the
catalyst nanoparticle dewetting process as well as subsequent changes in CNT tortuosity
and alignment, as measured by SEM. Finally, interlayer addition techniques were
presented to improve CNT adhesion to polysilicon substrates for applications as cold-
cathode field emission sources for MEMS integration.
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5. Improved Performance of Field Emission Vacuum
Microelectronic Devices for Integrated Circuits
Vacuum electronics based on thermionic emission and cold cathode emission
have been a focus of research and development for many years. It was the vacuum tube
amplifier that pioneered the use of vacuum electronics in numerous applications.
Eventually solid-state electronics consumed the market due to their improved efficiency,
versatility, and reliability when compared to the original vacuum tube. However,
vacuum electronics remained significant in select applications, specifically when high
power and high frequency were desired. As micro and nanofabrication technology
began to grow in the late 1960’s to 1980’s, so did the electronic device communities
interest in vacuum microelectronics. In addition to existing markets where vacuum
electronics already exist, there are others that could potentially benefit from high
performance and miniaturized forms of the existing vacuum technology. The feasibility
of developing reliable vacuum electronics on the micron or nano scale has continued to
grow with advances in micromachining techniques. Versatile vacuum microelectronic
devices that can serve as compliments, or even replacements, to solid-state electronics
currently face several roadblocks preventing their widespread adoption. It is these
challenges that have inspired much research in the field in the last decade.
Our research team from Duke University and RTI International, has dedicated
over a decade to the development of a novel vacuum microelectronic platform based on
MEMS technology and carbon nanotube cold cathode field emitters [109, 145-151]. The
113
platform has been explored for a variety of applications from a basic three terminal
active circuit element for integrated circuits, to a micro-ion source for mass spectrometer
and sensor development. The work presented in this chapter aims to improve the
performance of the previously investigated three terminal device. Specifically, this study
employs simulation and experiment to investigate two key concerns related to the
utilization of vacuum microelectronic devices (VMDs) in integrated circuits. Whereas
recent work in the community has shown great promise towards a device technology for
harsh environments, important issues with their performance on an integrated platform
have not been addressed. This chapter examines integrated structures to develop a
solution to device cross-talk caused by densely packing VMDs on a single substrate. This
is an important development for the realization of the integrated vacuum circuit.
Additionally, this chapter investigates another key performance concern with VMDs;
electron transmission (i.e., electron grid loss). A solution using novel designs and
operating modes to reduce grid loss by nearly 3x is demonstrated.
5.1 Introduction
The vacuum tube amplifier pioneered the communication industry and early
computing technology. However, the invention of the solid-state transistor in the late
1940’s [26], and the development of the integrated circuit in the late 1950’s [27, 28]
resulted in vacuum tubes being replaced in nearly all modern computing and related
fields. However, vacuum microelectronics, a field of science witnessing the return of
114
vacuum technology with micron-scale vacuum devices, has experienced incredible
growth recently. The development can be widely attributed to the continued
advancements in microfabrication processing technology as well as the pioneering work
of Spindt, Brodie, and many others in the 1960’s through 1990’s [7, 262, 263]. The
promising performance of vacuum microelectronic devices (VMDs) along with limited
ability of solid-state semiconductor microelectronics to perform in harsh environments,
such as severe temperatures or intense radiation, has inspired investigation of their use
in a variety of applications including: high-power/speed amplifiers and switches, field
emission displays, novel MEMS sensors, communication system components for
aviation, Hall Effect thrusters, electrodynamic tethers, traveling wave tubes, space
satellite communication and various types of radar), and finally key elements for VMD
based integrated circuits [4, 22, 122-124, 264-266]. Therefore, vacuum microelectronic
review articles are consistently published every few years capturing the essential
breakthroughs in the field [264, 267, 268]. Recently, researchers [269, 270] have even
shown that nanoscale dimension VMDs are possible.
High performance VMDs are accomplished via the integration of field emission
cathodes, often referred to as cold cathode field emitters, as well as leveraging the rising
maturity of semiconductor processing to fabricate field emission vacuum
microelectronic devices (FE-VMDs) [86, 264]. The physics of field emission in VMDs has
been described in detail previously [271]. Briefly, field emission is the process by which
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electrons are generated (i.e., emitted) via the application of an electric field between a
cathode material and an anode. This is in contrast to thermionic emitters which require
high temperatures to “boil” off electrons, thus creating the need for high input power
and inefficient operation. The use of a vacuum channel in the field emission cathode
reduces power loss and degradation of signal quality caused by electron crystal-lattice
scattering in solid state devices (SSD), whose mobility is dominated by collisions.
Therefore, these “junction-free” vacuum devices benefit from current densities greater
than 100 A/cm2, uninterrupted ballistic electron transport in a vacuum channel with a
velocity 1,000 times that of a SSD, less energy loss, and no carrier freeze-out [195, 272].
In regards to the aforementioned radiation benefits of FE-VMDs, a vacuum channel is
immune to defect generation (e.g. lattice displacement) and other ionization effects
caused by ionizing radiation and charged particles. Those two fundamental damage
mechanisms in crystalline material based microelectronics are the primary cause of
performance degradation (e.g. increased electronic noise, signal spikes, and minority
carrier depletion) and overall failure (e.g. a latchup or an ionizing dose surpassing the
devices threshold) that necessitate radiation-hardening techniques. With copious
potential benefits in circuit applications, a next logical step is to move the technology
towards integration of multiple VMDs, which others have started to explore [125, 126,
270]. However, the ability to densely pack VMDs on-chip without sacrificing individual
device or overall circuit performance, is an important concept that has not been explored
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in detail. Additionally, improving the performance of the individual VMD is also still of
concern.
Our previous work [146-150, 273, 274] presented the integration of MEMS-based
vacuum devices with a unique application of cold cathodes employing carbon nanotube
(CNT) electron field emitters to achieve a more reliable platform for FE-VMD circuits.
The devices are fabricated using the well-known PolyMUMPS [152] process, allowing
for seamless integration of three-dimensional conductive polysilicon electrode panels
that are locked in position orthogonal to the substrate for improved performance. To
date, we have investigated the development of an active vacuum circuit component
consisting of a cathode, extraction grid, and anode. The design is amenable to
integration, however, the effects of tightly packing FE-VMDs on the performance have
not previously been investigated. Furthermore, loss of current at a grid (i.e., poor
transmission properties) in a VMD is a performance concern that limits the capability of
integrated vacuum circuits. For example, devices with only 8% of the emission current
transmitting to the anode and 89% grid loss were utilized in a recent NASA and Air
Force Institute of Technology mission [275] launched in late 2013 to study carbon
nanotube emitter array efficiencies in space [130, 276]. The overall effectiveness of their
CNT electron source was limited due to most of the electrons being captured by the gate.
Our previous microtriode designs averaged approximately 75% grid loss. Improving
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transmission through the vacuum channel by reducing the loss of electrons to the grid
will improve overall device performance.
This work presents a systematic study of proximity effects and transmission
efficiency in integrated FE-VMD devices as circuit components using both experimental
data and simulations. Experimental data reveals that electron transmission in the
vacuum channel is negatively influenced by neighboring devices with crosstalk on the
order of 10-14% in the absence of isolation structures. Electrostatic field and particle
simulation software was used to design optimal structures and modified device
geometries to nearly eliminate these proximity effects. Furthermore, simulations were
used to design geometries that improved electron transmission to the working anode by
more than 3x, from 25% to 80%. Finally, the improved devices were fabricated and
tested to validate the simulation results
5.2 Experimental Methods

The FE-VMD devices consist of a series of lateral polysilicon panels, and the
fabrication has been described in detail elsewhere [146, 273, 274]. Briefly, the devices
were fabricated in a well-known polysilicon MEMS micromachining process
(PolyMUMPS®, Memscap, Inc.). Iron catalyst for CNT growth was selectively deposited
on the cathodes using integrated MEMS masks, and CNT emitters were grown in a 915
MHz microwave plasma enhanced chemical vapor deposition (PECVD). The devices
were assembled by rotating and locking the electrodes into a vertical position. Because
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the fabrication of high-performance integrated vacuum microelectronic circuits such as
logic circuits and oscillators requires that multiple active devices operate in close
proximity to eliminate internal resistances, we investigated devices separated by less
than 100 µm. A modified dual microtriode design consisting of a shared cathode panel
was fabricated to allow for two devices to be placed in close proximity on-chip. A
schematic diagram depicting the geometry layout and biasing process for this design
can be seen in Figure 5.1a; the labeled IN and OUT represent the potential inputs and
output for logic circuit realization. A SEM image of the overall fabricated device is seen
in Figure 5.1b with an inset SEM of the CNT field emitter arrays. The versatility of the
fabrication process allowed us to demonstrate the addition of new structures and
significant geometry changes without increasing fabrication complexity (e.g. additional
photolithography steps). We designed new devices to investigate methods for reducing
device crosstalk and overall transmission (i.e., reduce grid loss). Two key designs were
fabricated: 1) a dual three panel traditional microtriode with center shielding electrode,
and 2) a new dual four panel microtetrode to investigate transmission benefits and
ultimately serve as a high-performance building block for a vacuum integrated circuit.
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Figure 5.1: (a) schematic diagram of dual CNT FE-VMD illustrating the physical
layout of panel electrodes with device #1 (left) and device #2 (right), location of CNT
emitters, and the biasing method. The labeled IN’s and OUT represent the potential
inputs/output for logic circuit realization; (b) SEM image of the fabricated device with
electrode panels rotated up and locked in place as described in [147, 271]. An SEM
image of the CNT field emitter arrays as grown on the cathode are shown in the inset.
Testing was conducted in a custom vacuum chamber including twelve electrical
feedthroughs for a variety of electrode biasing options. All measurements were
performed at room temperature with a base pressure of 1 x 10-7 torr. Custom LabVIEW
software controlling a multichannel semiconductor analyzer (Keithley 4200-SCS), and
four SourceMeter instruments (Keithley 2410s), was used to electrically characterize the
devices. The charged particle simulation software SIMION® 8.2 was used to evaluate
three-dimensional models of the vacuum circuits. Those models enabled rapid and
accurate simulation of numerous geometries to optimize device designs. A feedback
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loop was implemented between simulations and experiments to improve device
performance. The CNT emitter length was controlled through our growth recipes, and
determined the distance between the cathode and the grid, thereby influencing the
emission field requirements and overall DC device characteristics. A uniform surface
emission model was chosen for the simulations in which electrons were uniformly
emitted from the surface of the CNT emitter array bundles. This best represents the
emission taking place on the device as the CNT emitter arrays, as grown, consist of a
range of protruding emission tips across the bundle face which can be seen in Figure 5.1.

5.3.1 Determination of Proximity Effects
It is important to both understand and control the electron current that is emitted
from the CNT emitters, passes through the grid, and propagates across the vacuum
channel in order to establish viable transistor performance (e.g. overall power gain, clear
cutoff, saturation regions, and transconductance). Therefore, we measured cathode
emission current (Ic) as well as the current collected by the grid (Ig) and anode (Ia) as a
function of extraction grid voltages (Vg). Measurements were repeated for several
devices to validate statistical relevance. Fowler-Nordheim emission tunneling theory
[277] predicts increasing grid voltage will result in an exponential increase in the
cathode emission current. Furthermore, there is a threshold voltage (Vth) that must be
reached in order to achieve the necessary field strength to begin electron emission. In
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addition to forward biasing the cathode and extraction grid to achieve field emission,
the anode is biased so that electrons that pass through the grid continue towards the
anode, i.e. the output of the three-terminal device. If we consider biasing all three panels
as a device in ON mode, we observed that two ON devices in close proximity had little
effect on one another. Even though there was grid loss in the devices, adequate signal
was observed at both anodes. Figure 5.2a displays current-voltage (I-V) characteristic
curves to show the overall current collected from each of the two grids and two anodes
for one of the devices tested. The visible difference in turn-on voltage is due to small
differences in CNT emitter lengths between device 1 and device 2. For all tests, the
shared cathode was grounded and potentials above the threshold voltages were applied
to the grids and anodes to generate current through both devices. The cathode was held
at ground throughout all the tests and the varying parameter was the potential on the
grids and anodes. Each grid was incremented to a value that well surpassed their
threshold voltage in order to generate substantial emission current from the
corresponding CNT emitter arrays. We typically observed sizeable grid loss during
characterization experiments of the microtriodes. This means there was more current
registering on the grid than on the anode, and this undesired performance characteristic
was the basis for the work reported in later sections. Overall, however, we observed no
concerns with the dual operating mode as both devices performed as they should with
sufficient current reaching the anodes. Additionally, if we reverse biased the cathode
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and grid for each device, turning both of them OFF, we did not measure a current at
either anode as expected.
The difficulty arises when we attempt to operate one device ON and one device
OFF as shown in Figure 5.2b. This mode should register anode current only on the
device whose cathode and grid are in forward bias conditions. We observed, however,
unintended signal in the nominally OFF device when taking I-V curves from device 1. In
this operating mode the grid of device 2 was grounded to ensure no field emission was
attained from the CNT emitters of device 2. An additional parameter was also added
into the test; the potential on the anode of nominally OFF device 2 was incremented by 1
V after each I-V sweep of device 1; 160 V was used as a stopping point for that OFF
anode. The currents measured on the grid and anode of device 1 were relatively equal
for all I-V sweeps performed. The data is plotted such that the main plot displays the
current measured on the grid and anode of the ON state device (#1). The inset displays
the current measured on the grid and anode of the nominally OFF device (#2). We
observed that even though the current registering at the grid of the nominally OFF
device (#2) was essentially zero, there is significant current being collected at the anode
of device 2. This indicates a portion of the electrons from the ON state device are being
collected at the anode of the nominally OFF device. The same experiment was repeated
in the opposite configuration (device 1 OFF and device 2 ON) with similar results. On
average, 10-15% of the electron current from the ON device reached the nominally OFF
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device’s anode. This is an undesirable outcome if we are attempting to read a low signal
(or no current) at the nominally OFF anode. Efforts to mitigate the undesired crosstalk
between densely packed devices was then explored using simulation based modeling.
Figure 5.2: Current-voltage characteristics of a dual CNT FE-VMD revealing the

undesired proximity effects; (a) both devices are operating in the ON state (0 V on the
cathode, 200 V on the anode, and extraction potentials on the grids swept) with no
adverse effects; (b) device 1 in ON state with ground potential on the cathode, 200 V
on the anode, and the extraction potential on the grid swept from 0 V to 95 V, device 2
(inset) is in the nominally OFF state with 0 V on the cathode and 0 V on the grid; the
signal observed at the anode of device 2 is due to crosstalk (i.e. current from device 1’s
emitters being pulled across the vacuum channel).
5.3.2 Simulation Guided Analysis and Redesign
The SIMION® 8.2 software package was used to confirm the source of the
observed proximity effects as well as investigate and optimize the MEMS geometry to
mitigate the problem without compromising device performance. The software
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numerically solves the Laplace equations for the given potentials; a lattice with constant
mesh size is used to approximate the derivatives by finite differences with optimized
linear time solving. The MEMS electrodes were precisely defined using geometry files
with a mesh size of two voxels per micron to allow for extraction of the electric fields
and potentials at all points around the electrodes. Therefore we were able to
systematically model the electric potential distributions and electron trajectories around
each MEMS structure, and plot trajectories visibly and numerically to reveal all electron
paths in the device. Initial models were created to replicate the exact geometries and
potentials in the dual device setup. Support structures are included in the simulations to
establish realistic conditions as these structures have an impact on electron trajectories.
The simulation results given in Figure 5.3 provide insight as to why we measured
current on the nominally OFF device’s anode (Figure 5.3). The cathode, extraction grid,
and anode panels, being only 2 microns thick, are very thin in comparison to the support
structures and therefore have been accentuated with black lines in Figure 5.3 and Figure
5.4. The electric fields concentrated around the structures of the nominally OFF device
penetrate into the vacuum channel of the ON device altering the electron trajectories; the
electrons are therefore attracted towards and collected at the anode of the nominally
OFF device as shown in Figure 5.3. A portion of the red colored electrons (current from
the ON device) can be seen being pulled and collected at the nominally OFF device,
whereas we clearly observe all of the blue colored electrons (current from the nominally
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OFF device) are stopped by the grid of the nominally OFF device and are not
contributing to the current at the nominally OFF device’s anode. The simulation results
confirm the experimental data observed from earlier dual device tests; undesired anode
current magnitudes (i.e., the amount of current reaching the nominally OFF device’s
anode) were approximately 10-15% of the total CNT electron emission current in both
the experimental and simulation results.
Figure 5.3: A schematic diagram illustrating the potentials on each electrode and the
SIMION® simulation demonstrating the proximity effects experienced by the dual
CNT FE-VMD; (a) device 1 is biased for field emission (ON state) and device 2’s grid
is grounded, rendering it in a nominally OFF state; (b) simulation results show that
even though device 2 is OFF, its anode is receiving 10-15% of the electron current
from device 1 (similar to experimental results) resulting in an undesired ON state
signal at anode 2.
SIMION® was further employed to investigate additional geometry designs,
placement, and operating potentials to mitigate the crosstalk between devices without
adding significant complexity to the device. Simulations revealed that a dividing strip or
“shielding electrode” on the substrate produced sufficient isolation, or shielding, to the
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vacuum channels of neighboring devices. Simulation-based optimization was employed
to determine thickness, spacing, and operating potential that eliminated proximity
effects without interfering with the particle trajectories of the active devices. Figure 5.4
summarizes the effect of the shielding electrode. Figure 5.4a shows a scenario with one
ON and one nominally OFF device and the shielding electrode voltage off. Here we
recreate the crosstalk effects as seen in the previous design. Figure 5.4b uses the same
simulation parameters except with the shielding electrode grounded, thereby isolating
the vacuum channels of each device and eliminating the undesired current on the anode
of the nominally OFF device. A floor based electrode is simple in design and does not
add complexity during assembly; it is easily fabricated alongside the existing structures
during the MEMS process steps. The proposed redesigns were fabricated and tested
experimentally to validate the simulation results.
Figure 5.4: SIMION® simulation modeling with optimized center shielding electrode
to eliminate the crosstalk between neighboring devices; (a) two proximal devices with
the shielding electrode off and crosstalk taking place from the ON device 1 (left) to
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the OFF device 2 (right); (b) same design with the shielding electrode grounded,
effectively shielding the devices and their corresponding vacuum channels from one
another. Operating the shielding electrode at ground potential provided the best
shielding without interfering with individual device performance.
5.3.3 Simulation for Electron Transmission Analysis and Redesign
As mentioned previously, prior work has reported sizeable grid loss in the
MEMS microtriodes. Because electron field emission from the cathode is directly
coupled to the voltage on the grid, we inevitably cannot use the grid to focus the
electron beam which results in poor electron transmission to the anode. Therefore
devices must be operated at larger emission currents to compensate, resulting in more
mechanical and electrical stress on the device, as well as higher power requirements.
Furthermore, coupling of the grid and cathode gives rise to poor transconductance, an
undesirable quality for designing high-performance integrated circuits. To date the best
measured transconductance for the MEMS microtriode is 2 µs [198]. SIMION® was
again used to investigate methods for improving the overall electron transmission
through the device. By adding additional polysilicon electrodes to optimally shape the
equipotential curves in the vacuum channel and around the device, we reduced the
angular and energy dispersion of the emitted electrons, thus improving the collimations
of the electron beam. The geometries from the original microtriode produced an average
transmission (i.e. electrons moving from the cathode, through the grid, and to the
anode) of 25% [147, 273] which we replicated in SIMION® simulations. Figure 5.5
shows the large number of electrons lost at the grid and not transmitting to the anode.
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SIMION® was used to determine the number, spacings, and potentials on the added
electrodes to optimize transmission. With the added electrodes, we were able to mimic
the effect of a Wehnelt cylinder lens used in electron optics [278]. The screening and
extraction electrodes were designed to create a pre-lens electric field effect around the
CNT emitter bundles to dramatically enhance the focusing properties of the electron
beam by 3x. The 25% grid transmission efficiency of the old geometries was improved to
80% with these new designs. The simulation results can be seen in Figure 5.5. The pre-
lens effect around the CNT emitters is seen by plotting the equipotential curves between
the electrodes (Figure 5.5b). The pre-lens effect is further supported by the flat
equipotential curves on the back side of the screening grid which significantly reduces
angular dispersion, resulting in improved beam focusing (Figure 5.5c). Another benefit
to this design is that we have now decoupled the extraction grid from the cathode.
Additional simulations have revealed that the electron beam emitted from the CNTs can
be left in constant emission mode and fully retarded via small changes in the screening
electrode voltage, similar to tetrode-style vacuum tubes. This can lead to improved
device transconductance, and these experiments will be the focus of future work.
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Figure 5.5: SIMION® simulation modeling of electron transmission properties of the
CNT FE-VMDs; (a) Simulated electron trajectories in the original microtriode device
with an average transmission of 25% (electrons passing through grid and collecting at
anode); (b) simulation showing equipotential lines of new geometry designed to
create pre-lens effect around CNT emitter bundles thereby enhancing focusing
properties; (c) simulated electron trajectories of new geometry showing an increased
grid transmission of 80%.
5.3.4 Experimental Confirmation
The simulations were verified experimentally with devices including the
shielding electrode and devices including the additional electrodes for improved
focusing. A schematic diagram depicting the geometry layout and biasing process for
the microtetrode design can be seen in Figure 5.6a; the labeled IN’s and OUT’s represent
the new potential inputs and output for logic circuit realization. An SEM image of the
newly fabricated microtetrode containing the center shielding electrode can be seen in
Figure 5.6b. The redesigned microtriodes with the center shielding electrode (not
shown) are similar just without the addition of the extra grid.
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Figure 5.6: (a) schematic diagram illustrating new physical layout of panel electrodes
with device #1 (left) and device #2 (right), location of CNT emitters, biasing method,
and new potential inputs/outputs for logic circuit realization with decoupled cathode
and extraction grid; (b) SEM image of redesigned fabricated device with electrode
panels rotated up and locked in place and center shielding electrode flat on the
substrate between the devices.
In order to compare and validate improvements of the dual microtriode device,
initial tests were performed with the center shielding electrode off to mimic the original
devices. Again, crosstalk was observed in similar percentages (10-15%), the results from
a device can be seen in Figure 5.7a. Again, the main plot displays the currents collected
at the grid and anode of the ON device, and the inset displays the currents collected at
the gird and anode of the nominally OFF device. Results show current collected at the
OFF anode without current at the OFF grid. The tests were repeated with a ground
potential applied to the shielding electrode and the current collected at the anode of the
nominally OFF device was observed to decrease from the 15% to 1-2% on average. This
is an order of magnitude decrease is crosstalk current. The results of the significantly
reduced anode current at the nominally OFF device are plotted in Figure 5.7b. These
results show a grounded center electrode properly isolate the vacuum channels.
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Figure 5.7: Center shielding electrode effect on proximity effects. Left device is ON
and the right device is OFF; (a) with shielding electrode grounded, crosstalk current
on the order of 10-15% is measured at the anode of the OFF device; (b) with the
shielding electrode electrically grounded the crosstalk current measured at the anode
of the OFF device is decreased by an order of magnitude (1-2% on average).
Potential transmission benefits were investigated using one side of the dual
microtetrode design. The current reaching the anode was approximately 2.6 to 2.8 times
more than in the microtriode device. Transmission values of 65-70% on average were
measured. Figure 5.8 compares the results from an old microtriode device to a new
microtetrode. Figure 5.8a shows most of the current being intercepted by the grid in the
old microtriode design with an average of 25% of the emitted current reaching the
anode. Figure 5.8b shows much less grid loss in the new 4 panel microtetrode design
with 65-70% of emitted current reaching the anode. The failure to reach the 80%
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transmission predicted by the simulation may be due to small misalignment between the
CNT emitters and the grid holes.
Figure 5.8: (a) original 3-panel microtriode operated with cathode = 0V, extraction grid
swept (0-140 V), and anode = 150 V. Pie chart inset shows average distribution of
emitted current at maximum extraction potential (25% reached the anode, 58%
intercepted by the grid, and 17% lost); (b) 4-panel geometry driven in the new
operating mode with cathode = 0V, screening electrode = 20 V, extraction grid swept
(0-125 V), and anode = 150 V. On average, 67% of the current reached the anode, 23%
was intercepted by the grid, and 10% was lost.
5.4 Conclusion
Densely packed FE-VMDs using a novel MEMS and CNT emitter based platform
were fabricated and tested. Undesired proximity effects in the form of current crosstalk
between devices caused by the biasing potentials required for single device operation
was observed. On average, 10-15% of the emission current from one device is
inadvertently collected by the nominally OFF device. It was determined these proximity
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effects could not be neglected in the operation of high-performance vacuum
microelectronic device circuits. Simulation modeling was used to understand the root
cause, design structural solutions, and improve overall device performance by methods
that could be easily integrated into the device fabrication process. Simulation modeling
was also used to investigate the reduction of grid loss and improve the overall
transmission of electrons from the cathode to the anode from 25% to 80%, an important
parameter improving power gain in the key active vacuum circuit component. This
improvement was achieved by adding an additional electrode panel that decoupled the
cathode and grid and improved the focusing of the emitted electrons. Finally, devices
were fabricated and tested to validate the simulations. The crosstalk mitigation structure
effectively reduced current crosstalk by an order of magnitude from 10-15% to 1-2% on
average. For transmission improvements, experimental data revealed an increase in
transmission from 25% to 65-70% on average. The additional understanding gained from
this work, combined with the improved device performance, will help to advance the
level of circuit integration and scalability of VMDs.
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6. Low Temperature Co-fired Ceramic Packaged MEMS
Micro-ion Source for Miniature Mass Spectrometry
Applications
In chapter four, the interface between CNT electron emitters and MEMS platforms
was investigated and improved. Chapter five utilized this knowledge and improved
active circuit elements from the CNT field emission MEMS devices. The device can also
be utilized as an ion source in mass spectrometry. This has been demonstrated by
generating and collecting ion current on-chip using integrated panel electrodes [147, 150,
151]. While this was a successful proof of concept, it is limited in its application due to
large energy and angular dispersion of the ions and the limited ability to direct the ions
to a mass analyzer. If CNT FE-MEMS devices are to be realized as practical components
in miniaturized mass spectrometer development, these concerns must be addressed.
Thus, this chapter investigates improving the technology through a redesign of device
geometry and the introduction of new operating modes to achieve orthogonal ejection of
ions relative to the source, thus allowing them to be directed into a mass analyzer.
Additionally, this chapter introduces the development of a novel packaging solution
that provides a 3D scaffold for the MEMS micro-ion source, as well as integrated
apertures needed for ion focusing and spatial filtering.
Device improvements and redesign were accomplished through extensive
parametric characterization, simulation of new design concepts, and failure analysis of
existing devices and test structures to determine performance limiting elements. The
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development involved three key areas: mechanical, electrical, and materials. The
mechanical properties investigated structural integrity of the panel electrodes during
operation, locking mechanisms and latch configuration, hinging mechanisms, alignment
of electrodes, and contamination during materials integration (i.e., during CNT growth).
The electrical studies investigated the current carrying capacity of all structures,
operating modes, failure by electrostatic discharge and the electrical overstress
susceptibility of the MEMS structures, electric field edge-gradient effects, and current-
voltage characteristics. Finally, the materials, or more specifically, the nanomaterials
properties that were investigated, focused primarily on the CNT emitters and methods
to improve their performance within the device. This included array size and placement,
as well as control over the length of the CNT emitters between cathode and grid. The
spacing between CNT tip and grid establishes the field for electron emission, therefore
CNT length correlates directly to the potentials required to operate at a specific current.
Failure analysis (FA) was conducted and mitigation techniques were proposed,
evaluated, and implemented in new designs.
Novel packaging for the MEMS micro-ion source was realized by utilizing low
temperature cofired ceramic (LTCC). Layer by layer fabrication allows for placement of
required bonding pads, electrical traces, and connector pads in order to house the
source, apertures, and micro-connectors. Design considerations centered on assisting ion
current extraction from the micro-ion source, as well as focusing of the ions through a
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spatial filter based on coded apertures [279, 280]. Gas inlet and exhaust ports were
integrated into the LTCC to allow for delivery of analytes to the ion source. Simulations
of micro-ion source operation within the package, as well as fabrication techniques and
assembly methods are discussed in this chapter.
6.1 Introduction
Miniature mass spectrometers have a plethora of potential applications in
environmental monitoring, security and defense, point of care medicine, and space
exploration. The ion source, a critical component in any mass spectrometer, has been
developed in a variety of classes including electron ionization, chemical ionization,
electrospray ionization, field ionization, fast atom bombardment, photoionization, and
laser desorption/ionization. The use of microelectromechanical systems (MEMS)
components in mass spectrometer miniaturization is particularly attractive due to their
small size and scalability [281, 282]. MEMS have been investigated for use in several
subcomponents from ion sources [283-288], to mass analyzers [289-295] and detectors
[296-300]. The MEMS fabrication process combines micron scale lithography and thin-
film deposition methods to consistently outperform conventional machining of small-
scale geometries. MEMS provide a path towards wafer-scale full system development.
Carbon nanotubes (CNTs) have attracted much attention as a high-performance
electron field emission source [301-303]. They offer several benefits over traditional
thermionic filament emitters in terms of power use, lifetime, and current density [304].
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Additionally, Low Temperature Cofired Ceramic (LTCC), a technology used to package
integrated circuits in multichip ceramic modules for nearly 20 years, has been
recognized as one of the most significant recent developments for packaging and
integrating sensors and microelectronics [305, 306]. LTCC materials have been used to
construct ion mobility spectrometers [307] and arrays of ion trap mass analyzers [308], as
well as for packaging solutions for a variety of microelectronic devices [309-311].
Our group has pioneered the development of miniature electron ionization
sources and VMDs combining the versatile Polysilicon Multi-User MEMS Processes
(PolyMUMPs) with integrated CNT cold-cathode field emitters [146-150, 198, 273, 274].
To date, ion currents have been measured on-chip using integrated MEMS ion collectors
for various analytes over a wide pressure range [147, 149]. However, until now they
have been of limited use due to both large energy and angular dispersion and limited
ability to direct the ions to a mass analyzer. Fabrication of an ion source that provides
better control over electron energies and their corresponding ionization cross-sections,
as well as improved focusing properties of electron and ion trajectories, would allow
further development and integration of the current MEMS ion source platform in a
complete MS instrument. The development of a scalable, non-restrictive packaging
solution that could integrate the ion source with the necessary apertures to move ion
collection off-chip, would allow for a drop-in source solution for miniaturized
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instruments. Together, the integration of the microfabricated ion source and package
would be of both scientific and technological importance.
To address the limitations of current miniature ion sources, this chapter discusses
the development of a Nier type electron ionization source [156, 312] combining a MEMS
chip and integrated field emission cathode with a low-temperature cofired ceramic
(LTCC). The LTCC provides a 3D substrate and ion optics for the MEMS device. The
new MEMS geometry, field emission cathode, and LTCC scaffold together create a fully
packaged miniature ionization source. In the ion source design, the MEMS chip contains
the CNT electron source, grid, repeller, and anode, while the LTCC provides a scaffold
for making electrical connections to the MEMS chip as well as positioning the extraction
aperture, spatial filter, and sample inlet. The ion source focuses ions formed at the
MEMS substrate vertically and uses electrode structures to minimize undesired energy
and angular dispersion. In the following sections we detail the design and simulation,
fabrication, and experimental characterization of this new miniature ion source.
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Figure 6.1: Schematic diagram of a Nier-type geometry ion source.
6.2 Design and simulation

6.2.1 Components of a Nier-type Ion Source
A traditional Nier-type ion source (Figure 6.1) is composed of various electrodes
including electron beam inlet, an electron source (or cathode and grid), anode, extraction
aperture, and repeller arranged in a cubical geometry. The potential on each electrode
and geometry of the electrode is chosen to direct ions through the extraction aperture
towards the spatial filter with minimal energy and angular dispersion. Ion trajectories
along a non-uniform equipotential surface and through a non-uniform equipotential
volume results in an undesired spread in energy of the ejected ions. Uniform electric
fields in an ion source that introduces minimal deviation from as-formed m/z ions leads
to reduced distortions in peak shape and loss of resolution [153, 183]. Therefore,
electrode placement and operating potential arrangements are especially important in
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order to achieve a uniform and parallel field across the ionization volume. For
miniaturized sources, where the ions are created in a smaller volume resulting in shorter
trajectory path lengths, this is especially important.
Proper placement of extraction apertures and electrical connections are equally
important to control electric fields, ion trajectories, and injection and ejection efficiencies.
Several additional apertures can be added after the extraction aperture to collimate the
ion beam. A spatial filter is typically placed at the exit of the ion source and entrance of
the mass analyzer, and the sample inlet is a small hole in the ionization volume.
Typically the ionization volume is constructed using metal plates for the electrodes
separated by insulating spacers. The electrical connections are made by attaching wires
to the various electrodes. The conventional method of constructing the ion source and
ionization volume described above is adequate for large instruments; however, when
miniaturizing, it becomes prohibitively difficult to assemble and electrically connect the
various electrodes.
6.2.2 High Performance Ion Source Characteristics
A high performance ion source has two main characteristics. First, the ions are
created over a small potential difference. This results in an ion beam with a small energy
dispersion. Second, electrodes should be positioned such that the equipotential lines are
as parallel to the substrate as possible. This results in minimized angular dispersion.
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6.2.2.1 Ionization Volume Impact on Resolution
The 1st important characteristic is energy distribution of ions. The goal of the ion
source is to create ions that can travel through the mass analyzer and onto a detector.
The mass analyzer provides the resolving power of the instrument; and the resolution
depends inversely on the dispersion at the analyzer outlet [312]. Since analyzers separate
ions based on mass + charge, a broader range of energies will lead to broader “peaks” in
the analyzer, thus a narrow range is better. This is very important to both mass
resolution and accuracy. Therefore, reducing the energy and angular dispersion at the
source will assist in achieving the best resolution at the mass analyzer output. Energy
dispersion is dictated by the properties and efficiency of the ionization volume. Ideal
performance, i.e., low energy dispersion, dictates that the ions are created in a volume
with a small potential gradient [312], or zero electric field ideally as illustrated in the
schematic of Figure 6.2a. The volume between the grid electrodes and floor, which
constitutes the ionization region, must remain small such that the ions need only to
cover a very short distance. The small potential gradient minimizes energy dispersion. If
the potential gradient of the ionization region is large, the ions are accelerated to varying
kinetic energies and therefore will not follow the same trajectories through the magnetic
fields [312]. By utilizing microstructures, the ionization volume can be designed such
that the potential gradient is very small.
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6.2.2.2 Parallel Equipotential Surfaces
The 2nd important characteristic the angular dispersion, or the diverging velocity
properties of the ions. Angular dispersion is dictated by the electric field and the
trajectory the ions take through that field. For the analyzer, all ions should be traveling
in the same direction, or collimated, to improve resolution and accuracy as seen in the
schematic of Figure 6.2b. The equipotential field lines are shaped by the electrodes and
the extraction apertures in the source. The electric fields will guide the ions throughout
the volume. To minimize angular dispersion, ions should move along a path of parallel
equipotential field lines (Figure 6.2b), in respect to the substrate, as they move towards
the mass analyzer. Any divergence imparted onto them from non-parallel field lines
could increase once they are inside the mass analyzer, resulting in large angular
dispersion and lower resolution. In order to improve collimation of the ion beam, and
reduce angular dispersion, the electric field can be engineered in such a way to focus the
ions towards the apertures.
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Figure 6.2: schematic showing the two important characteristics of a high performance
ion source; (a) ions should be formed in a region of small potential difference, or zero
electric field, in order to reduce energy dispersion; (b) the equipotential field lines
above the ionization region should be flat in order to minimize angular dispersion.
6.2.3 Proposed Solution
Each component of the packaged miniature ion source was evaluated and
designed to minimize dispersion by maintaining a small ionization volume and parallel
equipotential surfaces, with respect to the substrate, throughout the device. The
structures considered were as follows: cathodes, grids, ion repeller (i.e., floor), latches,
extraction aperture, spatial filter, sample inlet, and electrical connections/traces.
6.2.3.1 MEMS
Cathode and Grid. The cathode and grid are the primary contributors to the
electric fields that enable field emission from the CNT emitters. The absence of thermal
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load present in a thermionic emission source means that the grid can be placed close to
the cathode, reducing the voltage required to achieve the electric fields necessary for
electron emission. Previously, we have investigated ion source performance with a
triode arrangement consisting of a cathode, grid, and anode. For this design, the anode
was eliminated and an additional cathode/grid pair was placed in its location. Starting
from the left side of the chip, the electrodes moving left to right now consist of a
cathode, grid, floor, another grid, and the final cathode. Having two symmetric
cathode/grid pairs as seen from the center of the device looking out, creates relatively
parallel and equal equipotential field lines across the device. However, in standard
operating mode, the cathode is held at a negative potential with respect to the grid. This
creates a strong negative field on the order of tens of volts that distorts the parallel
equipotential field lines in the ionization region. Therefore, the grids were designed to
be taller than the cathode to shield the negative fields from penetrating the ionization
volume.
Repeller (i.e. Floor). In traditional Nier-type sources, a repeller electrode is fixed
within the ionization region in order to direct ions and move them towards the mass
filter [153]. In order to accomplish similar goals, we utilized the MEMS process to
fabricate a floor electrode on the substrate. This floor electrode, located beneath the
ionization region, completes the cuboidal ionization volume and, along with the
extraction aperture, directs ions orthogonally away from the substrate in the z-direction.
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This is similar to previous work with the MEMS micro-ion source where ions were
pulled towards side panels fabricated on chip where ion current was collected and
measured [149, 151]. However, the change here is the direction (off-chip instead of
remaining on-chip) and the distance the ions travel (hundreds of microns instead of
10’s). The H-shape of the repeller electrode is important to maintain field uniformity for
ion extraction. Without the proposed shape, the potentials from the cathodes, grids, and
supporting structures dominate the far field boundary conditions and negatively impact
the ion trajectories. The H-shape minimizes the impact of other electrodes that would
otherwise reduce performance. Together with both grids, a symmetric cuboid-like
ionization space is created. The vertical extraction approach allows for placement of
required apertures parallel, and above, the substrate; thus creating a vertically stacked
device above the symmetric ionization region.
6.2.3.2 LTCC
Utilizing a multilayer LTCC package option allows for placement of the MEMS
chip in the desired location, as well as the placement of extraction and focusing
apertures at controlled distances from the substrate to enhance uniformity in ion
extraction, creating an ideal ionization volume. Several sets of LTCC layers containing
cavities, vias, and electrodes for electrical connections were used. The combined layers
form a 3D scaffold for assembly of the electron source, ionization volume, sample inlet,
and ion optics. 3D CAD design software SOLIDWORKS® was used to design the LTCC
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parts for the ion source package. LTCC starts as a semi-flexible substrate called tape.
Vias can be punched, conductive material screen printed, and patterns can be cut.
Various numbers of layers can be stacked and cavities created where layers have
different cut patterns. Cavities were cut in some of the layers to hold the electron source,
ionization volume, collimation optics, spatial filter, and sample inlet. Electrodes were
screen printed using gold, and vias were punched and filled to enable electrical
connection to the electron source, ionization volume, collimation optics, and spatial
filter. Fabrication and firing of the LTCC layers utilizing the ion source package designs
were completed by DuPont USA and OMEGA Micro Tech. The extraction apertures and
spatial filter (coded apertures) that were inserted and electrically connected to the LTCC
were machined by National Aperture, Inc.
Extraction Aperture. In order to assist the ion movement into the mass filter, an
extraction aperture was also considered. Using a negative potential on an extraction
aperture allows positive ions to gain kinetic energy and follow trajectories off-chip in the
z-direction. If a large hole was used as an extraction aperture, the parallel equipotential
field lines in the ionization region would be distorted and would increase dispersion of
the ions. To minimize increasing the energy or angular dispersion of the ions, the
extraction aperture was designed with large open area, using small bar widths at a large
pitch. This resulted in flat field lines around the aperture.
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Spatial Filter. In order to allow miniaturization without a commensurate
decrease in performance, aperture coding was integrated into the design of the ion
source. Aperture coding breaks the historical trade-off between throughput and
resolution and enable smaller volumes of miniature instruments to maintain the
throughput of a much larger instruments. It has been described for mass spectrometry
in detail previously [280]. Throughput gains of more than 10x with no loss in resolution
over conventional slits have been reported in magnetic sector mass spectrometry [279].
Sample Inlet. An important component in a mass spectrometer instrument is the
inlet system which allows the analyte of interest to enter the ionization source. The inlet
system can be as simple as a port through which the sample is injected or drawn due to
a pressure differential. A port was integrated into the LTCC by patterning cavities in
each of the corresponding layers. Pumping speed and range was considered when
designing an appropriate port to facilitate proper delivery of the sample to the
ionization source.
Electrical Connections. The connections to the ion source, and its corresponding
electrode panels, is an important part of the system. They are integrated onto the LTCC
using screen printed gold and wire bonds were used to connect from the LTCC to the
MEMS. All electrical traces contribute to the electric field gradients in the system and
must be considered in order to avoid adverse effects on the ion trajectory. Because the
desired path of the ions is in the vertical z-direction, electrical connections were also
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designed to be equal on all sides of the device, thereby minimizing distortions to the
parallel equipotential field lines. Connections from wires to the electrode traces on the
substrate was done through wire bonding, which also has an effect on the fields as the
wire bonds are large relative to the other components on the micro-ion source.
Therefore, designs extended the metal traces far away from the ionization region. This
allowed bonding to be done far enough away so as to have no observable effect on the
ion trajectories.
6.3 Design Details

6.3.1 MEMS
The MEMS micro-ion source utilized in this work is derived from previously
reported sources [109, 146, 147, 149, 151, 273, 274]; therefore, the fabrication process is
similar. Briefly, the devices were fabricated with a well-known polysilicon MEMS
micromachining process (PolyMUMPS®, MEMSCAP, Inc.). Iron catalyst for CNT
growth was selectively deposited on the cathode substrate using integrated MEMS
masks, and CNT emitters were then grown on the substrate in a 915 MHz microwave
plasma enhanced chemical vapor deposition. The devices were assembled by rotating
and locking the electrodes into a vertical position. The charged particle simulation
software SIMION® 8.2 was used for modeling, evaluating, and redesigning the micro-
ion source. Design considerations were separated by component. A 2D schematic of the
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redesigned MEMS micro-ion source and legend providing component identifiers is
given in Figure 6.4a.
6.3.1.1 Observed Failure Mechanisms and Mitigation Techniques
Micro-ion sources were originally designed with MEMS springs that served two
purposes: electrical contact (i.e. current carrier) from bond pad to electrode panel, and
restoring force for vertical alignment of panel. A common failure point observed was
overheating and damage to the spring or spring contacts due to overcurrent as can be
seen in Figure 6.3a. This occurred as a result of the joule heating of the polysilicon
springs, which is resistive in comparison to a metal. This failure mechanism was
observed in two situations: 1) devices were operating around 150 µA according to
device statistics, and 2) a temporary direct short was made between the cathode and
grid or grid and anode electrodes. The latter is caused by high fields between the
cathode and grid, resulting in the snapping together of panels in Figure 6.3b.
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Figure 6.3: SEM failure analysis of microtriodes; (a) spring failure due to overcurrent,
(b) panel snapping from high fields or mechanical failure, (c) loss of CNT adhesion
and cathode-grid shorting, (d) latch failure with panel snapping.
Direct shorts were also observed due to CNT emitters that extended across the
extraction region between the cathode and grid Figure 6.3c. High fields, as well as CNT
damaging effects discussed earlier, can result in loss of adhesion between the emitter
and MEMS cathode. In the event of panel overextension, such as the case with panel
snapping, structural integrity of the latches would fail as is seen in Figure 6.3d. Often
temporary voltage spikes occurred, as is the case with current controlled voltage lifetime
testing, which resulted in momentary snapping of the panels. The period in which
panels were touching in this case was too short for overcurrent and burning of the
spring to occur, however, latch failure resulted in panels falling and rendering the
device destroyed.
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It has been observed [313] that grain boundary size and dopant atoms effects
phonon scattering and therefore thermal conductivity. In heavily doped thin films on
the order a few microns, which is the case with our devices 2 µm MEMS polysilicon,
smaller grain sizes are present due to shortened annealing times for dopant activation
[314]. These grain sizes, along with increased phonon scattering sites due to phosphorus
dopants, lowers the thermal conductivity of the polysilicon leading to variability and
poor tolerance to transient overloading. Furthermore, it is well known that contact
resistance between two MEMS layers is large due to band alignment and mobility
change at the junction. Calculated values from run data provided by MEMSCAP
foundry is 3060 Ω/μ2 for poly0-poly1, 3150 Ω/μ2 for poly0-poly2, and 1530 Ω/μ2 for
poly1-poly2. We believe this explains the structural failures. Using sheet resistance and
additional run data attained from MEMSCAP, and 1st principle calculations based on
standard resistivity equations, structures were redesigned to larger dimensions and
have been tested to currents as high as 250 µA without failure. Latches were also
modified to improve mechanical stability and serve as current carrying structures in
order to remove the springs from the devices all together. The curved latches act as a
bent spring with a specific spring tension. Primary forces considered in the redesign
include the spring tension, electrostatics, and friction as gravity and weight are not
substantial. The spring tension was increased by making the legs thicker and by
doubling the thickness by adding a second poly layer through the use of poly1-poly2 via
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etching layers. Latch legs were designed to be effective current carrying conductors and
an additional bond pad connection path was added thus supplying two electrical
contacts to each electrode panel. This divides the current between structures and
provides a backup conductor in the event the spring fails. For structural redesign,
theoretical calculations were conducted to approximate specifications. Then, a series of
simple test structures were designed, fabricated, and tested before being permanently
included in subsequent runs.
A failure mechanism related to the device as a whole was observed and was
associated to device shorting due to the existence of a thin conductive film on the
surface. It was detected using I-V characterization combined with SEM analysis and 4-
point probe testing. Devices that visually appeared ok would occasionally experience
shorting between electrodes. SEM analysis would confirm that panels were not in
contact, and often reveal the existence of a thin film on device surfaces. 4-point probe
would confirm the existence of a conducting film that was not desired. It was
determined the film was of organic nature and most certainly a thin carbon film that was
deposited during growth on the device surface. A process using a matrix plasma asher
and a short duration, low power O2 plasma was developed to remove the film, and
restore open circuit function, while not harming the CNT field emitters.
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6.3.1.2 Cathode and Grid
The cathode panels were fabricated with a height of 55 microns and a width of
460 microns. The CNT emitters were grown in a 2x16 array of 5x5 micron bundles as
shown in Figure 6.4b. The width of the CNT regions were 360 microns. The CNT arrays
were patterned this way to create a flat and wide electron beam for ion generation. The
small variance in height is such that ions are created on approximately the same plane
above and parallel to the substrate. The grids were placed 40 microns away from the
cathodes and oriented such that the CNT emitter bundles were center aligned with the
grid holes as seen in Figure 6.4c. The designed height of the grid was 90 microns and the
width was 735 microns. The symmetric cathode and grid pair were spaced 300 microns
apart and parallel to each other to create, in conjunction with the floor, a cuboid
ionization region. The cathodes have a thickness (polycrystalline silicon film thickness)
of 2 microns. The grids also have a thickness of 2 microns.
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Figure 6.4: (a) Top-down schematic of new micro ion source; (b) SEM of fully
assembled symmetric micro ion source; CNT field emitters (inset) are synthesized to
specific lengths directly on cathode prior to assembly; (c) SEM image of precise
alignment between CNT emitter bundles and grid holes; (d) SEM image showing
thicker latch arms (current carriers) and improved electrical contact point.
6.3.1.3 Repeller (i.e., Floor)
The repeller (floor) electrode was designed to be 160 microns wide, 800 microns
in length, and spaced 60 microns away from each grid to allow for adequate spacing and
avoid any shorts between electrodes. The geometry and placement of the floor electrode
is an important consideration in order to best shape the equipotential surfaces seen by
the ions along their path from the substrate to the extraction aperture. The floor is held
at a similar potential as the grids to create the cuboid ionization volume at the center of
the device. Because the floor must be biased, it needs an electrical trace connecting it to a
bond pad. However, extending a trace down one side only would distort the symmetry
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in the device. So the floor was extended down each side of the chip to maintain
symmetry and balance the equipotential surfaces; shown in Figure 6.4a. The
polycrystalline silicon floor has a thickness of 1.5 microns, slightly thinner than the panel
electrodes as it is fabricated in a separate processing step in the MEMS fabrication.
6.3.1.4 Wire Bonding Pads
The device requires biasing to operate, and therefore gold wire bonding is
required for all MEMS micro-ion sources. Because each electrode is independent from
one another, multiple wire bonding pads are included on chip. However, due to the
micron scale of the device, the thin bond wires still have an impact on the fields
surrounding the device due to their comparatively large size. Therefore, the pads were
spaced out far from the device using electrical traces as shown in Figure 6.4b. All traces
were fabricated directly in the MEMS fabrication with no additional processing steps.
The wire bonding electrodes were nominally1 1 mm in length and 150 microns wide.
Wire bonds were attached at the outermost edge of the electrodes to minimize their
impact on the equipotential field lines.
6.3.1.5 Latches
The latches, also fabricated using MEMS poly-Si layers, have two roles in the ion
source. The first is to supply a mechanical locking mechanism to hold the panel vertical.
1nominally is used to indicate that the dimensions are the designs dimensions of the device and do not
account for minor processing errors in the dimensions.
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The second is to bias the panels which is accomplished at the electrical contact point as
seen in Figure 6.4d. The latch arms serve as the current carriers and therefore must
withstand the total electrode current to avoid failure and breakage due to overcurrent.
The latches geometrical dimensions were designed to accommodate well over the
maximum current requirements of the device (approx. 150 micro amps). Test structures
were fabricated and used to validate the current carrying ability of the structures.
6.3.2 LTCC
Design of the LTCC package was accomplished by evaluating each of the
integrated components individually. Each component was simulated at multiple stages
in the design. Two iterations (i.e., generations) of the LTCC designs were fabricated and
evaluated. Design changes were made after experimental experience was gained on the
first generation.
6.3.2.1 LTCC Layer Specifics
Figure 6.5a shows an exploded view of the 1st generation of the LTCC scaffold.
The “MEMS device” reference indicates the location where the MEMS chip, and the
heart of the ionization volume, is bonded into the LTCC using epoxy. The assembly is
comprised of 4 LTCC layers; each layer is comprised of 5 pieces of LTCC tape, or
sublayers.
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Figure 6.5: (a) Exported CAD image showing exploded view of the LTCC layers with
labels indicating various components, (b) cutaway view of the assembled LTCC
package.
The first layer includes electrical connections and vias to the additional layers as well as
a cavity for the MEMS device and a channel for sample outlet. The second layer includes
a cavity for the ionization volume as well as a larger cavity which exposes screen printed
electrical traces where electrical connection can be made to the ionization volume and
electron source. The third layer includes a cavity to enclose the electrical connections in
the ionization volume and electron source. The third layer also contain a smaller cavity
as well as a screen printed trace for electrical connection to an extraction aperture. In this
design, the extraction aperture is a single layer of metallized LTCC with a small hole cut
in it. The area around and inside the hole is covered with screen printed conductor. The
third layer also includes a cavity for the sample inlet. The fourth layer contains the
cavity where the spatial filter (i.e., coded aperture) is placed, along with electrical traces
to bias it. In this 1st generation, the spatial filter is a metal plate with a series of holes,
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placed over a cavity in the LTCC slightly smaller than the metal plate. Figure 6.5b (right)
shows a cutaway view of the fully assembled scaffold with device inside. Not shown in
the CAD image is gold that was deposited on as much of the surface as possible to
shield the mass analyzer from the electric fields inside the packaged device. Therefore,
some gold was applied post fabrication using manual masking and electron beam
deposition.
Figure 6.6: Exploded view of the 2nd generation of the LTCC scaffold with labels
Figure 6.6 shows an exploded view of the 2nd design iteration (i.e., 2nd generation)
of the LTCC. Image (a) gives a top down view, where image (b) provides a bottom up
view to show the clearance cavities, vias, and micro-connectors that bias the electrical
traces. Layers are arranged similar to the first generation, but cavities, electrical traces,
and vias are modified to accommodate insertion of large MEMS chips, and to allow for
better centering of the device under the apertures. The layers have been reduced to three
total, with the 1st layer containing 10 sublayers and the 2nd and 3rd layer containing only
5 sub layers. Additionally, traces and contact points between layers were reduced
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significantly to improve assembly of the multi-layer stacks. In the 1st generation, more
than 12 pads needed to be aligned and secured with conductive epoxy in order to have a
functional scaffold. In this new embodiment, only 6 were needed, greatly improving the
yield during assembly. Additionally, micro-connectors were added to provide simple
biasing to the traces without the need to bond to a test PCB. In this generation, the
extraction aperture is a metal sheet with a hole replacing the LTCC with a hole in the
first design. Figure 6.7 (a) shows a magnified image of layer one with the newest design
iteration of the MEMS chip secured within. Additionally, a cutaway view of the
complete structure is shown indicating the location of the extraction and coded aperture.
SEM images of the apertures and the MEMS ion source are included.
Figure 6.7: (a) Magnified image of the 1st layer with MEMS micro-ion source secured
within the cavity, SEM images of source given; (b) cutaway view of the complete
scaffold with locations of apertures shown, SEM images of extraction and coded
aperture shown.
6.3.2.2 Assembly Details
The vias of LTCC layers 1 and 2 were fitted with conductive silver epoxy via a
screening process and joined manually. Precision alignment was performed using a Suss
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Microtech FC150 Flip Chip Bonder in order to properly align the top and bottom vias.
An assembled MEMS chip (details provided in section 6.2) was secured into the exposed
cavity using Loctite Black Max 380 Cyanoacrylate Adhesive. The MEMS chip was wire
bonded to the bond pads exposed on layer 2. Each bonding pad on the MEMS chip was
routed to a separate bonding trace on the layer. After initial device testing to verify
proper operation, the 3rd LTCC layer, with extraction aperture secured within, was
attached onto the 2nd layer. After initial electrical testing (details provided in section 6.4),
the 4th layer, with coded aperture secured within, was attached onto the 3rd layer.
6.3.2.3 First Generation
Figure 6.8 shows several optical images of the 1st generation packaged miniature
ion source. Image (a) shows the 1st generation of the MEMS chip secured into the 1st
layer. Wire bonds are used to secure the device to the 2nd layer of the LTCC. Care is
taken to ensure the wire bonds do not touch the edge of the substrate, and also to ensure
they do not extend too high and make contact with the 3rd layer when secured on top.
Images (b) and (c) show the packaged ion source mounted on a PCB test board with the
exit outlet of the ions placed directly over a hole in the PCB. Image (d) shows the
mounted device fitted with a copper plate over the hole on the backside of the PCB to
act as a collector for ions during testing. A wiring harness was used to connect the board
to the electrical feedthroughs of the vacuum chamber. Image (e) is the vacuum testbed
used for device testing.
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Figure 6.8: Optical images of the 1st generation of the packaged miniature ion source;
(a) device secured in the cavity and wire bonded to the 2nd layer of the LTCC, (b)
bottom half of LTCC secured onto test board, (c) after capping with final two layers,
packaged device is mounted upside down on PCB and bonded for testing, (d) a
copper plate is used to collect emitted ions, (e) the UHV testbed used.
6.3.2.4 Second Generation
Figure 6.9 gives an image of the 2nd generation of the packaged source in two
different stages. Image (a), “before capping,” shows a MEMS chip secured within the
cavity and wire bonded to the LTCC. This is the stage at which initial electrical
characterization is performed by plugging the micro-connectors into the harness of the
vacuum test chamber. Image (b), “after capping,” shows the state of the device once the
final two layers have been secured on top. This is the state at which ion testing is
performed; ion current can be measured at the outlet of the top aperture (i.e., coded
aperture). Additional details on electrical characterization are given in section 6.4.
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Figure 6.9: Optical image of the 2nd generation of the LTCC scaffold prior to the 1st and
2nd stage of electrical characterization; a) before capping; b) after capping.
The 2nd generation of the LTCC and MEMS packaged miniature ion source was
able to maintain a very small potential gradient in the ionization region, as well as
maintain relatively parallel equipotential field lines in the region of the ion trajectories.
The slotted extraction aperture also assists in maintaining the flat field lines. This results
in improved energy and angular dispersion. This can be seen in the simulation results
shown in Figure 6.10. The images give two different vantage points of the device. The
left column is the view from the side showing both cathode/grid structures on the left
and right side. The right column shows a cross-section view down the middle of the
device from the center of the floor towards a grid. These two perspectives provide good
visual understanding of the electric field lines. Images (a) and (b) show the device with
no field lines plotted. Images (c) and (d) show the field lines plotted with no ions
simulated. Images (e) and (f) show the plotted field lines with simulated ions indicating
their orthogonal path from the ionization region to the extraction aperture. Images (g)
gives a top down view of the device with plotted field lines showing the cubic ionization
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volume. Finally, image (h) shows the distribution of simulated ions passing through the
spatial filter. The red and green regions indicate more ions than the purple.
Figure 6.10: simulation results of 2nd generation miniature ion source; (a), (c), and €
provide a side view; (b), (d), and (f) provide a view from the center of the floor
looking towards a grid; (a) and (c) show the device with no field lines or ions plotted;
(c) and (d) show the field lines plotted; (e) and (f) show field lines and simulated ion
trajectories plotted; (g) and (h) are top down views with field lines and ion spatial
mapping through the coded spatial filter, respectively.
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6.4 Characterization of Packaged Micro-ion Source
Device testing was conducted in a custom vacuum chamber with the device
either on a PCB test board or plugged directly into a harness. Bias was applied through
twelve electrical feedthroughs which allowed for a variety of electrode biasing options.
All measurements were performed at room temperature with a base pressure of 7 x 10-7
torr. Custom LabVIEW software controlling a multichannel semiconductor analyzer
(Keithley 4200-SCS), and SourceMeter instruments (Keithley 2410s) was used to
electrically characterize the devices. In order to perform angular and energy dispersion
measurements, a 1704 channel capacitive transimpedance amplifier array detector from
the University of Arizona [315] was utilized. The detector included custom CMOS
integrated circuits with a 3.3 V, 0.35 micron process. Each detector finger has a separate
preamplifier, logic, and sample and hold on the custom IC. Characterization of the
MEMS micron-ion source was performed in two stages. The first stage involved
characterization of the electrical properties of the device prior to complete packaging.
The second stage involved characterization of the fully packaged device.
6.4.1 Electrical Characterization
6.4.1.1 Electrons
Both stages of electrical characterization were similar but the addition of ion
collection was added during the second stage. In the 1st generation of the packaged
source, the LTCC was wire bonded to a test board to provide electrical bias to all
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contained components. In the 2nd generation, micro-connectors secured to the LTCC
were plugged into a wiring harness connected to the vacuum chamber testbed. Electrical
characterization was performed in a similar matter to what has been previously reported
[149-151, 273]. Briefly, IV characterization was performed between each cathode and
grid to determine turn-on voltage and threshold voltage. These voltage settings were
then used once the device was completely sealed in a package. Additionally, triode
characterization curves were taken by operating the opposite grid as an anode. This
provided information into the ability of the electrons to transmit across the ionization
region where ions are created. The Fowler-Nordheim model was fitted to the I-V data to
verify field emission was occurring. Figure 6.11 shows the results from a device that has
undergone the three tests performed during electrical characterization.
Figure 6.11: Electrical characterization performed on a device prior to capping; (a) IV

characteristics; (b) Triode characteristics; (c) Fowler-Nordheim model fitted to IV data
to verify field emission.
A burn-in process was developed to improve the performance of devices before
using them in application. Constant current emission from the CNTs reduced
amorphous carbon and other absorbates from CNT tips through joule heating. The
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developed current controlled voltage lifetime (i.e. constant emission current) LabVIEW
program is used to drive new emitters at a constant emission of 1 µA for one hour. It
was observed that devices subjected to burn-in operated with better performance than
those without. An example of an I-V curve taken from a device is shown in Figure 6.12a.
That same device was then immediately subjected to the developed burn-in process
Figure 6.12b. Finally, another I-V curve was taken and is shown in Figure 6.12c. The
results demonstrate an improvement in turn-on and threshold voltage. The burn-in
shows the reduction in required voltage to maintain the desired current after one hour.
Figure 6.12: These three plots illustrate the process of burn-in on a device; (a) An
initial I-V curve is taken showing a VTO of approximately 160 V, (b) a one hour burn-
in is conducted where the VTO is reduced, (c) improved I-V curve after burn-in.
After characterization, IV sweeps were conducted between each set of electrodes
in the system to verify no shorting of electrodes was present, i.e., cathode-grid, grid-
floor, cathode-floor, grid(1)-grid(2), cathode-extraction aperture, grid-extraction
aperture, and all electrodes to ground. I-V analysis of devices at various stages of build
confirmed performance. Initial I-V curves and burn-in tests were used to condition the
samples, resulting in I-V performance with improved stability and control. Tests of
167
various magnitudes of current emission were performed to establish threshold voltages
for various emission current magnitudes. Figure 6.13 shows two I-V characterization
curves taken for a packaged device (i.e., after capping). Plot (a) gives the initial I-V test
performed to determine the turn-on voltage (VTO) of the device. This is why the device
was only biased until emission was achieved and the y-axis indicates nano-amps of
current. For this device, the VTO was approximately 85 V. Plot (b) reveals the threshold
voltage I-V analysis performed after the VTO sweep. The VTH for this device was
approximately 130 V to emit 1 micro-amp of current.
Figure 6.13: Electrical characterization plots of a packaged MEM micro-ion source;

both turn-on and threshold voltage I-V analysis plots are shown.
6.4.1.2 Ions
Ion current measurements were conducted at the outlet of the coded aperture.
Pressure was increased in the chamber until ion current was detected on the collector.
Ion extraction transient experiments were performed by cycling potentials on the
electrodes that govern ion extraction (e.g. floor and extraction apertures). By cycling
168
these control voltages OFF and ON, we can see the ion current respond accordingly, as
shown in Figure 6.14. With increased CNT emission current and increased sample inlet
pressure, ion current was increased.
Figure 6.14: Ion current measurements from a packaged micro-ion source. Chamber
pressure was increased until ion current was detected. Repeller and extraction
aperture voltages were then cycled to establish a periodic measurement of ions.
6.4.2 Dispersion Measurements
6.4.2.1 Simulation
Simulations used to design and evaluate performance of the packaged source
were also used to evaluate ion beam collimation and evaluate the energy and angular
dispersion. An example of a SIMION simulation on a packaged source can be seen in
Figure 6.15. Equipotential lines, electrons, and ions were plotted to give insight into the
trajectories and the field lines. Energy and angular dispersion values were then
169
extracted from the simulations. Average energy and angular dispersion were 14 +/- 4 eV
and 13 +/- 1 degree, respectively.
Figure 6.15: SIMION energy and angular dispersion results for the packaged device.
Ion trajectories, plotted in tan, are focused vertically off-chip and through the series
of apertures and through the outlet which would lead to a mass analyzer. The energy
dispersion is 14 +/- 4 eV. Angular dispersion is approximately 13 degrees.
6.4.2.2 Experimental
After packaging, the dispersion of the packaged miniature ion source was
investigated experimentally. Experimental measurements of energy dispersion were
conducted through stopping potential experiments. A retarding grid was placed
between the ion exit point of the packaged device and the detector. Ion current from the
device was established and measured on the detector. Early stopping potential
experiments presented difficulties in obtaining accurate measurements due to an
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abundance of electron current interfering with ion measurements. The experimental
setup was modified to include a new aluminum mount for the packaged device and
retarding grid. The mount included magnets on each side of the device to create a
magnetic field to collimate the electrons and prevent their escape from the ionization
regions, thus eliminating their interference with the ion current. In testing, the retarding
grid potential was swept from 0 V up to 40 V to successfully stop the ions from reaching
the detector. Approximately 10 sets of detector data per retarding grid step size were
averaged to establish a single data point on the stopping potential plot shown in Figure
6.16. A derivative of the data was then taken and the full width half max was calculated
to reveal the energy of the ions as well as the energy dispersion. Average energy of the
ions was 22 eV +/- 6 eV. For angular dispersion measurements, the packaged device
secured in the aluminum mount was oriented so that the ion exit point (i.e., the coded
aperture) was pointed directly at the detector as seen in Figure 6.16. The device was
operated at its threshold voltage to establish ion current. The pressure inside the
chamber was held at 5x10-5 torr using lab air. The ion current was collected and its peak
width was measured at the detector as seen in the bottom left plot in Figure 6.16. The
ions strike the detector at a specific pixel range, centered at the 1125th pixel, providing
the exit angle of the ions. This angle is calculated using the peak data and is recorded for
each sample. The average angular dispersion from the micro-ion source was
approximately 13° which matches values shown in simulation (Figure 6.15).
171
Figure 6.16: Dispersion measurements of the packaged micro-ion source; (top)
schematic diagram showing arrangement of electrodes on the MEMS device,
apertures, and orientation with the detector, and camera picture of the packaged
micro-ion source secured in the aluminum mount; (middle) magnified camera
packaged source directed at the detector for dispersion measurements, and image of
the ion exit point showing the strike points on the detector during angular dispersion
measurements; (bottom) angular dispersion data on the detector showing the average
angular dispersion of 13 degrees, and energy dispersion data showing ion current on
detector on the left y-axis, sweeping retarding grid potential on the x-axis, and the
derivative of the stopping potential data on the right y-axis. Average energy of the
ions was 22 eV with an average energy dispersion of 6 eV.
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6.5 Conclusion
A packaged miniature ion source was designed using a MEMS platform with
integrated CNT field emission cathodes and a LTCC 3D scaffold with integrated ion
optics. The packaged ion source was designed to operate similar to a Nier-type ion
source. The MEMS chip contained a CNT electron source, grid, repeller, and anode,
while the LTCC provided the scaffold for making electrical connections to the MEMS
chip, as well as positioning the extraction aperture, spatial filter, and sample inlet. Ion
current was generated from electron ionization that occurred in the ionization region
located close to the MEMS substrate. The design permitted generated ions to be
extracted vertically off-chip. The ion source focused the ions and used electrode
structures to minimize undesired energy and angular dispersion. The packaged
miniature ion source was evaluated using both simulation and experimental results.
Simulation was used to model the energy and angular dispersion of the packaged
device. Experimentally, the device was characterized electrically and angular dispersion
of the source was determined to be 13 °. Energy dispersion was not successfully
measured experimentally and will be the focus of future publication.
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7. Summary and Recommendations for Future Work
In this research, novel field emission vacuum electronic and microelectronic
devices using integrated carbon nanotube field emitters for a variety of advanced
applications have been developed. Additionally, details on their fabrication,
characterization, and application specifics have been discussed. The summary and
conclusions per chapter will be presented in order of their appearance in this work.
7.1 CIMS CNT Electron Source

A fully packaged CNT field emission device was developed and employed in a
prototype commercial mass spectrometer as an electron source to obtain chemical
ionization mass spectra in both positive and negative modes. The electron source
demonstrated performance benefits over standard filament thermionic emitter sources,
establishing itself as a candidate for CI and EI mass spectrometry applications. A
summary of key conclusions is as follows:
 Substrate and growth procedures were developed to improve device performance;
specifically device assembly techniques (important for scaling) and lifetime at
operating pressures (important for commercial viability when utilized in an
instrument) were addressed
o Substrate partial pre-dicing was developed to target final CNT emitter die size to
reduce CNT emitter damage when assembling devices. Undesired film liftoff
was a primary reason for device shorting and failure.
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o Thin film deposition of polycrystalline on top of the low resistive single
crystalline silicon substrate was investigated to reduce contact resistance
between the device scaffold bias electrode and the base of the CNT emitter.
Utilizing a conductive silver epoxy spread to the poly-Si region during assembly
reduced turn-on voltages and improved lifetime
 Constant-on lifetimes of 320 hours was demonstrated for the CNT electron sources
during ex-situ characterization. If operated at a 25% on-time cycle as expected
during real-time security checkpoint deployment, this equates to approximately 4
months of operation without replacement required.
 Cycling benefits (ability to turn the source on and off with succession) over standard
filament thermionic sources were demonstrated. This equates to reduced power
consumption and improved lifetime as cycling does not degrade performance of
cold cathode emitters, as is the case with thermionic.
 Device functionality was demonstrated and compared side by side to thermionic
emitters in the same mass spectrometer instrument. No loss in performance or
sensitivity was seen, and collected EI and CI spectra closely matched those collected
with the thermionic source, as well as those in literature.
7.1.1 Recommendations for Further Investigation
The following recommendations to enhance the electron source have been developed
from this research:
175
 By design, device extraction grids were positioned at a relatively large distance away
from the CNT emitters, approximately 200 µm. This was a parameter limited by the
electrode stand-off used to support and bias the grid. As a result of the distance, the
voltage requirements to achieve desired current values were relatively large. The
standard filament thermionic emitters were typically operated at 200 µA. Due to
voltage requirements from the CNT device, 50 µA was typically used. Whereas low
current is beneficial in portable instruments, with improvements to the emission
properties of the CNTs, the same low current could be achieved at lower voltages.
This would result in lower power requirements.
 The addition of focusing lenses and a small magnetic field integrated on the device
could assist in columniation of the electron beam. This would improve the total flux
into the ionization region.
 A proposed method for achieving both of the previously mentioned
recommendations is an embodiment that incorporates the emitters into a recessed
cavity in a silicon substrate which can then be directly secured to a PCB scaffold for
integration into the instrument. The extraction grids and option focusing grids could
then be deposited lithographically with oxide buffer layers to electrically isolate the
grids and cathode. Biasing could be achieved similarly to the design discussed in the
work, but turn-on voltages would reduce as a function of the separation, which
would be small given the distance is a factor of the insulating oxide layer.
176
Investigations into this method were initiated, and minor electrical characterization
was performed for proof of concept. Cavities were etched using photolithography
methods and deep reactive ion etching (DRIE). Catalyst was deposited into the
cavities and CNT growth was controlled such that the emitters remained well
underneath the surface. Further investigation is needed to demonstrate viability as
an instrument source. Figure 7.1 shows several versions of the preliminary device,
SEMs of the devices with magnified and cross section views of the emitters in the
cavity, and electrical characterization showing performance. Preliminary results
show capabilities of the device to reach emission currents nearly 8-10 times greater
than previous designs at similar voltages. Placement of one chip directly on the
previously developed PCB platform could result in a better performing electron
source.
177
Figure 7.1: (top left and right) Camera and SEM images of several embodiments of the
preliminary device fabricated on Si substrates; (bottom left and right) electrical
characterization shows performance capabilities of 8-10x better than previous design.
7.2 CNTs and Poly-Si: Kinetics, Mechanisms, Adhesion

The growth of CNTs on polycrystalline silicon substrates was studied to improve
the design of CNT cold-cathode field emission sources when integrated with
microelectromechanical systems, specifically in vacuum microelectronic devices
applications. The kinetics of CNT growth on polysilicon were compared to growth on Si
(100) substrates using the model of Deal and Grove to understand the activation
energies and mechanisms for base-mediated growth using microwave PECVD.
Diffusivity values for growth on poly-Si vs Si were also investigated. Finally, methods to
178
improve adhesion of CNT films during operation as field emission sources were
investigated. Primary conclusions include:
 Activation energies for CNT growth in the temperature range of 825 – 875 °C on
polysilicon and on Si (100) substrates were discovered to be 1.61 and 1.54 eV for the
nucleation phase of growth, respectively, and 1.90 and 3.69 eV for the diffusion
limited phase on Si (100) and polysilicon, respectively.
 Diffusivity values for growth on polysilicon were notably lower with a value of 7.9 x
10-5 cm2/s at 850 °C than the corresponding values for growth on Si (100) at a value of
7.9 x 10-5 cm2/s. The growth process became diffusion-limited earlier in the case of
poly-Si. Evidence favors a surface diffusion growth mechanism involving diffusion
of carbon precursor species along the length of the CNT forest to the catalyst at the
base.
 Methods to integrate thin film interlayers between the CNTs and the poly-Si
substrate to improve adhesion were investigated. Addition of a thin film of titanium
equivalent to the catalyst thickness (i.e., 5 nm in this work) showed improved
adhesion benefits of approximately 2.5 times when compared to the control samples
without adhesion interlayers.
The following recommendations to enhance the CNT growth have been developed from
this research:
179
 Results in this work revealed improvement in adhesion through the use of titanium
interlayers, however, small effects in CNT growth uniformity and electrical
properties (i.e., field emission performance) were also seen. Future work would
investigate new materials that could be deposited to serve as an adhesion layer, but
also improved electrical properties by reducing contact resistance between the CNT
emitter and the poly-Si substrate.
 Additionally, depositing materials that would double as a diffusion barrier during
growth would provide improved control of the CNTs. The length of the CNT
emitters, an important parameter when growing emitters between electrodes of a
fixed spacing, is proportional to the catalyst during growth. Any loss of catalyst into
the substrate during growth reduces the overall control of desired parameters.
 The use of intermetallics, such as TiN (titanium nitride), have been reported recently
as ideal materials for both adhesion and diffusion barriers. Additionally, a variety of
intermetallics have allowed for investigation of CNT growth on conductive metal
substrates, such as copper, further reducing the contact resistance between emitter
and substrate.
7.3 Improved Performance of FE-VMDs for IC

Particle trajectory simulation and experimental characterization were used to
improve device performance of a MEMS CNT-FE VMD as an active circuit element. The
performance enhancements serve as important enablers for larger scale integration and
180
for the realization of complex vacuum microelectronic circuits. Solutions for the
operation of multiple devices in close proximity and for enhancing transmission (i.e.,
reducing grid loss).
 It was determined that proximity effects between closely packed VMDs, specifically
crosstalk current active devices, cannot be neglected in the operation of the devices
as high performance integrated circuits.
 Isolation structures were developed from integrated MEMS floor electrodes. Their
incorporation into revised design geometries reduced crosstalk between neighboring
devices from 15% on average, to nearly zero. This mitigation technique allows for
dense placement of VMD active circuit elements on a common substrate, a necessity
for integrated vacuum circuits.
 Poor transmission (i.e., large electron loss at the grid) was improved.
o Innovative geometries and a new operational modes reduced grid loss by nearly
3x, thereby improving transmission of the emitted cathode current to the anode
from 25% from previous designs to 70% on average.
The following recommendations to continue development of the CNT-FE VMD’s have
been developed from this research:
 The next logical step for this work is the integration of multiple active circuit
elements (i.e., CNT FE-VMDs). The knowledge gained in this work towards densely
181
packing devices can be used to explore more complex circuits (e.g. oscillators, logic
circuits)
o Preliminary work towards development of lateral field emission logic devices
was explored via the design and fabrication of chips including four compact
CNT field emission vacuum microelectronic devices with integrated shielding
electrodes. This all-inclusive device, consisting of four sub-devices, can be wired
on or off chip to explore OR, XOR, and NAND gate logic. Figure 7.2a and Figure
7.2b provide a schematic diagram and microscope image of the multi logic
device in its planar state (not assembled). Image ‘a’ gives an example of a logic
OR configuration if both anodes are tied together. The device is equipped with a
multitude of bonding pads which will allow electrodes to be electrically
connected together in the desired state. Figure 7.2c shows a fabricated oscillator
circuit comprised of four CNT-FE VMD active circuit elements. Characterization
has not yet been investigated.
182
Figure 7.2: (a) Schematic diagram of logic OR gate configuration for CNT-FE VMD;
(b) microscope image of designed/fabricated quad logic device test platform; (c) SEM
image of designed/fabricated oscillator circuit composed of four CNT-FE VMDs.
7.4 LTCC Packaged MEMS Micro-ion Source

Microelectromechanical systems, carbon nanotube field emitters, and low
temperature cofired ceramic were utilized to develop a Nier type electron ionization
source for use in miniature mass spectrometer applications. MEMS fabrication was used
to outperform conventional machining of small-scale geometries and enable wafer-scale
full system development. Integrated CNT field emitters were utilized to achieve a high-
performance and reliable electron source with several benefits over traditional filament
thermionic emitters in terms of power use, lifetime, and current density. LTCC was used
as a 3D scaffold to integrate the MEMS device, integrated ion optics (i.e., extraction
183
apertures), and spatial filters (i.e., coded apertures). Specific work summaries and
conclusions include:
 New micro-ion source designs were envisioned to produce a complete symmetric
Nier type EI source. Symmetry was achieved in both geometry and equipotential
surfaces. Integrated MEMS repeller electrodes on the substrate were developed, and
together with the symmetric equipotential surfaces, vertical extraction of generated
ion current was attainable.
 Improvements to support structures (i.e., panel electrodes, latches, etc.) through
failure analysis and iterative design and test was conducted. Improved structures
were implemented to improve mechanical and current carrying stability of the
MEMS ion source.
 LTCC scaffold was designed such that all ion source components, i.e. gas inlet and
exhaust, electron source, ion optics, and spatial filter, could be integrated into a small
form factor package.
 Characterization of the packaged ion source was conducted and verified using both
simulation and experimental results. Electron and ion current measurements were
conducted for numerous devices to fully characterize the performance of the
packaged ion source. Angular dispersion measurements of the emitted ion current
from the packaged was measured.
184
The following recommendations to continue development of a miniature mass
spectrometer have been developed from this research:
 To complete electrical and performance relevant characterization of the packaged ion
source, energy dispersion measurements must be completed. A full understanding
of the energy and angular dispersion of the ion source would allow for improved
understanding of the complete miniature mass spectrometer instrument.
o Preliminary attempts to measure energy dispersion were performed a similar
mount used for angular dispersion. A retarding grid was fixed between the ion
current exit point (i.e., coded aperture) and the detector. Ion current was
generated and the retarding grid potential was swept in an attempt to retard the
ion current and measure their energy. Inconsistencies in measurements due to
the presence of escaping electron current and the experimental setup presented
inconclusive results. Methods to surround the electron source portion of the ion
source with a magnetic field, to collimate the electron beam and reduce electron
escapement, was underway at the time of this writing.
 The next logical step after full characterization of the packaged ion source is
integration with the complete miniature mass spectrometer. Development of the
miniature mass spectrometer instrument is a combined effort and the result of the
entire research team. The packaged ion source was designed to integrate directly
185
with a cycloidal mass analyzer with orthogonal electrical and magnetic field,
vacuum components, and additional miniature components for full system
realization. The packaged ion source fits inside the electric sector and the emitted
ions follow a cycloidal path as seen in the schematic diagram of Figure 7.3(top left).
CAD images of the electrical sector, its integration with the detector, and the
complete integration into the vacuum manifold can be seen in Figure 7.3. The
magnet is fitted around the vacuum manifold. This work will be the focus of future
publications.
Figure 7.3: (top left) Schematic diagram of ion trajectories leaving the packaged ion
source and traveling a cycloidal path within the electric sector due to the orthogonal
uniform electric and magnetic field; (top right) CAD image of electric sector, cutaway
view shown; (bottom left) CAD image of electric sector situated in its guide with the
detector in place; (bottom right) entire assembly placed inside a vacuum manifold; the
magnet (not shown) wraps around the vacuum manifold.
186
Appendix A
Current-Voltage Characterization: Program developed to control two (2)
Keithley 2410 SourceMeter Source Measure Unit (SMU) Instruments for the purposes of
measuring the current response due to an applied voltage on each electrode (the sample
and the counter electrode.) Keithley low level VIs provided by the manufacture were
integrated to set both instruments in source voltage, measure current mode. The
initialization was abstracted into a separate VI titled “Initialize Keithley for IV” which
presets all of the instruments before the main loop of the program is initiated. The
program also sets the measurement speed, compliance, range, and the voltage start,
stop, and step levels. The data is plotted on screen and saved to an excel file.
187
188
189
Lifetime Characterization: Program developed to control two (2) Keithley 2410
SourceMeter Source Measure Unit (SMU) instruments for the purposes of characterizing
the lifetime capabilities of a sample. The instruments are setup such that one electrode is
placed into a voltage controlled current mode in order to source a fixed current from the
sample by automatically modulating the voltage required to maintain that current. The
other instrument is set into a voltage bias mode in order to maintain a specific voltage
bias as a counter electrode. The instruments set the compliance and range values, as well
as the bias levels and hours to test. The plots measure both the applied voltage on the
cathode as well as the current.
190
191
192
Appendix B
Calibration Gas Spectra Discussion. Normalized mass spectra of
perfluorotributylamine (PFTBA) are shown in Figure A1. Electron ionization (EI)
spectra for both the carbon nanotube (CNT) field emission and filament thermionic
emission sources (Figure A1a and Figure A1d, respectively) closely match each other as
well as NIST reference EI spectra. PFTBA spectra were also collected in both negative
chemical ionization (NCI) (Figure A1b and Figure A1e) and positive chemical ionization
(PCI) (Figure A1c and Figure A1f) modes using both the thermionic emission source as
well as the CNT field emission source.
The PFTBA fragment ion peaks in NCI spectra taken with the CNT field emission
source (Figure A1b) reveals nearly identical peaks to that of the filament thermionic
emission source (Figure A1e). Strong peaks are observed at m/z 452 and 633 which is
consistent with the reference spectra of PFTBA [316] and indicate chemical ionization
conditions occurring with the CNT field emission source. The PCI mode revealed some
differences, including the absence of the m/z 264 peak (a common PFTBA fragmentation
peak) in the CNT field emission source that appears in the filament thermionic emission
source spectra. Additionally, it should be noted that the spectra taken with the filament
thermionic source in PCI mode stopped at m/z 600, so the m/z 654 peak that appears on
the CNT field emission source spectra is not visible in the filament source spectra. Also,
arguably the PFTBA is a much larger molecule (molecular weight 671 g/mol) with far
193
more fragmentation pathways than the smaller nitro compounds (eg. TNT, molecular
weight 227 g/mol). Thus, small differences in electron energies during the ionization
step might have a much greater influence on the PFTBA spectra and could have
contributed to the small differences in the spectra collected.
Because the ionization energy of N2 is greater than that of many typical organic
analytes, Hunt and Crow [186] state that “it is not surprising that nitrogen CI and
conventional EI spectra are essentially identical.” Oxygen, also present in significant
abundance in our ion source, similarly has an ionization energy greater than most
organics and should behave like nitrogen in Reactions 3 and 4. We would not assert that
our PCI PFTBA data taken with the CNT source is identical to the EI data, but it is
similar. Therefore, the existence of additional peaks present in the PCI data taken with
the CNT source spectra (Figure A1c), such as m/z 40 and m/z 69, could be explained by
some unavoidable EI taking place. Additionally, the higher pressure in the source region
under CI conditions seems to favor the production of higher m/z ions, likely because of
increased collisional cooling of the high energy electrons injected into the region. While
the CNT and filament PCI spectra in Figure A1c and Figure A1f, respectively, are not
identical, they are much more similar than spectra collected under EI conditions.
Moreover, the EI data is far more similar to the NIST reference EI spectra than either PCI
spectrum. The PCI PFTBA spectrum of both sources (CNT and filament) show an
194
increase in higher m/z ion intensity relative to the lower m/z ion intensity when
collected in PCI mode versus EI mode, consistent with previous observations [317].
Calibration curves were collected and analyzed for the trace explosives. The
calibration curves were generally linear, as expected. The data for the TNT calibration
curve can be seen in Figure A2.
195
B.1: PFTBA spectra collected in the explosive trace detection mass spectrometer with
the CNT field emission source (left column) and the filament thermionic emission
source (right column). Three modes are illustrated, including an initial electron
ionization (EI) mode to test for proper source operation, followed by both negative
and positive chemical ionization (NCI and PCI) modes. (a) EI spectra with CNT
source (b) NCI spectra with CNT source (c) PCI spectra with CNT source (d) EI spectra
with filament source (e) NCI spectra with filament source (f) PCI spectra with
filament source. Analysis shows spectra are nearly identical for both EI and NCI
modes, whereas PCI mode is visually different, with several indications that chemical
ionization is occurring. For example, signal peaks at m/z 502 exceed that of both m/z
131 and m/z 69.
B.2: A calibration curve of desorbed TNT is shown and is linear, as expected. Trace
explosive amounts were consistent with trace standards in the security field.
196
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Biography
Erich Justin Radauscher was born on August 28, 1984 in Brooklyn, NY. He
moved to Florida when he was 4 and grew up in beautiful Sarasota/Bradenton Fl. He
obtained his Bachelor’s degree in Electrical Engineering in May of 2012 from the
University of South Florida, Tampa, FL. He then moved to NC to pursue his doctoral
degree in Electrical and Computer Engineering at Duke University in June of 2012. He
concurrently worked as a research assistant at RTI International, Engineering and
Applied Physics Division throughout his time in the Ph.D. program. His research
interests include investigation of material properties and applications involving thin
film materials and micro/nano electronic technologies. Specifically, vacuum
microelectronics, carbon based materials growth and applications in field emission,
MEMS devices, and miniaturized instruments and sensors.
Publications:
1. Gilchrist, KH and Radauscher EJ; Piascik, JR; Stoner, BR; Amsden, JJ; Parker, CB;
Glass, JT; (2014). “Platform for Integrated Vacuum Microelectronic Circuits.” IEEE
International Vacuum Electronics Proceedings, IVEC. 155-156
2. Radauscher, EJ; Keil, AD; Wells, M; Amsden, JJ; Piascik, JR; Parker, CB; Stoner, BR;
Glass, JT; (2015). “Chemical Ionization Mass Spectrometry Using Carbon Nanotube
Field Emission Electron Sources.” Journal of The American Society for Mass
Spectrometry. 26(9): 1633- 1640
3. Radauscher, EJ; Gilchrist, KH; Di Dona, ST; Russell, ZE; Piascik, JR; Parker, CB;
Stoner, BR; Glass, JT; "Eliminating proximity effects and improving transmission in
field emission vacuum microelectronic devices for integrated circuits," 2015 IEEE
International Electron Devices Meeting (IEDM), Washington, DC, 2015, pp. 33.2.1-2.4.
4. Radauscher, EJ; Gilchrist, KH; Di Dona, ST; Russell, ZE; Piascik, JR; Amsden, JJ;
Parker, CB; Stoner, BR; Glass, JT; “Improved Performance of Field Emission Vacuum
Microelectronic Devices for Integrated Circuits,”
(submitted for publication)
5. Ubnoske, SM; Radauscher, EJ; Meshot, ER; Parker, CB; Stoner, BR; Glass, JT; (2015-
2016). “Integrating Carbon Nanotube Forests into Polysilicon MEMS: Growth
Kinetics, Mechanisms, and Adhesion.”
6. Radauscher, EJ; Amsden, JJ; Di Dona, ST; Herr, P; Gilchrist, KH; Hall, SD; Carlson, JB;
Parker, CB; Stoner, BR; Glass, JT; “Low Temperature Co-fired Ceramic Packaged
MEMS Micro-ion Source for Miniature Mass Spectrometry Applications”
227
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Design, Fabrication, and Characterization of

Thesis · January 2015

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Nanotube Field Emission Devices for Advanced Applications

Erich Justin Radauscher

Department of Electrical and Computer Engineering

Dissertation submitted in partial fulfillment of

Design, Fabrication, and Characterization of Carbon

Nanotube Field Emission Devices for Advanced Applications

Erich Justin Radauscher

Department of Electrical and Computer Engineering

An abstract of a dissertation submitted in partial fulfillment of

electron field emission (FE) cathodes in integrated FE devices. These nanostructured

and related electron emission devices in several advanced applications.

confine the performance and application of CNT-FE devices. Characterization studies

and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical

microelectronic device (VMD) applications.

Improved growth allowed for design and development of novel cold-cathode FE

FE electron source was developed and evaluated in a commercial desktop mass

demonstrated low power requirements, pulsing capabilities, and average lifetimes of

without sacrificing performance. Additionally, a novel packaged ion source for

source demonstrated improvements in energy and angular dispersion as well as the

Simulations and experimental design, fabrication, and characterization were used to

make these improvements.

Finally, novel CNT-FE devices were developed to investigate their potential to

perform as active circuit elements in VMD circuits. Difficulty integrating devices at

particle trajectory simulation and experimental characterization, device performance in

an integrated platform was investigated. Solutions to the difficulties in operating

of complex vacuum microelectronic circuits.

To my beloved parents, Erich and Sandra, and brother, Matthew

To my amazing baby boy, Aiden

Table of Contents ...................................................................................................................... viii

List of Tables ...............................................................................................................................xiv

List of Figures .............................................................................................................................. xv

List of Symbols and Abbreviations ........................................................................................xxii

Acknowledgements ................................................................................................................ xxiii

1. General Introduction ................................................................................................................ 1

1.1 Electronic Materials for Cold Cathode Field Emission ............................................... 2

1.2 Vacuum Microelectronics Overview ............................................................................. 7

1.3 Motivation and Objectives of this Research................................................................ 11

1.4 Dissertation Outline ....................................................................................................... 12

2. Background - Carbon Nanotubes (CNT), Field Emission (FE), FE Vacuum

2.2 Carbon Nanotubes ......................................................................................................... 15

2.2.1 Significance of CNT Research .................................................................................. 16

2.2.2 Structure ..................................................................................................................... 17

2.2.3 Growth Mechanisms of CNTs ................................................................................. 19

2.2.4 Properties of CNTs .................................................................................................... 21

2.2.4.1 Mechanical .......................................................................................................... 21

2.2.4.2 Electronic ............................................................................................................. 22

2.3 Field Emission Fundamentals....................................................................................... 25

2.3.1 Electron Emission ...................................................................................................... 26

2.3.1.1 Probability of Escape ......................................................................................... 26

2.3.1.2 Emission Processes ............................................................................................ 28

2.3.1.3 Emission Metrics Specific to FE ....................................................................... 31

2.3.2 The Fowler-Nordheim Theory ................................................................................ 32

2.3.2.1 Correction to the F-N Equation ........................................................................ 37

2.3.3 Field Emission from CNTs ....................................................................................... 38

2.3.3.1 Unique FE Properties of CNTs ......................................................................... 38

2.4 Field Emission Devices .................................................................................................. 42

2.4.1 FE Device Classifications .......................................................................................... 43

2.4.1.1 Spindt Cathode ................................................................................................... 43

2.4.1.2 Silicon Field Emitters ......................................................................................... 44