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IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 7, NO.

6, NOVEMBER 2008 693

A Single Palladium Nanowire Via Electrophoresis


Deposition Used as a Ultrasensitive Hydrogen Sensor
Yushi Hu, David Perello, Usman Mushtaq, and Minhee Yun, Member, IEEE

Abstract—We have successfully fabricated and demonstrated deposition (CVD) has been widely used in nanowire fabrication,
the use of a single metallic nanowire as a hydrogen sensor with especially semiconductor nanowires synthesis [12], [13]. One of
extremely high sensitivity via a very simple fabrication process. In the most utilized CVD processes, the vapor–liquid–solid growth
this paper, single palladium (Pd) nanowires were electrodeposited
within 100-nm-wide polymethylmethacrylate nanochannels using process [14], [15], was demonstrated as an effective fabrication
a Pd electrolyte solution. Via this method, nanowires were grown method for nanowires. However, the CVD methods require not
with widths ranging from 50 to 100 nm, and lengths from 3 to only high temperatures and proper catalysts for growth, but also
7 µm. The nanowires were successfully used to sense hydrogen a sophisticated fabrication process with specialized facilities.
concentrations as low as 5 ppm at room temperature. The growth As a controllable and feasible alternative growth method, elec-
control of single Pd nanowires, as well as the primary sensing
mechanism, is addressed in detail in this paper. trophoresis deposition could be performed using only a probe
station at room temperature ambient conditions and a proper
Index Terms—Electrophoresis deposition, hydrogen sensor, electrolyte solution. We previously demonstrated a hydrogen
single nanowire, palladium (Pd).
gas sensor based on a single palladium (Pd) nanowire that used
the aforementioned electrophoresis deposition method [16]. In
I. INTRODUCTION
this paper, we demonstrate ultrahigh sensitivity and growth con-
OTH semiconducting [1] and metallic [2] nanowires have
B attracted a great deal of attention in recent years. Some of
the proposed new and/or enhanced functions based on nanowires
trol, further enhancing the feasibility of this method.
Highly sensitive hydrogen sensors are important for safety
in many professions due to the dangers of even small amounts
include FETs based on semicondutor nanowires [3], [4] light- of leaked hydrogen. For instance, in aerospace crafts, early de-
emitting diodes [5], biosensors [6], chemical sensors [7], and tection of hydrogen leakage is critical to prevent fatal disasters.
thermocouples [8]. Due to their small size and high surface- For the advancement of future hydrogen-related environment-
to-volume ratio, nanowire-based nanosensors are emerging as friendly industries, such as automobiles based on hydrogen en-
a powerful class of ultrasensitive sensors, capable of directly ergy and hydrogen fuel cells, sensors capable of monitoring
detecting biological and chemical species [9]. One important extremely small hydrogen concentrations are necessary to pro-
category of chemical sensors, gas sensors, have previously been tect humans as well as the environment.
fabricated based on metallic nanowire arrays [7], [10] and bun- Different types of hydrogen sensors have been reported using
dles [11]. They display increased sensitivity and response times FET structures [17], [18] and diode [10] structures, as well as
compared to conventional sensors but are based on the over- Pd nanowire arrays and bundles [7], [11]. Though Pd-based
all performance of a collection of individual nanowires. This nanowire sensor arrays and bundles are favored for the ease of
collective behavior might undermine the advantages that sin- fabrication, they are generally less sensitive (not lower than 100
gle nanowires would possess. For this reason, the use of single ppm). On the other hand, it is commonly recognized that FET
quasi-1-D nanowires as sensors shows the best potential for structures should have an advantage in sensitivity, assuming that
future increases in sensitivity. they are properly “tunable” through the use of an applied back
In spite of the inherent advantages of single nanowire de- gate voltage [19]. As proof, NO2 and NH3 sensors based on
vices, fabricating and aligning single nanowires have presented a nanowire FET structures have been reported to have sub-ppm
formidable challenge that has deterred progress. Chemical vapor sensitivity [20]. For hydrogen sensing, however, a nanowire
FET structure is effectively useless due to the metallic nature of
Manuscript received June 9, 2008; revised September 8, 2008; accepted the two most commonly used materials: Pd and platinum. The
September 9, 2008. First published September 30, 2008; current version pub-
lished December 24, 2008. This work was supported by the Air Force Office of gate only minimally controls the conduction in the nanowires,
Scientific Research (AFOSR) and the National Science Foundation (NSF) un- and hence the nanowire FET hydrogen sensors [21] based on
der Grant ECCS 0824035. The review of this paper was arranged by Associate them have failed to sense concentrations below 10 ppm. In
Editor E. T. Yu.
Y. Hu, D. Perello, and M. Yun are with the Electrical and Computer Engineer- addition, using a back gate can complicate the fabrication of
ing Department, University of Pittsburgh, Pittsburgh, PA 15261 USA (e-mail: simple nanowire sensors.
hu.yushi@gmail.com; dperello16@gmail.com; yunmh@engr.pitt.edu). While semiconductor nanowires have been widely used in
U. Mushtaq was with the Department of Electrical and Computer Engineer-
ing, University of Pittsburgh, Pittsburgh, PA 15146 USA. He is now with the sensors, metallic nanowires are rarely mentioned or utilized
Department of Civil Engineering, Queen’s University, Kingston, ON KYL 3N6, because of sensitivity or fabrication issues. In this paper, we have
Canada (e-mail: mushtaq.usman@gmail.com). fabricated superthin Pd nanowires with sub-100-nm diameters
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org. using electrophoresis deposition; these nanowires successfully
Digital Object Identifier 10.1109/TNANO.2008.2005978 sense hydrogen concentrations as low as ∼5 ppm. Compared

1536-125X/$25.00 © 2008 IEEE


694 IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 7, NO. 6, NOVEMBER 2008

Fig. 1. Fabrication process template for 100 nm PMMA channels. (A) 100-nm-thick SiO 2 growth. (B) Photoresist spin-coating. (C) Development of photoresist.
(D) e-Beam evaporation of 5-nm-thick Ti layer as adhesion layer followed by 95-nm-thick gold layer as electrode. (E) PMMA spin-coating. (F) e-Beam lithography
and development of PMMA to pattern 100-nm-wide nanochannels.

with previous hydrogen sensors based on Pd nanowires, our trodes is then monitored during the growth process. A wire is
devices have much better sensitivity. Hence, the advantage of grown and connected between the electrodes when the voltage
single nanowires over nanowire bundles or arrays is clearly drops near zero. Different currents ranging from 20 to 100 nA
demonstrated. As for FET and diode hydrogen sensors, our are applied during this process and result in different nanowire
results demonstrate competitive sensitivity but are much simpler growth. Fig. 2(a) displays one such V − t curve with a cor-
to fabricate. Given the proper electrolyte solution, this method responding sharp drop in the voltage across the nanochannel.
can also be extended to other materials that would sense various Current supply is stopped several seconds after voltage drop to
other chemicals, such as NO2 , NH3 , etc. ensure stable connection between nanowire and electrode, and
avoid excessive lateral growth. A grown nanowire between two
Au electrodes is shown in Fig. 2(c). Based on the earlier elec-
II. EXPERIMENTAL
trophoresis deposition, nanowires with resistance ranging from
Pd nanowires were electrodeposited in 100-nm-wide poly- 100 Ω to 100 kΩ can be fabricated.
methylmethacrylate (PMMA) channels patterned between two The gas sensing system used for testing the nanowires is il-
Au electrodes. The Au electrodes and PMMA channels were lustrated in Fig. 3. Using Labview (National Instrument, Inc.,
fabricated on 4-in (100 mm) Si wafers. See Fig. 1 for a de- USA), two gas lines, supplying hydrogen gas and nitrogen gas,
tailed template of the fabrication process. In step A, a layer of respectively, can be controlled by an MKS flow controller sys-
100 nm SiO2 is thermally grown as an insulation layer. In steps tem (MKS Multi Gas Controller 647 C, MKS Instruments, Inc.,
B and C, a layer of positive photoresist is spun on the surface, USA). Two hydrogen gases with different concentrations are
and the Ti/Au electrodes are patterned using optical lithogra- used in sensing. The first gas is 10% hydrogen and the second is
phy. In step D, 5 nm Ti and 95 nm of Au are deposited by manufacturer-certified 0.1% hydrogen with nitrogen gas as bal-
electron-beam (e-beam) evaporation. Unwanted metal areas are ance gas (Matheson Tri Gas, Inc., USA). To achieve the desired
removed with a lift-off technique, and the remaining Ti/Au re- hydrogen test concentration, 99.999% pure nitrogen gas is used
gions serve as electrodes for the electrophoresis deposition. In as a mixing gas to dilute the hydrogen. To ensure proper gas
steps E and F, 100 nm of PMMA is spin-coated on the surface mixing, the two lines are connected to a gas mixing chamber
of substrate. Afterward, 100-nm-wide channels are patterned before going to the reaction chamber. The mixing chamber has
by e-beam lithography, and nanochannels are formed when the one gas outlet that leads to the reaction chamber with an inner
resist is developed. volume of 12.6 mL. With proper flow rates of hydrogen gas and
The nanowire deposition is completed using a probe station. pure nitrogen, it is possible to produce any desired hydrogen
A drop of Pd electrolyte solution consisting of diamminepalla- concentration from 10% to 2 ppm with this system. The sensing
dium nitrite (Pd(NH2 )2 (NO2 )2 ) (10 g/L) and ammonia sulfa- chamber is where the nanowire sensor is placed. It has a gas
mate (NH4 SO3 NH2 ) (100 g/L) is placed on the channel between inlet connected to the mixing chamber outlet and a gas outlet
the electrodes by a micropipette [16]. A constant current is then that directly connects to the ambient. The test does not require
applied to adjacent Ti/Au electrodes using a semiconductor an- a pumping system and is operated at room temperature.
alyzer (Agilent B1500 A), as shown in Fig. 2(a). A side view is The actual sensing process begins by applying a constant 2.5-
shown in Fig. 2(b). The corresponding voltage across the elec- mV dc voltage across the nanowire using a current amplifier
HU et al.: SINGLE PALLADIUM NANOWIRE VIA ELECTROPHORESIS DEPOSITION USED AS A ULTRASENSITIVE HYDROGEN SENSOR 695

(SigmaPlot 9.0, SYSTAT Software, Inc., USA). R represents


resistance of Pd nanowire during detection and R0 represents
its initial resistance before detection.

III. RESULTS AND DISCUSSION


We fabricated nanowires with diameters consistently ranging
from 100 nm to less than 50 nm. Depending on certain physical
traits, these nanowires can be categorized into three different
kinds: 1) plain structure; 2) grain structure; and 3) hairy struc-
ture. SEM images for the three different kinds of structures are
shown in Fig. 4(a)–(e). Plain structure nanowires, as shown in
Fig. 4(a) and (b), are composed of very tightly bound particles
that are well connected to each other with no gaps. The diameter
of this kind of nanowire is relatively uniform along the channel,
and the surface is relatively plain. As shown in Fig. 4(c) and
(d), the grain structure nanowires consist of small nanosized
nodes, each barely connected to others by a very small neck.
The diameter of this kind of nanowire varies along the channel,
and the neck part can be as small as 10 or 20 nm. The typi-
cal size of individual grains or nodes ranges from 50 to 100
nm. Hairy structure nanowires, shown in Fig. 4(e) and (f), are
similar to a tree structure. They have a trunk in the center and
many dendrite-like branches reaching outward. The length of
individual branches is limited by the width of the channel.
Through extensive testing of different nanowires, a relation-
ship between the growth condition and the structure has been
found. In these tests, the same 6-µm length and 100-nm width
were used, while the growth current was varied. It was discov-
ered that the growth is highly dependent on the electric field
within the channels. As shown in Fig. 5(a)–(c), three SEM im-
ages with three different growth currents of 500 nA (a), 100 nA
(b), and 50 nA (c) indicate a clear relationship between current
and nanowire structure. With a higher current [Fig. 5(b)], the
electric field between the electrodes and the region inside the
channel is higher, and the nanowire tends to grow very quickly
and produce more dendrites. With a lower current [Fig. 5(c)],
the actual electric field is correspondingly lower and the growth
is comparatively slower, allowing seeds inside the channel to
grow and produce a grain structure. Interestingly, with an in-
termediate current, the nanowire could show grain structure on
cathode (left) side and hairy structure on anode (right) side, as
Fig. 2. Electrophoresis deposition of Pd nanowire. (a) Voltage signal across shown in Fig. 5(b). As the nanowire starts growing from the left
the nanochannel during electrophoresis deposition shows a voltage drop to side in the images of Fig. 5, the electric field is relatively weak
∼0 V when nanowire connects the Ti/Au electrodes at the completion of the
growth process. (b) Cross-sectional diagram of the nanochannel structure dur- since the distance between the cathode and anode is large. In
ing electrodeposition. (c) SEM image of a grown Pd nanowire between two this case, the grain structure growth is favored. However, as the
electrodes. nanowire grows close to the anode, a relatively larger electric
field is produced at the leading edge of the Pd growth; thus,
(Keithley 428, Keithley, Inc., USA). The current amplifier is also hairy structure growth appears dominant.
used to measure (and amplify) the respective current through The behavior of these structures when exposed to hydrogen
the Pd nanowire. The output voltage signal from the current gas also varied according to their structural type. The exper-
amplifier is then collected by a data acquisition system (Keithley iments showed that the three types of nanowires have three
2701, Keithley, Inc., USA) that is interfaced to a computer with different sensing behaviors. For the plain structure nanowires,
Labview for data storage. The collected output signal is utilized measurements showed increased resistance when exposed to
to sense the hydrogen gas in the sensing system. The recorded hydrogen. The original resistance was recovered after the sens-
voltage versus time data are converted into resistance change ing chamber was purged with nitrogen. An SEM image and a
ratio or (R − R0 )/R0 versus time and plotted by Sigma Plot 5000-ppm hydrogen sensing signal of a plain structure nanowire
696 IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 7, NO. 6, NOVEMBER 2008

Fig. 3. Schematic graph of hydrogen sensing system. Two different gases, hydrogen and nitrogen dilution gas, are connected to two separate gas valves and the
flow rates are controlled by a computer. The two gases are mixed in a separate chamber prior to the reaction chamber where the nanowire is located during sensing.
The current through the nanowire is monitored and amplified by a current amplifier into a voltage signal, which is recorded by a Keithley data acquisition system
interfaced to a Labview data collection program on the computer.

Fig. 4. SEM images for three different kinds of grown nanowires. (a) and (b) Plain structure nanowire with 85 nm diameter. (c) and (d) Grain structure nanowires
with diameter ranging from 100 to 150 nm. (e) and (f) Hairy structure nanowires with ∼100 nm diameter.

Fig. 5. SEM images for nanowires grown using three different currents. (a) 500 nA growth current. (b) 100 nA growth current. The upper left inset is magnification
for the left side and bottom right inset is right side magnification. (c) 50 nA growth current.

are shown in Fig. 6(a) and (b). The diameter of the nanowire are preferred because of their much higher surface-to-volume
was around 100 nm, and from Fig. 6(b), it can be seen that the ratio; thus, any small change of surface resistance due to hydro-
resistance change ratio is positive when exposed to hydrogen. gen adsorption exerts a larger impact on whole structure. The
This positive change corresponds to an increase of resistance. It fact that we were not able to get any sensing signal for plain
is well known that Pd has two special properties when exposed structure nanowire with diameter larger than 100 nm in our ex-
to hydrogen [22]. The first property is resistivity change; the periment may be a proof of this statement. In addition, unlike
resistivity of β phase PdH0.7 is ∼1.85 times that of α phase Pd other specific nanowire-based hydrogen sensors [7], [11], this
at room temperature and at ambient conditions [7]. The second kind of nanowire senses hydrogen purely based on the intrinsic
property is swelling of the lattice size. The lattice constant of properties of hydrogen compounds, rather than from structural
Pd changes from 3.889 Å of α phase Pd to 4.025 Å for β phase change. Even so, the wire has considerable sensitivity and proves
PdH0.7 , resulting in a 10.4% volume expansion [22]. Plain the advantage of single nanowire structures for sensing instead
structure nanowires act in the same way as normal Pd hydro- of bundles or arrays.
gen sensors do when exposed to hydrogen, such as those based We noted that a small yet steady increase of resistance is
on thin films. They show an increase of resistivity based on presented in the signal during the measurements. Two possible
the first (resistance) effect. However, plain structure nanowires reasons could result in this phenomenon. First, a gradual
HU et al.: SINGLE PALLADIUM NANOWIRE VIA ELECTROPHORESIS DEPOSITION USED AS A ULTRASENSITIVE HYDROGEN SENSOR 697

Fig. 6. (a) SEM image of a plain structure nanowire with ∼110 nm diame-
ter. The green box inset shows a magnified picture of the center of the wire.
(b) 5000-ppm hydrogen sensing signal of this nanowire. The resistance of the
nanowire is increased when hydrogen is on.

accumulation of hydrogen on the surface of Pd during detection


process could gradually increase the surface resistance of
nanowire. Second, the positive temperature coefficient of Pd
under hydrogen environment could lead to a steady increase
of resistance due to the heating of nanowire in detection
process [23]. A gas system with better gas transportation and
thermal conduction should help minimize this signal drifting.
Fig. 7. (a) SEM image of a grain structure nanowire with the grain size
The grain structure nanowires were found to exhibit the high- ranging from 40 to 100 nm. The insets are magnified images of specific parts
est sensing ability among these three types, accurately sensing of the nanowire. (b) 1000- to 5-ppm hydrogen sensing signal of this nanowire.
hydrogen concentrations as low as 5 ppm. Detection of 5 ppm The resistance of nanowire is decreased when hydrogen is on. (c) Illustration of
sensing mechanism of grain structure nanowires. The nano-sized necks between
is the highest sensitivity found in the literature for any structure particles are crushed by neighboring particles when hydrogen gas flow is on
based on pure Pd. The resistance of grain structure nanowires inside the sensing chamber.
decreased upon hydrogen exposure, quite unlike plain struc-
ture nanowires. SEM images of one grain structure nanowire β phase PdH0.7 to α phase Pd. Rather, it is caused by a structural
together with the hydrogen sensing signal for concentrations as change of the nanowire itself. The resistance of the nanowire
low as 5 ppm are shown in Fig. 7(a) and (b). It is clear that this appears to be dominated by hopping between the nanoparticle
nanowire is composed of many small nanoparticles with diam- contacts instead of the bulk of the Pd. The changing contact
eters from 40 to 80 nm. The nanoparticles are either in close area between neighboring nanoparticles, which results from the
contact or connected by a small neck. As shown in Fig. 7(b), the volume expansion during hydrogenation, appears to be the dom-
sensing is cycled with different hydrogen concentrations from inant factor. The first mechanism for the contact change is due
1000 to 2 ppm, and voltage rises (and thus, resistance drops) to the volume expansion of the neck itself. A more dominant
whenever the nanowire is exposed to hydrogen. In this structure, mechanism results from the expansion of neighboring parti-
the change is no longer attributed to the resistivity change from cles. The neighboring particles, whose sizes are typically in the
698 IEEE TRANSACTIONS ON NANOTECHNOLOGY, VOL. 7, NO. 6, NOVEMBER 2008

Fig. 8. Two different hairy structure nanowires with different sensing signals. (a) SEM images for a 100-nm-diameter hairy structure nanowire. The green box
inset is a magnified image. (b) A 1% (10 000 ppm) sensing signal for the nanowire in (a). The resistance is decreased when hydrogen is on. (c) SEM images for a
hairy structure closely resembling that of a plain structure nanowire with a trunk diameter ranging from 30 to 90 nm. (d) One percent (10 000 ppm) sensing signal
for the nanowire in (c). The resistance is increased when hydrogen is on.

range of 100 nm, are much larger than the neck. As illustrated For the hairy structures, we have found even more interest-
in Fig. 7(c), they will expand and cause the length of the neck to ing results regarding hydrogen sensing, since more complicated
decrease by compression. Simultaneously, the diameter of the sensing mechanism exists in this case. As mentioned before,
neck will be forced to expand. Hence, the contact area between hydrogen absorption in Pd could cause a resistivity increase via
neighboring nanoparticles would be greatly increased and the the change in the chemical composition of the wires, or a re-
nanowire resistance significantly decreased. sistance decrease via size swelling. We believe that the sensing
Pd nanowire hydrogen gas sensors based on Pd size change mechanism of this structure is a combination of the two, and the
have been reported and described by Favier et al. [7]. Past de- final resistance change of a specific nanowire depends on which
vices utilized similar volume expansion to act as a hydrogen of the two mechanisms is dominant. Interestingly, it has been
sensor switch. Unlike these previous structures, the nanowires found that both can be dominant in the hairy structure. SEM im-
considered in this paper consist of particles that are connected ages of two hairy structure nanowires with two different sensing
by small necks as opposed to discontinuities. This results in a mechanisms, together with their sensing signals, are shown in
completely different overall sensing mechanism. Our nanowires Fig. 8(a)–(d). When both were exposed to 10 000 ppm hydro-
are able to continuously sense hydrogen gas concentration down gen, the first nanowire [Fig. 8(a)] showed a resistance decrease
to an extremely low level because the contact area modulation [Fig. 8(b)], while the second one [Fig. 8(c)] showed a resistance
with respect to the original contact area is never trivial. Past increase [Fig. 8(d)]. It is easily seen that in the first nanowire,
devices had much larger particles and gaps between them, and the dendrites are closely twisted together and the gaps are rel-
hence, the critical threshold to close and open the gaps occurred atively small. When exposed to hydrogen, the size swelling of
at a concentration of about 5000 ppm (0.5%) [7]. However, even the nanowire could result in direct contact between dendrites
at concentrations as low as 2–5 ppm, a small decrease in resis- and the trunk, and thus, the effective diameter of the nanowire
tivity is measurable in our structure, since a small change of the is increased. This then produces an increased conductance and
nanoparticle size results in a big change of the contact area, and is very similar to the grain structure mechanism. In the second
hence, a big and continuous change in resistance. More investi- nanowire, however, the dendrites are loosely distributed, and the
gation is required to discern the exact effect of size swelling on big gaps between the dendrites prevent them from making more
the resistance change. contact with the trunk when exposed to hydrogen. In this case,
HU et al.: SINGLE PALLADIUM NANOWIRE VIA ELECTROPHORESIS DEPOSITION USED AS A ULTRASENSITIVE HYDROGEN SENSOR 699

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nanowires electro-deposited into anodized alumina template,” IEEE Sens.
J., vol. 6, no. 3, pp. 509–513, Jun. 2006.
[12] S. Mathur, H. Shen, V. Sivakov, and U. Werner, “Germanium Minhee Yun (M’05) received the M.S. and Ph.D. degrees from Arizona State
nanowires and core-shell nanostructures by chemical vapor deposition University, Tempe, in 1996 and 1998, respectively.
of [Ge(C5H5)2],” Chem. Mater., vol. 16, no. 12, pp. 2449–2456, 2004. He was a Postdoctoral and Research Scientist from 1998 to 2000. Then
[13] S. Hofmann, C. Ducati, R. J. Neill, S. Piscanec, A. C. Ferrari, J. Geng, he worked as a Junior and a Senior Engineering Staff at the Jet Propulsion
R. E. Dunin-Borkowski, and J. Robertson, “Gold catalyzed growth of Laboratory (JPL), National Aeronautics and Space Administration (NASA)
silicon nanowires by plasma-enhanced chemical vapor deposition,” J. from 2001 to 2005. In 2005, he joined the Electrical and Computer Engineering
Appl. Phys., vol. 94, no. 9, pp. 6005–6012, 2003. Department, University of Pittsburgh, Pittsburgh, PA, as an Assistant Professor.
[14] A. M. Morales and C. M. Lieber, “A laser ablation method for the synthesis His current research interests include single nanowire growth and its application
of crystalline semiconductor nanowires,” Science, vol. 279, no. 9, pp. 208– in sensing, development in carbon nanotube (CNT)-FET devices, and microbial
211, 1998. bio-fuel cell based on nanostructured materials.

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