Low Temperature Nitride Semiconductor Growth

Dr Scott (K.S.A.) Butcher, Dr Marie Wintrebert-Fouquet, Professor T.L. Tansley

October

Macquarie University hosts the premier nitride semiconductor growth laboratory in Australia. Work on the nitrides began here in the early 1980s. Our research has concentrated on the low temperature, low substrate damage growth of aluminium nitride, gallium nitride, indium nitride and their alloys. A state-of-the-art low temperature chemical vapor deposition (CVD) unit has been built for the growth of these semiconductors. The system includes an ArF excimer laser used to crack precursor gases using photolysis (laser induced CVD) and a remote microwave plasma source to supply precursor radicals, especially atomic nitrogen (remote plasma enhanced CVD). Indium nitride is also grown at Macquarie using a radio-frequency reactive sputtering unit, despite the simplicity of this method it still provides the best quality InN.

§         Why nitride semiconductors? Since the early 1990s the group III nitride semiconductor gallium nitride, sometimes alloyed with indium nitride and aluminum nitride, has been used to fabricate very bright blue, violet, blue-green and white light emitting diodes (LEDs). The white LEDs will replace standard light bulbs over the next few years. Laser diodes are also being developed for high density optical storage – the next generation of DVDs. In addition solar blind UV detectors and high speed high power transistor devices (HEMT and HBT) have also been developed. In less than a decade nitride semiconductors have become some of the hottest materials around.

§         Why low temperatures? At present best quality gallium nitride is grown above 1000o C, by a method called MOCVD, on expensive sapphire or SiC substrates. Growth at lower temperatures would allow less expensive substrate materials, such as glass, to be used. It is also important that the atomic spacing of the substrate and the nitride films should match as closely as possible to inhibit strain in the film i.e. a close lattice match is required. Sapphire and gallium nitride do not have a close lattice match, but some temperature sensitive materials, such as ZnO, have only a very small lattice mismatch with gallium nitride. By growing at lower temperatures we hope to be able to use cheaper substrates, and substrates that are closely lattice matched to GaN.

§         Indium Nitride Emerges. Over twenty years ago the world’s purest indium nitride was grown at Macquarie University by Trevor Tansley and Cathey Foley. This record has never been equaled. Now after more than two decades in the wilderness, international interest in indium nitride is being fueled by the potential to create higher mobility (faster) high power nitride based transistor devices. The old apparatus used to create the highest mobility (fastest) indium nitride ever grown is still in existence at Macquarie University, and has recently been upgraded to attempt another Macquarie led assault on the old record. The hope here is to understand the film growth parameters to the point where high mobility material can be routinely grown at Macquarie. If this can be achieved then the University will begin to supply this material to research groups around the world on a commercial basis.

§         Some of the group history and achievements:

§         Highest mobility nitride film ever grown (1984)

§         Highest purity indium nitride ever grown (1984)

§         High quality aluminium nitride insulating films grown by LICVD (1993)

§         Gallium nitride with 200 cm2·V-1·s-1 carrier mobility grown at 650o C using RPE-LICVD (1996)

§         Highest mobility n-type gallium nitride film ever grown on glass (2000)

§         Ultra-high resistivity aluminium nitride grown at room temperature (2001)

Currently, we are extending our studies to include device applications of low temperature grown GaN, in the direction of heteropolar devices such as light emitting diodes grown on glass and heterojunction bipolar transistors.

Recent Funding:

We graciously acknowledge the funding recently received by us from NICOP in partnership with the U.S. Office of Naval Research. In particular we acknowledge Dr Colin Wood and Dr Jaime Freitas Jr. for their roles in this support. These funds have been instrumental in allowing the update of our low temperature metalorganic CVD growth system, and has allowed us to greatly forward our understanding of low temperature growth processes. The U.S. Office of Naval Research also provides a useful on-line semiconductor based facility - the U.S. National Compound Semiconductor Roadmap.

Funding from the Australian Institute of Nuclear Science and Engineering (AINSE) has allowed us access to a Cameca 5f SIMS system for the analysis of the composition of our nitride films. Through AINSE we also have access to a DLTS facility that allows us to probe the electronic defect structure of our films.

 

Macquarie logoNot least of all in this list we must thank Macquarie University, the Division of ICS and the Physics Department for their continuing support. Dr K. S. A. Butcher is particularly thankful for the support of a Macquarie University Research Fellowship (MURF).

 

Selected publications include:

For Aluminum Nitride:

Ultra-High Resistivity Aluminium Nitride Deposited on Mercury Cadmium Telluride

K. S. A. Butcher and T. L. Tansley

J. Appl. Phys. 90 (2001) 6217-6221.

 

Pre-deposition UV Treatment for Adhesion Improvement of Thin Films on Mercury Cadmium Telluride,

K. S. A. Butcher, T. L. Tansley, K. Prince and P. W. Leech

J. Vac. Sci. Tech. A 19 (2001) 90-96.

 

Improvements in the Dielectric Properties of Aluminium Nitride Through Passivation

K. S. A. Butcher and T. L. Tansley

2000 International Semiconducting and Insulating Materials Conference,
SIMC-XI (Editors C. Jagadish and N. J. Welham, IEEE Publishing, 2000) 59-63.

 

X-ray Photoelectron Spectroscopy Depth Profiling of Aluminium Nitride Thin Films,

K. S. A. Butcher, T. L. Tansley and Xin Li, Surf. Interface Anal. 25 (1997) 99-104.

 

Photolytic Absorbate Removal During the Growth of Aluminium Nitride by Remote Microwave Plasma Chemical Vapour Deposition,

K. S. A. Butcher, T. L. Tansley, Xin Li and Bing Zhou, Solid-St. Electron. 41 (1997) 305-314.

 

Dielectric Properties of AlN Films Prepared by Laser-Induced Chemical Vapour Deposition

Xin Li, T L Tansley and V W L Chin, Thin Solid Films, 250 (1994) 263-267.

 

Characterization of AlN/n-GaAs Heterointerfaces Determined by Energy-Resolved Correlation DLTS,

X.Li, T. L. Tansley, K. S. A. Butcher and D. Alexiev, Solid-St. Electron. 36 (1993) 381-385.

 

Laser-Induced Chemical Vapour Deposition of AlN Films

Xin Li and T L Tansley,  J. Appl. Phys., 68, (1990) 5369-5371.

 

 

 

For Gallium Nitride:

 

Gallium and Oxygen Accumulations on GaN surfaces following argon ion milling in ultra-high vacuum conditions

K. S. A. Butcher, Afifuddin, T. L. Tansley, N. Brack,  P. J. Pigram, H. Timmers, K. E. Prince and R. G. Elliman

Applied Surface Science 230 (2004) 18-23.

 

Atomic layer deposition of ZnO thin films and dot structures

M. Godlewski, K. Kopalko, A. Szcerbakow, E. Lusakowska, M. M. Godlewski, E. M. Goldys, K. S. A. Butcher and M. R. Phillips

Proceedings of the Estonian Academy of Sciences. Physics, Mathematics, 5 (2003) 277-288.

 

Progress at Macquarie University’s Low Temperature Nitride Growth Facility

K. S. A. Butcher, M. Wintrebert-Fouquet, P.  P. -T. Chen, Z. Zheng, I. L. Guy and T. L. Tansley, Proceedings of the 27th A&NZ Condensed Matter and Materials Meeting, Charles Sturt University, Wagga Wagga, NSW 4 - 7 February, 2003. Editors J. Cashion, T. Finlayson, D. Paganin, A. Smith and G. Troup (Australian Institute of Physics, 2003) 11.

 

Comparisons of Gallium Nitride and Indium Nitride Properties after CF4/Argon Reactive Ion Etching

 M. Wintrebert-Fouquet, K. S. A. Butcher and S. K. H. Lam

Accepted for publication Material Research Society 2002 Fall Meeting. Material Research Society Symposium Proceedings Vol. 743 (2003) 267-272.

 

Optical and Structural Analysis of GaN Grown by Remote Plasma Enhanced Laser Induced Chemical Vapour Deposition
Afifuddin, K. S. A. Butcher, H. Timmers and T. L. Tansley

Physica Status Solidi C 0 (2002) 499-503.

 

Studies of the Plasma Related Oxygen Contamination of Gallium Nitride Grown by Remote Plasma Enhanced Chemical Vapour Deposition
K. S. A. Butcher, Afifuddin, P. P.-T. Chen and T. L. Tansley

Physica Status Solidi C 0 (2002) 156-160.

 

Recrystallization prospects for freestanding low temperature GaN grown using ZnO buffer layers

K. S. A. Butcher, Afifuddin, P. P.-T. Chen, M. Godlewski, A. Szcerbakow, E. M. Goldys, T. L.Tansley, and J. A. Freitas Jr

Journal of Crystal Growth 246 (2002) 237-243.

 

Crystal Size and Oxygen Segregation for Polycrystalline GaN

K. S. A. Butcher, H. Timmers, Afifuddin, P. P.-T. Chen, T. D. M. Weijers, E. M. Goldys, T. L.Tansley, R. G. Elliman, J. A. Freitas Jr

Journal of Applied Physics 92 (2002) 3397-3403.

 

Spatial Fluctuations and Localisation Effects in Optical Characteristics of p-doped GaN Films

E. M. Goldys, M. Godlewski, E. Kaminska, A. Piotrowska and K. S. A. Butcher

Physica Status Solidi B. 228 (2001) 365-369.

 

Cathodoluminescence Investigations of Interfaces in InGaN/GaN/ Sapphire Structures

M. Godlewski, E. M. Goldys, K. S. A. Butcher, M. R. Phillips, K. Pakula and J. M. Baranowski

Physica Status Solidi B. 228 (2001) 179-182.

 

Correlation of Oxygen Content and Crystal Size in Polycrystalline Gallium Nitride

H. Timmers, B. Hecking, K. S. A. Butcher, T. D. M. Weijers, R. G. Elliman, Afifuddin and T. L. Tansley

ANA-2001: Fourth Conference on Nuclear Science and Engineering in Australia, October 2001, Kings Cross, NSW, Australia (Sutherland, Australian Nuclear Association, 2001) 131-134.

 

UV Moderation of Nitride Films During Remote Plasma Enhanced Chemical Vapour Deposition

K. S. A. Butcher, Afifuddin, P.-T. Chen, E. M. Goldys and T. L. Tansley

Submitted to Physica Status Solidi A 188 (2001) 667-671.

 

Glass Substrates for GaN Using ZnO buffer Layers

K. S. A. Butcher, Afifuddin, Patrick P.-T. Chen, M. Godlewski, A. Szczerbakow,

E. M. Goldys, T. L. Tansley and J. A. Freitas Jr.

2000 Conference on Optoelectronic and Microelectronic Materials and Devices Proceedings, Melbourne Australia, 6-8 December 2000 (2000, IEEE Piscataway NJ) 535-538.

 

Growth and Characterisation of GaN Grown by Microwave Plasma Assisted Laser-induced Chemical Vapour Deposition

Afifuddin, K.S.A. Butcher, Patrick P.-T. Chen, E. M. Goldys, T. L. Tansley

2000 Conference on Optoelectronic and Microelectronic Materials and Devices Proceedings, Melbourne Australia, 6-8 December 2000 (2000, IEEE Piscataway NJ) 129-132.

 

The Properties of GaN films grown by plasma assisted laser-induced chemical vapour deposition, and the influence of heavy ion irradiation

Afifuddin, K. S. A. Butcher, T. L. Tansley, H. Timmers, R.G. Elliman, T.D.M. Weijers and T.R.Ophel,

2000 International Semiconducting and Insulating Materials Conference,
SIMC-XI, Editors C. (Jagadish and N. J. Welham, IEEE Publishing, 2000) 51-54.

 

Characterisation of microcrystalline GaN Grown  on quartz and on sapphire by laser and microwave plasma enhamced metalorganic chemical vapour deposition

M.J. Paterson, E.M. Goldys, H.Y. Zuo, T.L. Tansley, Jpn. J. Appl. Phys. 37 (1998) 426-431.

 

Photoconductive Decay in LCVD/PECVD Low Temperature Grown GaN

Bing Zhou, K.S.A.Butcher, H.Zou, X.Li and T.L.Tansley

Solid-St. Electron. 41 (1997) 279-281.

 

 

Microwave Plasma Assisted LCVD Growth and Characterisation of GaN

Bing Zhou, Xin Li, T.L.Tansley and K.S.A.Butcher

Appl. Surf. Sci. 100/101 (1996) 643-646.

 

Growth Mechanisms in Excimer Laser Photolytic Deposition of Gallium Nitride at 500o C.

Bing Zhou, Xin Li, T.L.Tansley and K.S.A.Butcher

J. Crystal Growth 160 (1996) 201-206.

 

Growth of GaN Films by Combined Laser and Microwave Plasma Enhanced Chemical Vapour Deposition

Bing Zhou, Xin Li, T.L.Tansley, K.S.A.Butcher and M.R.Phillips

J. Crystal Growth 151 (1995) 249-253.

 

Growth of Optoelectronic Materials of AlN, GaN and InN Films by UV Laser Induced MOCVD

Xin Li, Bing Zhou, K.S.A.Butcher, E.Florido, N.Syakir and T.L.Tansley

Proceedings of the 1994 Australian Compound Optoelectronic Materials and Devices Conference (Sydney, Semiconductor Science and Technology Laboratories Macquarie University, 1995) 43-48.

 

Growth and Characterisation of GaN Grown by Microwave Plasma Assisted LCVD

Bing Zhou, Xin Li, K.S.A.Butcher and T.L.Tansley.

13th International Vacuum Congress/ 9th International Conference on Solid Surfaces, September 1995, Yokohama, Japan.

 

GaN Growth and Characterisation Measurements using an ArF Excimer Laser

Bing Zhou, Xin Li, K.S.A.Butcher and T.L.Tansley

Proceedings of the 1994 Australian Compound Optoelectronic Materials and Devices Conference (Sydney, Semiconductor Science and Technology Laboratories Macquarie University, 1995) 171-173.

 

For Indium Nitride:

 

Nitrogen Depletion of Indium Nitride Films During Elastic Recoil Detection Analysis

S. K. Shrestha, H. Timmers, K. S. A. Scott Butcher, M. Wintrebert-Fouquet and  P. P.–T.  Chen

Nuclear Instruments and Methods in Physics Research B 234 (2005) 291-307.

 

InN, Latest Development and a Review of the Band-gap Controversy

K. S. A. Butcher and T. L. Tansley

Superlattices and Microstructures 38 (2005) 1-37.

 

Non-stoichiometry and Non-homogeneity in InN

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.-T. Chen, K. E. Prince,  H. Timmers, S. K. Shrestha, T. V. Shubina, S. V. Ivanov, R. Wuhrer, M. R. Phillips and B. Monemar

Physica Status Solidi C 2 (2005) 2263-2266.

 

Resonant Raman Spectroscopy on InN

M. Kuball, J. W. Pomeroy, M. Wintrebert-Fouquet, K. S. A. Butcher, Hai Lu, W. J. Schaff, T. V. Shubina, S. V. Ivanov, A. Vasson and J. Leymarie

Physica Status Solidi A 202 (2005) 763-767.

 

Revisiting Electrochromism in InN

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.–T.  Chen, R. Wuhrer and M. R. Phillips

Physica Status Solidi C 2 (2005) 2293- 2296.

 

Optical Properties of InN with Stoichiometry Violation and Indium Clustering

T. V. Shubina, S. V. Ivanov, V. N. Jmerik, M. M. Glazov, A. P. Kalvarskii,

M. G. Tkachman, A. Vasson, J. Leymarie, A. Kavokin, H. Amano, I. Akasaki,

K. S. A. Butcher, Q. Guo, B. Monemar, and P. S. Kop’ev

Physica Status Solidi A 202 (2005) 377-382.

 

Variations in the Apparent Optical Band-gap of RPE-CVD Grown Indium Nitride Thin Films

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.-T. Chen, T. L. Tansley and K. E. Prince, Proceedings of the 28th A&NZ Condensed Matter and Materials Meeting, Charles Sturt University, Wagga Wagga, NSW 3 - 6 February, 2004. Editor N. Savvides (Australian Institute of Physics, 2004) TP16.

 

Piezoelectricity in Indium Nitride

I. L. Guy, Z. Zheng, M. Wintrebert-Fouquet, K. S. A. Butcher , P. Chen, and T. L. Tansley

Journal of Crystal Growth  269 (2004) 72-76.

 

InN grown by remote plasma enhanced chemical vapor deposition

M. Wintrebert-Fouquet, K. S. A. Butcher, P. P. –T Chen

Journal of Crystal Growth 269 (2004) 134-138.

 

Indium nitride materials properties: experimental and theoretical

D. Alexandrov, K. S. A. Butcher and M. Wintrebert-Fouquet

Journal of Crystal Growth  269 (2004) 77-86.

 

Visible Emissions Near 1.9-2.2 eV From Hexagonal InN Films Grown By Electron Cyclotron Resonance Plasma-Assisted Molecular-Beam Epitaxy

T. Yodo, Y. Kitayama, K. Miyaki, H. Yona, Y. Harada K. E. Prince and K. S. A. Butcher

Journal of Crystal Growth  269 (2004) 145-154.

 

A Raman spectroscopy study on InN

M. Kuball, J.W. Pomeroy, M. Wintrebert-Fouquet, K.S.A. Butcher, Hai Lu,

and W.J. Schaff

Journal of Crystal Growth 269 (2004) 59-65.

 

Nitrogen Rich Indium Nitride

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.–T.  Chen, T. L. Tansley, H. Dou, S. K. Shrestha, H. Timmers, M. Kuball, K. E. Prince and J. E. Bradby

Journal of Applied Physics 95 (2004) 6124-6128.

 

Reliable ERD analysis of group-III nitrides despite severe nitrogen depletion

S. K. Shrestha, K. S. A. Scott Butcher, M. Wintrebert-Fouquet and H. Timmers

Nuclear Instruments and Methods in Physics Research B 219-220 (2004) 686-692.

 

Energy Band Gaps of InN Containing Oxygen and of the InxAl1-xN Interface Layer Formed during InN Film Growth

D. Alexandrov, K. S. A. Butcher and M. Wintrebert-Fouquet

Journal of Vacuum Science and Technology A 22 (2004) 954-961.

 

Accurate Stoichiometric Analysis of Polycrystalline Indium Nitride Films with Elastic Recoil Detection

S. K. Shrestha, H. Timmers, K.S.A. Scott Butcher and  M. Wintrebert-Fouquet.

Current Applied Physics 4 (2004) 237-240.  

 

Detailed Analysis of Absorption Data for Indium Nitride

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.–T. Chen, H. Timmers and S. K. Shrestha, submitted for the proceedings of the International Symposium on Non-Stoichiometry and Point Defects in Semiconductors (ISPN2003), Sendai Japan, March 2003.

 

A Study of Indium Nitride Films Grown Under Conditions Resulting in Apparent Band-gaps from 0.7 eV to 2.3 eV

K. S. A. Butcher, M. Wintrebert-Fouquet, Motlan, S. K. Shrestha, H. Timmers, K. E. Prince and T. L. Tansley

Material Research Society 2002 Fall Meeting. Material Research Society Symposium Proceedings Vol. 743 (2003) 707-712.

 

High sensitivity, high resolution X-ray photoelectron analysis of InN

M. Wintrebert-Fouquet, K. S. A. Butcher and Motlan.

Phys. Stat. Sol. C 0 (2003) 2785-2789.

 

Detailed Analysis of Absorption Data for InN

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.–T. Chen, H. Timmers and S. K. Shrestha

Materials Science in Semiconductor Processing 6 (2003) 351-354.

 

Indium Nitride Emerges

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.-T. Chen, T. L. Tansley, S. Srikeaw, S. Shrestha, R. G. Elliman and H. Timmers

Proceedings of the Australian Institute of Physics Biennial Congress 2002 (Editor D. Neilson, Causal Productions, Adelaide Australia, 2002) 340-342.

 

High Mobility Nitrides

K. S. A. Butcher, M. Wintrebert-Fouquet, P. P.-T. Chen, T. L. Tansley and S. Srikeaw

Material Research Society Symposium Proceedings Vol. 693 (2002) 341-346.

 

Ultraviolet Raman and Optical Transmission Studies of RF Sputtered Indium Nitride

K. S. A. Butcher, H. Dou, E. M. Goldys, T. L. Tansley and S. Srikeaw

Physica Status Solidi C 0 (2002) 373-376.

 

Electrical Properties of InN,

T. L. Tansley and E. M. Goldys in “Gallium Nitride and Related Semiconductors”, Eds J. H. Edgar and S. Strite (INSPEC, London 1999) 129-134

 

Physical Properties of InN,

T. L. Tansley and E. M. Goldys in “Gallium Nitride and Related Semiconductors”, Eds J. H. Edgar and S. Strite (INSPEC, London 1999) 123-8.

 

Analysis of indium nitride surface oxidation

C. P. Foley and J. Lyngdal, J. Vacuum Sci. & Tech. A, 5, (1987) 1708-1712.

 

Infrared absorption in indium nitride,

 T. L. Tansley and C. P. Foley, J. Appl. Phys, 60 (1986) 2092-2095.

 

Optical band gap of indium nitride.

T. L. Tansley and C. P. Foley, J. Appl. Phys., 59 (1986) 3241-3244.

 

Pseudopotential band structure of indium nitride.

T. L. Tansley and C. P. Foley , Phys. Rev. B.33 (1986)1430-1433.

 

Morphology and structure of indium nitride films

T. L. Tansley and C. P. Foley, Appl. Surf. Sci, 22-23 (1985) 663-669.

 

Polycrystalline indium nitride films.

T. L. Tansley and C. P. Foley, Semi-Insulating III-V materials (Shiva Publishing 1984, Nantwich, UK) 497-500.

 

Electron mobility in indium nitride,

T. L. Tansley and C. P. Foley, Electronics Letters, 20 (1984)1066-1068.

 

Proceedings Edited

 

Proceedings of the First International Indium Nitride Workshop

Editor: K. S. A. Butcher

Journal of Crystal Growth 269 (Elsevier, Amsterdam, 2004) 1-180.

 

European Materials Research Society 2004, Symposium L. InN, GaN, AlN and Related Materials, Their Heterostructures, and Devices

Editors: O. Briot, K. S. A. Butcher, B. Gil, C. Wetzel and A. Yoshikawa

Superlattices and Microstructures 36 issues 4-6 (2004) 369-909.