Fundamentals Thin Films Technology

C. N. Hsiao, Ph.D. ITRC, NARL

Outline
1. Vacuum technology
Introduction Pump and Gauge System description

2. Thin films technology

Physical vapor deposition Chemical vapor deposition Atomic layer deposition

Why Use Vacuum for Thin Films Deposition?

Cleanliness: low pressure => low number of molecules of

potential contaminants extend formation time for native oxides reduce or eliminate impurities incorporated during processing

Plasma generation: plasmas can easily be created and

sustained in a low pressure environment used for etching, deposition, epitaxy, and ion implantation

Lower molecular interference:

increase mean free path for ions used in sputtering

History of Vacuum

developed the first crude barometer pressure unit (torr) is named after him

Otto von Guericke - 1663 invented a piston vacuum pump Magdeburg hemispheres demonstration

1 torr = 1 mm Hg = 1/760 atmospheric pressure

17 and 19 th centuries

Boyle air pump

Robert Boyle

Thomas Hobbes

Gaseous discharges

1 atm =1,013,250 dyne/cm2=14.7 lb/in2 (psi) 1 atm=760 mm Hg=760 Torr=1013 mbar 1 bar = 106 dyne/cm2=0.98692 atm=105 Pa 1 Pa=1 N/mm2(ISO, SI unit)=133 Torr

The development of vacuum science and technology

AVS

1950

1970

1980

1990
CNLA PVD

2006

ITRC

Measure Work Performed by Vacuum System

Pumping Speed(S=V/T): the rate at which a vacuum pump

removes gasses from a system. volume/time, liters/second or ft3/minute (CFM)

Quantity of Gas: gas load, torrliter Thoughput(Q=PS): PV/T, torrl/secatmcm3/hr

Vapor pressure and outgassing

Working Pressure Ranges of Pumps

Ultra-high Vacuum <10-7 mbar <10-5 Pa high Vacuum 10-7..10-3 mbar 10-5 ..10-1 Pa Med Vacuum 10-3..1 mbar 10-1 ..101 Pa Rough Vacuum 1.ca.103 mbar 102.ca.105 Pa Piston Pump Diaphragm Pump Liquid-Ring Pump Sliding Vane Rotary Pump Multiple-Vane Rotary Pump Rotary Piston Pump Rotary Plunger Pump Roots Pump Turbine Pump Gaseous-Ring Pump Turbomolecular Pump Liquid Jet Pump Vapor Jet Pump Diffusion Pump Diffusion Ejector Pump Absorption Pump Sublimation Pump Sputter-Ion Pump Cryo Pump 10-14 10-13 10-12 10-11 10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 mbar 100 101

Intake Press

 Pump
Displacement: Screw, Roots, Rotary van Momentum transfer: Diffusion, Tourbo Extrapment: Cryo, Ion, Ti-sublimation

Gauge
Direct: Capacitance diaphragm Indirect: TC, Pirani, Cathode Ion, SRG

Vacuum hardware
Valve: Gate, Butterfly, Bellow Feedthrough: Motion, Electric

Pumps

Working Pressure Ranges of Vacuum Gauges

Ultra-high Vacuum <10-7 mbar <10-5 Pa high Vacuum 10-7..10-3 mbar 10-5 ..10-1 Pa Med Vacuum 10-3..1 mbar 10-1 ..101 Pa Rough Vacuum 1.ca.103 mbar 102.ca.105 Pa Liquid Level Manometer Elastic Element Gauge Compression Gauge Pressure Balance Viscosity Gauge Thermal Conductivity Gauge Thermomolecular Gauge Radioactive Ionization Gauge Penning Gauge Cold-cathode Magnetron Gauge Cold-cathode Inverted Magnetron Gauge High-frequency Vacuum Test Hot-cathode Ionization Gauge High-pressure Ionization Gaugue Bayard-Alpert Gauge Modulator Gauge Suppressor Gauge Extractor Gauge Bent Beam Gauge Hot-cathode Magnetron Gauge 10-14 10-13 10-12 10-11 10-10 10-9 10-8 10-7 10-6 10-5 Intake Pressure 10-4 10-3 10-2 10-1 100 101 mbar 102 103

Gauges

System description
1. Materials, out gassing, vapor pressure 3. Plasma, In-situ monitoring, hardware

2. Design

4. Leak detection, Calibration

Conformal Coverage

ALD CVD

PVD

ALD High-k TAF III

RSI ALD TCO TAF

1980

1990

2000

2008

2012

TAF

(ALD) 12 In-line ALD PLD

PE-ALD Laser MBE

In-line

PVD

CVD

Processes, Systems, and Materials of Thin Films in Vacuum Technology Division, ITRC
Process System Materials

PVD
IBAD Sputtering PLD

CVD
CBE PECVD PEALD

ALD
Thermal ALD

Optical Thin films TCO Thin films solar cell Nitride-based Metallurgy coating Multi-constitution films Nanostructure growth and conformal coating

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Physical Vapor Deposition

Evaporator Ion beam assisted deposition Ion beam sputter Sputtering Pulsed laser deposition Molecular beam epitaxy

Optical thin film coatings : Ion beam assisted deposition

RF ion source

IAD system
Improving stability and durability of films, which can be measured by the refractive index.

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RF ion source
RF (13.56 MHz) plasma Ar or O2 source Hollow cathode (Ta tube, 2300-2400 K emission electron), filament free Anode (attract emitted electron) grid (size and shape of ion source) RF neutralizer, RFN
Veeco Instruments Inc.

The 16cm gridded RF ion source is a broad uniform ion beam source for use in reactive processes with a wide range of operation (50 to 1500eV, 75 to 700mA) The 6 x 66cm gridded RF ion source is used for uniform processing of large-scale substrates.
The Mark II gridless ion source is an industry standard for optical coating systems and the most widely used assist source. For a broad range of thin films, the Mark II ion source provides a high beam current for controlling film stress and stoichiometry. Its broad application base is suitable for reactive and inert gases and high power densities. The flexible integration permits a compact system design and broad beam angle.

Film materials modified by Ion-Beam Process

Enhancement of adatom surface mobility Stimulation of the early, stages of film formation, e.g., nucleation, growth, and coalescence Development of preferred crystal orientation Lower substrate temperature for the onset of epitaxy Crystallization of amorphous films and amorphization of crystallization films Increased film/substrate adhesion Stimulation of film-sorption effects and film surface reactivity

12

Remote Sensing Instrument, RSI

Silver main mirror

100

Main mirror
Reflectance (%)

80

Ag Mirror
60

Multi-spectral Filters array Formosa satellite 2, NSPO

40

20

400~900 nm, T: 98% ASTM 3359 B: 5B

0 200

300

400

500

600

700

800

Wavelength (nm)

Optical thin films filter: B, G, R, NIR and Pan cromatic

Transmittance (%) 100
100

80 60

80

40
Transmittance
60

20

40

100
20

80 60
400 500 600 700 800 900 1000 1100

Wavelength

40 20 0 300
100

Admittance Loci analysis

100

400

500

600

700 800 900 Wavelength (nm)

1000 1100 1200

90
80

80 70

Transmittance

60

60

40

%T

50 40 30 20 10 0 400 500 600 700

B1 B1 35 Krad B1 1 Mrad

20

HRTEM image of B1 filter,

400 500 600 700 800 900 1000 1100

Wavelength

IAD process spectrum

Alternating H/L refractive index materials.

800

900

1000

1100

nm

13

 - Band pass filter coating

AR coating on PMMA by IBAD Process at Lower temperature

100 96 92 88 84

%T

80 76 72 68 64 60 400 500 600 700 800

AR PMMA

nm

Lower deposited temperature for flexible optical plastic substrate.

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Ion Beam Sputter

Characteristics of IBSD Amorphous thin films Low substrate temperature High packing factor (voids, moisture free) Stable optical properties (narrow band pass filter) Stable deposition rates

Veeco Instruments Inc.

RF-Megnetrons Sputter

15

Additional magnetic field traps electrons longer in the plasma region (Lorentz force) higher sputter rate at lower pressure, higher film purity, less diffuse scattering of sputtered atoms, localization of plasma.
100

95

90 T (%)

85 AR coating Quartz

80

75

70 200

300

400

500 600 Wavelength (nm)

700

800

HfO2/SiO2 4 layers UV AR-coat

Influence of sputtering parameter on the optical and electrical properties of zinc-doped indium oxide thin films

The IZO films deposited in pure argon atmosphere at room temperature with a resistivity of 2.4104 -cm, rms roughness of 0.416 nm, and optical transmittance of 80 %.

J. Vac. Sci. Technol. A, Vol. 23, No. 4, Jul/Aug 2005

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Film

Material (examples)

Magnetron sputtering process DC DC DC MF pulse reactive, RF MF pulse reactive MF pulse reactive (stationary)

Metals Alloys Multi layers Binary compounds Ternary compounds Gradient films

Al, Cr, Cu Ni/Al, NiV7 CrNiCo/Cr Al2O3, AlN, SiO2, Si3N4, TiO2 SiOxNy, AlOxNy Al2O3 -> AlNxO y -> AlN

Applied film

Innovation in multi-chamber design for advanced web coater:

Winding zone Pre-treatment zone Deposition zone (ITO) Deposition zone (SiO2) Un-winding zone
Chamber Winding Vacuum Coating drum cooling

Web Coater Systems

Control

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Pulsed Laser Deposition, PLD

Rapidly non-equilibrium thermodynamics condition

Complicated stoichiometric multiconstitution films Small-uniformity area films

Thin Films Deposited by Pulsed Laser Methods

Property
High-temperature supperconductivity Ferroelectricity

Applications
Microwave filters and delay lines, digital electronics, sensors DRAM capacitor, nonvolatile RAMs, optoelectronics, microwave devices MicroelectricalMechanical(MEN) devices

Metarials
YBa2Cu3O7

Pb(Zr)TiO3, (Sr,Ba)TiO3

Piezoelectricity

Pb(Zr)TiO3

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AlN/GaN superlattice grown by PLD: a HAADF STEM study

Molecular beam epitaxy

GEN2000, Veeco

7x6

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Chemical vapor deposition

Thermal chemical vapor deposition Low pressure vapor deposition Plasma enhanced chemical vapor deposition Chemical beam epitaxy Metal organic chemical vapor deposition Atomic layer deposition Plasma enhanced atomic layer deposition

PECVD: Characteristics and Reactor

The RF frequencies employed range from about 100 kHz to 40 MHz. In the reducedgas pressure environment, typically sustained between 50 mtorr and 5 torr. Electron and positive ion densities number between 109 and 1011/cm3, and average electron energies range from 1 to 10 eV. The net effect of the interactions among these reactive entities is to cause chemical reactions to occur at much lower temperatures. Slicon nitride 300 /min, 500 W

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PECVDA-Si

AKT

Solar Cells
Single crystalline (15-25%) Bulk Poly-crystalline (14-21%) Si-based Thin film Amorphous Si:H, SiGe, (8-13%)

Single crystalline Solar Cells Compound Poly-crystalline

GaAs, InP, (18-30%)

CdTe, CdS, CuInSe2, CuInGaSe2, (15-20%)

Organic thin film

Dye-sensitized (7-11%) Organic polymer (3-5%)

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Flexible Solar Cell

www.britisheco.com

www.powerportstore.com

Air Force Research Laboratory

Institut fur Textil- und Verfahrenstechnik

Photovoltaic Silicon Thin Film Solar Cell

Applied film

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Roll-to-roll CVD

Web type and width: 300 mm - web width ( stainless steel and PET available) Plasma source: 2 VHF-PECVD and 1 ECR-CVD Process temperature: below 100oC

Roth & Rau

CIGS Thin Film Solar Cell

Nano-Solar0.99 ISETCIGS 5%

0.05/3 m 100 nm 0.5-1.5 m 50 nm 50 nm

Ni/Al

Sputtering Chemical bath deposition

Vacuum method Co-evaporation Sputtering+selenization Co-evaporation+selenization Non vacuum method

1.5-2 m

0.5-1.5 m

Electrodeposition+selenization Printing+selenization

Sputtering

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 - PECVDPVDRTP LCDLED Flexible CIGS Thin Film Solar Cell Si wafer CIGS $/W

The MOCVD growth system

Wafer Capacity (GaAs) 95 x 2" 25 x 4" 5 x 10"

Aixtron AIX 3000 reactor

15 x 2" or 8 x 3" or 5 x 4"

AIX 2000 / 2400 HT

Multiwafer high temperature reactor for Sapphire (1200) or SiC (1600) applications

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PE-MOMBE (CBE)

III group nitride Energy gap engineering

Optical Emission Spectrum of RF Nitrogen Plasma Source

Atomic N Molecular Nitrogen

N* plasma

25

Single crystal GaN nanorods array and epitaxial InN film

Intensity (a.u.)

Energy gap of InN measured by PL is around 0.83 eV

900 1200 1500 1800 2100 2400

Wavelength (nm)

Catalyst-free growth of indium nitride nanorods by chemical-beam epitaxy

The nanorods are synthesized nearly unidirectionally along the 001 direction and the diameters varied in the range of 2040 nm with In/N flow ratio. Single-crystalline wurtzite structure is verified by x-ray diffraction and transmission electron microscopy. Raman measurements show that these wurtzite InN nanorods have sharp peaks E2 high at 491 cm1 and A1 LO at 593 cm1. APPLIED PHYSICS LETTERS 88, 233111 2006

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Optical properties of indium nitride nanorods by CBE

The emission peaks of PL spectra range from 0.69 to 0.79 eV, showing a blue shift as the rod size decreases from 40 to 5 nm APPLIED PHYSICS LETTERS 88, (2006) 233111 Nanotechnology 17 (2006) 39303932

ATOMIC LAYER DEPOSITION (ALD) High step coverage and large-area uniformity films grown by ALD process resulted from a unique sequential self-limiting surface reaction.

6 inch wafer

8 inch wafer

12 inch wafer

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Self-limiting surface reactions

(a) BY AX XY

(b)

(c)

Applications of thermal ALD : Lower equivalent oxide thickness of high

(d)

dielectric constant MOS gate oxides. Storage capacitor dielectrics. Solar energy, organic electronics, catalysis, micro-systems and biological.

(a)

(b)

(c)

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Nanosphere array

CNT

Gaq3

Butterfly Scale A replica of photonic crystal

PEALD

PEALD 3D design : 1. 2. 3. 4. RF generator and quartz chamber for plasma (ICP). Vacuum chamber, Pumping set, and manipulator. In-situ measurement preserved ports. Precursor delivery system.

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10-100 mTorr

30

Pt nano-particles
Q: Ar 1.5 Torr, O2 0.5 Torr Pt 0.5 sec O2 10 sec, purge 5sec Pt 60 ICP Power 100 W

TaNTiN Cu RuPdPt

Applications : 1. Cu interconnect and barrier 2. Ag high aspect ratio coating

Al2O3HfO2 TiNTaN WRu WTiN

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Criteria Thickness Uniformity control Film quality

ALD < 200 Excellent stoichiometry, low pinhole count, stress control possible 100% step coverage in 60:1 AR No particles due to gas phase reactions <1% dependency on 10 % process parameter changes Near transparent from 200300mm regarding process result No limite Medium

CVD >100 10 Excellent stoichiometry, low pinhole count, stress control possible 100% step coverage in 10:1 AR Particles due to gas phase reactions Strong dependency on process parameter change Major parameter changes needed for same process results from 200-300 mm 90-65 nm technology Medium

PVD >200 50 Limited stoichiometry, high pinhole count, Limited stress control possible 50% step coverage in 10:1 AR Particles due to sputtering Very dependent on vacuum integrity Major throughput hit when going from 200-300 mm

Conformality Cleanliness Process window

Scalability

Extendibility Vacuum requirement

100 nm technology High

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THANKS

Reference
Helmut Poppa, High resolution, high speed ultrahigh vacuum microscopy, J. Vac. Sci. Technol. A 22( 5), 2004, pp. 1931-1947. P. A. Redhead, Vacuum science and technology: 19502003, J. Vac. Sci. Technol. A 21(5), 2003, pp.12-14. J. P. Hobson, Fifty years of vacuum science, J. Vac. Sci. Technol. A 21(5), 2003, pp.7-11. Philip A. Lessard, Dry vacuum pumps for semiconductor processes: Guidelines for primary pump selection, J. Vac. Sci. Technol. A, Vol. 18, No. 4, 2000, pp.1777-1781. M. H. Hablaniana, Major advances in transfer pumps: 19532003 , J. Vac. Sci. Technol. A 21(5), 2003, pp.15-18. Kimo M. Welch, Major advances in capture pumps in the last 50 years , J. Vac. Sci. Technol. A 21(5), 2003, pp.19-24. P. A. Redhead, Measurement of vacuum; 19502003, J. Vac. Sci. Technol. A 21(5), 2003, pp.1-6. Theodore E. Madey, Early applications of vacuum, from Aristotle to Langmuir, J. Vac. Sci. Technol. A 2 (2), 1984, pp.110-117. Phil Danielson, A Journal of Practical and Useful Vacuum Technology , , , Vacuum Technology, Jozwiak, 2002 Leybold Vacuum, products and reference book, 2003 Basic Vacuum Practice, 3 rd edition, Varian Alcatel Vacuum Technologies, products catalogues

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