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Gallium arsenide

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Gallium arsenide
Names
IUPAC name
Gallium arsenide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.013.741 Edit this at Wikidata
  • Ga#As
Properties
GaAs
Molar mass 144.645 g/mol
Appearance Gray cubic crystals
Melting point 1238 °C (1511 K)
< 0.1 g/100 ml (20 °C)
Structure
Zinc Blende
Linear
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
1
1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Gallium arsenide (GaAs) is a compound of two elements, gallium and arsenic. It is an important semiconductor and is used to make devices such as microwave frequency integrated circuits (ie, MMICs), infrared light-emitting diodes, laser diodes and solar cells.

Preparation and chemistry

Gallium arsenide can be prepared from the elements and a number of industrial processes use this, for example[1]:

  • the crystal growth using a horizontal zone furnace (Bridgman-Stockbarger technique) where Ga and Arsenic vapour react and deposit on a seed crystal at the cooler end of the furnace.
  • LEC (liquid encapsulated Czochralski) growth

Alternative methods for producing films of GaAs include[2][1] :

2Ga + 2AsCl3 → 2GaAs + 3Cl2
Ga(CH3)3 + AsH3 → GaAs + CH4

Wet etching of GaAs industrially uses an oxidising agent e.g. hydrogen peroxide or bromine water[3], 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"[4]e.g.:

GaAs + H2O2 + "HA" → "GaA" complex + H3AsO4 + 4H2O

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 (tBuGaS)7[5]

Comparison with silicon

GaAs advantages

GaAs has some electronic properties which are superior to those of silicon. It has a higher saturated electron velocity and higher electron mobility, allowing transistors made from it to function at frequencies in excess of 250 GHz. Also, GaAs devices generate less noise than silicon devices when operated at high frequencies. They can also be operated at higher power levels than the equivalent silicon device because they have higher breakdown voltages. These properties recommend GaAs circuitry in mobile phones, satellite communications, microwave point-to-point links, and some 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).

Due to its high switching speed, GaAs would seem to be ideal for computer applications, and for some time in the 1980s many thought that the microelectronics market would switch from silicon to GaAs. The first attempted changes 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 vapour 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.

Silicon advantages

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.

The second major advantage of Si is the existence of silicon dioxide—one of the best insulators. Silicon dioxide can easily be incorporated onto silicon circuits, and such layers are adherent to the underlying Si. GaAs does not form a stable adherent insulating layer.

The third, and perhaps most important, advantage of silicon is that it possesses a much higher hole mobility. 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 logic circuits have much higher power consumption, which has made them unable to compete with silicon logic circuits.

Unlike silicon cells, GaAs cells are relatively insensitive to heat. On the other hand, GaAs has an absorptivity so high it requires a cell only a few microns thick to absorb sunlight (crystalline silicon requires a layer 100 microns or more thick) [6].

Other applications

Solar cells and detectors

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 Zhores Alferov and his team in the USSR.[7][8][9] 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.

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.[10]

Light emission devices

GaAs has been used to produce (near-infrared) laser diodes since the early 1960s.[11]

Single crystals of gallium arsenide can be manufactured by the Bridgeman technique, as the Czochralski process is difficult for this material due to its mechanical properties. However, an encapsulated Czochralski method is used to produce ultra-high purity GaAs for semi-insulators.

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

Safety

The toxicological properties of gallium arsenide have not been thoroughly investigated. On one hand, due to its arsenic content, it is considered highly toxic and carcinogenic. On the other hand, the crystal is stable enough that ingested pieces may be passed with negligible absorption by the body. When ground into very fine particles, such as in wafer-polishing processes, the high surface area enables more reaction with water releasing some arsine and/or dissolved arsenic. 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.[12]. California lists gallium arsenide as a carcinogen[13]

See also

References

  1. ^ a b S. J. Moss, A. Ledwith (1987) The Chemistry of the Semiconductor Industry, Springer, ISBN 0216920051
  2. ^ Lesley Smart, Elaine A. Moore, (2005), Solid State Chemistry: An Introduction ,CRC, ISBN 0748775161
  3. ^ M. R. Brozel, G. E. Stillman (1996)Properties of Gallium Arsenide, IEE Inspec, ISBN 085296885X
  4. ^ Oxidative dissolution of gallium arsenide and separation of gallium from arsenic, United States Patent 4759917, Coleman, J. P.,Monzyk, B. F (1988)
  5. ^ Chemical vapor deposition from single organometallic precursors, A. R. Barron, M. B. Power, A. N. MacInnes, A. F.Hepp, P. P. Jenkins, US Patent 5300320 (1994)
  6. ^ http://www1.eere.energy.gov/solar/tf_single_crystalline.html
  7. ^ 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))]
  8. ^ Nanotechnology in energy applications, pdf, p.24
  9. ^ Nobel Lecture by Zhores Alferov, pdf, p.6
  10. ^ Glasgow University report on CERN detector
  11. ^ R. C. Miller, F. M. Ryan and P. R. Emtage, “Uniaxial Strain Effects in Gallium Arsenide Laser Diodes,” 7th Intl. Conf. Phys. Semicond., Academic Press, Paris, 1964.
  12. ^ Environment, health and safety issues for sources used in MOVPE growth of compound semiconductors; D V Shenai-Khatkhate, R Goyette, R L DiCarlo and G Dripps, Journal of Crystal Growth, vol. 1-4, pp. 816-821 (2004); doi:10.1016/j.jcrysgro.2004.09.007
  13. ^ http://www.oehha.org/prop65/prop65_list/Newlist.html
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