Gallium arsenide

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Gallium arsenide
Samples of gallium arsenide
Gallium arsenide crystal.jpg
Identifiers
CAS number 1303-00-0 YesY
PubChem 14770
ChemSpider 14087 YesY
EC number 215-114-8
UN number 1557
MeSH gallium+arsenide
RTECS number LW8800000
Jmol-3D images Image 1
Properties
Molecular formula GaAs
Molar mass 144.645 g/mol
Appearance Very dark red, vitreous crystals
Odor garlic-like when moistened
Density 5.3176 g/cm3
Melting point 1,238 °C (2,260 °F; 1,511 K)
Solubility in water insoluble
Solubility soluble in HCL
insoluble in ethanol, methanol, acetone
Band gap 1.424 eV (at 300 K)
Electron mobility 8500 cm2/(V·s) (at 300 K)
Thermal conductivity 0.55 W/(cm·K) (at 300 K)
Refractive index (nD) 3.8[1]
Structure
Crystal structure Zinc blende
Space group T2d-F-43m
Lattice constant a = 565.35 pm
Coordination
geometry
Tetrahedral
Molecular shape Linear
Hazards
MSDS External MSDS
GHS pictograms The skull-and-crossbones pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The environment pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)
GHS hazard statements H301, H331, H410
GHS precautionary statements P261, P273, P301+310, P311, P501
EU classification Toxic T Dangerous for the Environment (Nature) N
R-phrases R23/25, R50/53
S-phrases (S1/2), S20/21, S28, S45, S60, S61
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g., phosphorus Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 N (verify) (what is: YesY/N?)
Infobox references

Gallium arsenide (GaAs) is a compound of the elements gallium and arsenic. It is a III/V semiconductor, and is used in the manufacture of devices such as microwave frequency integrated circuits, monolithic microwave integrated circuits, infrared light-emitting diodes, laser diodes, solar cells and optical windows.

GaAs is often used as a substrate material for the epitaxial growth of other III-V semiconductors including: InGaAs and GaInNAs.

Preparation and chemistry[edit]

In the compound, gallium has a +3 oxidation state. Gallium arsenide single crystals can be prepared by three industrial processes:[2]

  • The vertical gradient freeze (VGF) process. Most GaAs wafers are produced using this process.[3]
  • Crystal growth using a horizontal zone furnace in the Bridgman-Stockbarger technique, in which gallium and arsenic vapors react, and free molecules deposit on a seed crystal at the cooler end of the furnace.
  • Liquid encapsulated Czochralski (LEC) growth is used for producing high-purity single crystals that can exhibit semi-insulating characteristics (see below).

Alternative methods for producing films of GaAs include:[2][4]

2 Ga + 2 AsCl
3
→ 2 GaAs + 3 Cl
2
Ga(CH
3
)
3
+ AsH
3
→ GaAs + 3 CH
4
4 Ga + As
4
→ 4 GaAs

or

2 Ga + As
2
→ 2 GaAs

Oxidation of GaAs occurs in air and degrades performance of the semiconductor. The surface can be passivated by depositing a cubic gallium(II) sulfide layer using a tert-butyl gallium sulfide compound such as (t
BuGaS)
7
.[5]

Semi-insulating crystals[edit]

If a GaAs boule is grown with excess arsenic present, it gets certain defects, in particular arsenic antisite defects (an arsenic atom at a gallium atom site within the crystal lattice). The electronic properties of these defects (interacting with others) cause the Fermi level to be pinned to near the center of the bandgap, so that this GaAs crystal has very low concentration of electrons and holes. This low carrier concentration is similar to an intrinsic (perfectly undoped) crystal, but much easier to achieve in practice. These crystals are called "semi-insulating", reflecting their high resistivity of 107–109 Ω·cm (which is quite high for a semiconductor, but still much lower than a true insulator like glass).[6]

Etching[edit]

Wet etching of GaAs industrially uses an oxidizing agent such as hydrogen peroxide or bromine water,[7] and the same strategy has been described in a patent relating to processing scrap components containing GaAs where the Ga3+
is complexed with a hydroxamic acid ("HA"), for example:[8]

GaAs + H
2
O
2
+ "HA" → "GaA" complex + H
3
AsO
4
+ 4 H
2
O

This reaction produces arsenic acid.

Comparison with silicon[edit]

GaAs advantages[edit]

Some electronic properties of gallium arsenide are superior to those of silicon. It has a higher saturated electron velocity and higher electron mobility, allowing gallium arsenide transistors to function at frequencies in excess of 250 GHz. Unlike silicon junctions, GaAs devices are relatively insensitive to heat owing to their wider bandgap. Also, GaAs devices tend to have less noise than silicon devices, especially at high frequencies. This is a result of higher carrier mobilities and lower resistive device parasitics. These properties recommend GaAs circuitry in mobile phones, satellite communications, microwave point-to-point links and higher frequency radar systems. It is used in the manufacture of Gunn diodes for generation of microwaves.

Another advantage of GaAs is that it has a direct band gap, which means that it can be used to emit light efficiently. Silicon has an indirect bandgap and so is very poor at emitting light. Nonetheless, recent advances may make silicon LEDs and lasers possible.

As a wide direct band gap material with resulting resistance to radiation damage, GaAs is an excellent material for space electronics and optical windows in high power applications.

Because of its wide bandgap, pure GaAs is highly resistive. Combined with the high dielectric constant, this property makes GaAs a very good electrical substrate and unlike Si provides natural isolation between devices and circuits. This has made it an ideal material for microwave and millimeter wave integrated circuits, MMICs, where active and essential passive components can readily be produced on a single slice of GaAs.

One of the first GaAs microprocessors was developed in the early 1980s by the RCA corporation and was considered for the Star Wars program of the United States Department of Defense. Those processors were several times faster and several orders of magnitude more radiation hard than silicon counterparts, but they were rather expensive.[9] Other GaAs processors were implemented by the supercomputer vendors Cray Computer Corporation, Convex, and Alliant in an attempt to stay ahead of the ever-improving CMOS microprocessor. Cray eventually built one GaAs-based machine in the early 1990s, the Cray-3, but the effort was not adequately capitalized, and the company filed for bankruptcy in 1995.

Complex layered structures of gallium arsenide in combination with aluminium arsenide (AlAs) or the alloy AlxGa1-xAs can be grown using molecular beam epitaxy (MBE) or using metalorganic vapor phase epitaxy (MOVPE). Because GaAs and AlAs have almost the same lattice constant, the layers have very little induced strain, which allows them to be grown almost arbitrarily thick. This allows for extremely high performance high electron mobility, HEMT transistors and other quantum well devices.

Silicon advantages[edit]

Silicon has three major advantages over GaAs for integrated circuit manufacture. First, silicon is abundant and cheap to process. Si is highly abundant in the Earth's crust, in the form of silicate minerals. The economy of scale available to the silicon industry has also reduced the adoption of GaAs.

In addition, a Si crystal has an extremely stable structure mechanically and it can be grown to very large diameter boules and can be processed with very high yields. It is also a decent thermal conductor, thus enabling very dense packing of transistors that need to get rid of their heat of operation, all very desirable for design and manufacturing of very large ICs. Such good mechanical characteristics also makes it a suitable material for the rapidly developing field of nanoelectronics.

The second major advantage of Si is the existence of a native oxide (silicon dioxide), which is used as an insulator in electronic devices. Silicon dioxide can easily be incorporated onto silicon circuits, and such layers are adherent to the underlying Si. GaAs does not have a native oxide and does not easily support a stable adherent insulating layer.[citation needed]

The third, and perhaps most important, advantage of silicon is that it possesses a much higher hole mobility.[citation needed] This high mobility allows the fabrication of higher-speed P-channel field effect transistors, which are required for CMOS logic. Because they lack a fast CMOS structure, GaAs circuits must use logic styles which have much higher power consumption; this has made GaAs circuits less able to compete with silicon logic circuits.

For manufacturing solar cells, silicon has relatively low absorptivity for the sunlight meaning about 100 micrometers of Si is needed to absorb most sunlight. Such a layer is relatively robust and easy to handle. In contrast, the absorptivity of GaAs is so high that only a few micrometers of thickness are needed to absorb all of the light. Consequently GaAs thin films must be supported on a substrate material.[10]

Silicon is a pure element, avoiding the problems of stoichiometric imbalance and thermal unmixing of GaAs.[citation needed]

Silicon has a nearly perfect lattice, impurity density is very low and allows very small structures to be built (currently down to 16 nm[11]). GaAs in contrast has a very high impurity density,[citation needed] which makes it difficult to build integrated circuits with small structures, so the 500 nm process is a common process for GaAs.

High-efficiency, triple-junction gallium arsenide solar cells covering the MidSTAR-1 satellite

Other applications[edit]

Solar cells and detectors[edit]

Another important application of GaAs is for high efficiency solar cells. Gallium arsenide (GaAs) is also known as single-crystalline thin film and are high-cost high-efficiency solar cells.

In 1970, the first GaAs heterostructure solar cells were created by the team led by Zhores Alferov in the USSR.[12][13][14] In the early 1980s, the efficiency of the best GaAs solar cells surpassed that of silicon solar cells, and in the 1990s GaAs solar cells took over from silicon as the cell type most commonly used for Photovoltaic arrays for satellite applications. Later, dual- and triple-junction solar cells based on GaAs with germanium and indium gallium phosphide layers were developed as the basis of a triple-junction solar cell, which held a record efficiency of over 32% and can operate also with light as concentrated as 2,000 suns. This kind of solar cell powers the rovers Spirit and Opportunity, which are exploring Mars' surface. Also many solar cars utilize GaAs in solar arrays.

GaAs-based devices hold the world record for the highest-efficiency single-junction solar cell at 28.8%.[15] This high efficiency is attributed to the extreme high quality GaAs epitaxial growth, surface passivation by the AlGaAs,[16] and the promotion of photon recycling by the thin film design.[17]

Complex designs of AlxGa1−xAs-GaAs devices can be sensitive to infrared radiation (QWIP).

GaAs diodes can be used for the detection of X-rays.[18]

Light-emission devices[edit]

Band structure of GaAs. The direct gap of GaAs results in efficient emission of infrared light at 1.424 eV (~870 nm).

GaAs has been used to produce (near-infrared) laser diodes since 1962.[19]

Safety[edit]

The environment, health and safety aspects of gallium arsenide sources (such as trimethylgallium and arsine) and industrial hygiene monitoring studies of metalorganic precursors have been reported.[20] California lists gallium arsenide as a carcinogen.[21] However, there is no evidence for a primary carcinogenic effect of GaAs.[22]

See also[edit]

References[edit]

  1. ^ Refractive index of GaAs. Ioffe database
  2. ^ a b Moss, S. J. and Ledwith, A. (1987). The Chemistry of the Semiconductor Industry. Springer. ISBN 0-216-92005-1. 
  3. ^ Scheel, Hans J., and Tsuguo Fukuda. (2003). Crystal Growth Technology. Wiley. ISBN 0471490598. 
  4. ^ Smart, Lesley and Moore, Elaine A. (2005). Solid State Chemistry: An Introduction. CRC Press. ISBN 0-7487-7516-1. 
  5. ^ "Chemical vapor deposition from single organometallic precursors" A. R. Barron, M. B. Power, A. N. MacInnes, A. F.Hepp, P. P. Jenkins U.S. Patent 5,300,320 (1994)
  6. ^ Dopants and Defects in Semiconductors, by Matthew D. McCluskey, Eugene E. Haller, pp. 41 and 66, ISBN 978-1439831526
  7. ^ Brozel, M. R. and Stillman, G. E. (1996). Properties of Gallium Arsenide. IEEE Inspec. ISBN 0-85296-885-X. 
  8. ^ "Oxidative dissolution of gallium arsenide and separation of gallium from arsenic" J. P. Coleman and B. F. Monzyk U.S. Patent 4,759,917 (1988)
  9. ^ Šilc, Von Jurij; Robič, Borut and Ungerer, Theo (1999). Processor architecture: from dataflow to superscalar and beyond. Springer. p. 34. ISBN 3-540-64798-8. 
  10. ^ Single-Crystalline Thin Film. US Department of Energy
  11. ^ Handy, Jim (17 July 2013) Micron NAND Reaches 16nm. thememoryguy.com
  12. ^ Alferov, Zh. I., V. M. Andreev, M. B. Kagan, I. I. Protasov and V. G. Trofim, 1970, ‘‘Solar-energy converters based on p-n AlxGa1-xAs-GaAs heterojunctions,’’ Fiz. Tekh. Poluprovodn. 4, 2378 (Sov. Phys. Semicond. 4, 2047 (1971))
  13. ^ Nanotechnology in energy applications. im.isu.edu.tw. 16 November 2005 (in Chinese) p. 24
  14. ^ Nobel Lecture by Zhores Alferov at nobelprize.org, p. 6
  15. ^ Yablonovitch, Eli; Miller, Owen D.; Kurtz, S. R. (2012). "The opto-electronic physics that broke the efficiency limit in solar cells". 2012 38th IEEE Photovoltaic Specialists Conference. p. 001556. doi:10.1109/PVSC.2012.6317891. ISBN 978-1-4673-0066-7. 
  16. ^ Schnitzer, I. et al. (1993). "Ultrahigh spontaneous emission quantum efficiency, 99.7% internally and 72% externally, from AlGaAs/GaAs/AlGaAs double heterostructures". Applied Physics Letters 62 (2): 131. doi:10.1063/1.109348. 
  17. ^ Wang, X. et al. (2013). "Design of GaAs Solar Cells Operating Close to the Shockley–Queisser Limit". IEEE Journal of Photovoltaics 3 (2): 737. doi:10.1109/JPHOTOV.2013.2241594. 
  18. ^ Glasgow University report on CERN detector. Ppewww.physics.gla.ac.uk. Retrieved on 2013-10-16.
  19. ^ Hall, Robert N.; Fenner, G. E.; Kingsley, J. D.; Soltys, T. J. and Carlson, R. O. (1962). "Coherent Light Emission From GaAs Junctions". Physical Review Letters 9 (9): 366–369. Bibcode:1962PhRvL...9..366H. doi:10.1103/PhysRevLett.9.366. 
  20. ^ Shenai-Khatkhate, D V; Goyette, R; DiCarlo, R L and Dripps, G (2004). "Environment, health and safety issues for sources used in MOVPE growth of compound semiconductors". Journal of Crystal Growth 272 (1–4): 816–821. Bibcode:2004JCrGr.272..816S. doi:10.1016/j.jcrysgro.2004.09.007. 
  21. ^ "Chemicals Listed Effective August 1, 2008 as Known to the State of California to Cause Cancer or Reproductive Toxicity: gallium arsenide, hexafluoroacetone, nitrous oxide and vinyl cyclohexene dioxide". OEHHA. 2008-08-01. 
  22. ^ Bomhard, E. M.; Gelbke, H.; Schenk, H.; Williams, G. M.; Cohen, S. M. (2013). "Evaluation of the carcinogenicity of gallium arsenide". Critical Reviews in Toxicology 43 (5): 436–466. doi:10.31.109/104084444.2013.792329/. 

External links[edit]