CN1190081A

CN1190081A - Chemical reduction process of preparing indium arsenide and gallium arsenide

Info

Publication number: CN1190081A
Application number: CN97101146A
Authority: CN
Inventors: 李亚栋; 段镶锋; 钱逸泰
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 1997-02-03
Filing date: 1997-02-03
Publication date: 1998-08-12
Anticipated expiration: 2017-02-03
Also published as: CN1082032C

Abstract

After the chloride of Ga or In and As in a certain ratio are mixed and to benzene, methylbenzene or other non-water organic solvent, reducing agent in 110-350% of stoichiometrical value is added and reacted under sealing condition and at 120-350 deg.c. After solid-liquid separation, successive washing with organic solvent, dilute hydrochloric acid and distilled water and vacuum drying, product InAs or GaAs is produced. Without using severe toxic gas AsH3, the said preparation process is simple and safe, and is suitable for industrial production.

Description

The chemical reduction process of preparing of a kind of indium arsenide, gallium arsenide

The present invention relates to the preparation method of the preparation method of semiconductor material, particularly indium arsenide, gallium arsenide.

The existing method for preparing indium arsenide, gallium arsenide mainly contains: 1. two-tube electric stove metal steam high temperature vapour deposition process, 2. molecular beam epitaxy technique (MBE), 3. organometallics chemical Vapor deposition process (MOCVD), 4. liquid-phase growth method (Solution-Liquid-Solid (irowth).

1956, on 1562 pages of U.S.'s " physical comment " (Physics Review) the 104th volumes, reported first the synthetic InAs method of vacuum high-temperature vapour deposition process, but require in high vacuum (＜10 ^-5τ), react under the two-tube electric furnace hot conditions (＞950 ℃), also must strict control As in the reaction process and the vapour pressure of In, otherwise the semiconductor compound that obtains is with the substantial deviation stoichiometric ratio.This method will realize quite difficulty of industrial production, still is unrealized so far.

1989, in U.S.'s " science " (Science), the 245th volume, the synthetic III-V family of the molecular beam epitaxy technique of 391 pages of reports semi-conductor.Nineteen eighty-three, in U.S.'s " Applied Physics communication " (Applied PhysicsLetters), the 43rd volume, 658 pages of metal organic chemical compound vapor deposition methods of having reported synthetic III-V family semiconductor compound.Nineteen ninety-five,, 1791 pages, adopt liquid-phase growth method successfully to synthesize InAs, GaAs at U.S.'s " science " the 270th volume.Aforesaid method all will be by the volatile organometallics of gallium or indium and the AsH of severe toxicity ₃Under comparatively high temps, react, and owing to the metal-organic preparation of reaction raw materials Ga, In, purifying are quite difficult, severe reaction conditions, process complexity, the cost height, reaction process is quite difficult to be controlled, and also requires to reach in the reaction process anhydrous, the oxygen free operation of strictness, requires high to equipment and synthetic control thereof, therefore increase the difficulty of aforesaid method greatly, on industrial production, lacked practicality.

The object of the present invention is to provide a kind of employing chemical reduction method to synthesize InAs, the method for GaAs compound can and be avoided hypertoxic AsH at lesser temps ₃Under the gas condition, can be raw material with the muriate of indium cheap and easy to get, gallium, arsenic, under simple reaction conditions, synthesize InAs, the GaAs compound semiconductor materials be to overcome the above-mentioned defective that exists in the prior art.

InAs of the present invention, the preparation method of GaAs is characterized in that the GaCl by chemical reaction metering ratio ₃And/or InCl ₃, with AsCl ₃Lump together, in benzene, toluene or other non-aqueous organic solvent, add by the reductive agent of reaction metering than 1.1 to 3.5 times, in airtight reactor, under 120～350 ℃ of temperature condition, react, solid-liquid separation then, product is washed till neutrality with organic solvent, 1-2mol/l dilute hydrochloric acid, distilled water successively, 40～80 ℃ of vacuum-dryings.

Because the present invention adopts the non-aqueous organic solvent system, reaction is sealed in the reactor carries out, equipment is simple, easy to operate and safe, avoid adopting operative technique anhydrous, that this class difficulty of anaerobic is bigger, overcome prior art and the hidden danger of leaking has easily taken place, and solvent is recyclable recycles because of hypertoxic gas raw material.

Employing the inventive method can be by control reaction temperature and InAs, GaAs nanometer superfine powder more than the reaction times acquisition median size 10nm.To satisfy the demand in different application field.

The inventive method is compared with existing method, since can be directly be raw material with the muriate of Ga, In, As, simple substance, oxide compound or other salt that these raw materials are easy to by them are transformed, so the inventive method has the starting material cheapness, is easy to get, equipment is simple, easy, the safety of operation control has avoided using hypertoxic gas AsH ₃Be difficult to prepare, the organometallics of unsettled Ga or In, both reduced cost, guaranteed the performance of product, reduced the threat of environmental pollution and the danger of production operation process again.This technology scope of application is extensive, and the product of acquisition can be widely used in the requirement in different application field, is easy to suitability for industrialized production.

Below prepare several embodiment of InAs, GaAs for the inventive method.

Embodiment 1. takes by weighing In ₂O ₃2.876 gram, As ₂O ₃1.978 gram, place beaker, add the dense HCl dissolving of 15ml, slowly heating is evaporated to 1/3 of original volume, changes over to then among the stainless steel reaction under high pressure Fu of inner liner polytetrafluoroethylene, add xylene solvent to 150ml, add zinc powder 2.145 grams, be sealed in the reactor, in 3 days (72 hours) of 180 ℃ of reactions, be cooled to room temperature, open still, suction filtration promptly gets the grey black product, washs two enlightening with the 20ml xylene solvent at every turn, use dilute hydrochloric acid (1-2mol/l) washing 3-4 time again, be washed with distilled water to neutrality again, at 40-80 ℃, vacuum-drying, promptly get purified InAs product, X-ray diffraction and chemical analysis identify that product is pure InAs, show the about 20-30nm of particulate median size by Electronic Speculum.

Embodiment 2. takes by weighing InCl ₃2.212 gram, AsCl ₃1.813 gram in autoclave, adds 150ml benzene, add 0.85 then and digest pure metal Mg powder, sealed reactor was 150 ℃ of reactions 2-3 days, cool to room temperature, suction filtration promptly gets the grey black product, through solvent benzol washing, dilute hydrochloric acid washing, use distilled water wash more earlier, drain the back in 60-80 ℃ of vacuum-drying, promptly get product InAs, through the identification of phases of X-ray diffraction thing and chemical analysis, product is pure InAs, and median size is about 20-30nm.

Embodiment 3. takes by weighing InCl ₃2.212 gram, AsCl ₃1.813 gram, place autoclave, add 150ml benzene, add Zn powder 2.2 grams, be enclosed in the autoclave reaction 3 days in 350 ℃, be cooled to room temperature, promptly get the grey black product, wash through benzene successively, the dilute hydrochloric acid washing, distilled water wash is drained back vacuum-drying under 60-80 ℃ of condition and is promptly got purified InAs, GaAs.The product median size is greater than 50nm.As the crystal of desire acquisition larger particles, can keep under the situation of original reaction conditions according to the crystal growth situation, prolong reaction times to crystal and grow to required size.

Embodiment 4. gets In ₂O ₃2.87 gram, As ₂O ₃1.97 gram, add 15ml concentrated hydrochloric acid dissolving after, slowly be evaporated to 1/3 of original volume, change in the autoclave, add benzene solvent 150ml, add NaH ₂PO ₂H ₂O2.5 gram or sodium Metal 99.5 4 grams are sealed in the autoclave 250 ℃ of reactions 3 days rapidly, and after the cooling, suction filtration, product are washed with distilled water to filtrate again and are neutral through rare HCl (1-2mol/l) washing 3-4 time, in 60-80 ℃ of drying, promptly get purified InAs product.

If with above-mentioned reaction raw materials InCl ₃Or In ₂O ₃Change the GaCl of equimolar amount into ₃, then products therefrom is GaAs.If InCl with certain proportioning ₃And GaCl ₃Replace above-mentioned InCl ₃Also can obtain (GaIn) As mixture.

Claims

1. InAs, the preparation method of GaAs is characterized in that the GaCl by chemical reaction metering ratio ₃And/or InCl ₃, with AsCl ₃Mix, in benzene, toluene or other non-aqueous organic solvent, add by the reductive agent of reaction metering than 1.1 to 3.5 times, in airtight reactor, under 120～350 ℃ of temperature condition, react, solid-liquid separation then, product is washed till neutrality with organic solvent, 1-2mol/l dilute hydrochloric acid, distilled water successively, 40-80 ℃ of vacuum-drying.