CN103147038A - Method of preparing GaAs thin-film material - Google Patents
Method of preparing GaAs thin-film material Download PDFInfo
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- CN103147038A CN103147038A CN2012105523656A CN201210552365A CN103147038A CN 103147038 A CN103147038 A CN 103147038A CN 2012105523656 A CN2012105523656 A CN 2012105523656A CN 201210552365 A CN201210552365 A CN 201210552365A CN 103147038 A CN103147038 A CN 103147038A
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Abstract
The invention discloses a method of preparing a GaAs thin-film material. The method comprises steps as follows: using Ga 203, As 203 and activated carbon C as raw materials; adding absolute ethyl alcohol corresponding to 50-100% of solid raw materials in weight; after grinding the materials uniformly, using 10-15 MPa of pressure to press the materials into a sheet with thickness of 1-10 mm; then placing the sheet in a reactor corundum crucible; vacuumizing with high-purity nitrogen; permuting the reactor corundum crucible until oxygen concentration reaches a ppm level; then using mixed gas to vacuumize and permute the reactor corundum crucible once or twice; vacuumizing to 7-13 Pa; controlling a rate of temperature increase to be within a range of 5-10 DEG C per minute; heating a reaction zone until the temperature of the reaction zone rises to a range of 1200-1250 DEG C; heating a sediment zone until the temperature of the sediment zone rises to a range of 600-800 DEG C; keeping the temperature constant for 3-4 hours when vacuum degree is kept no less than minus 0.08 MPa; cooling naturally until the temperature drops to the room temperature after the temperature of the reaction zone reaches a predetermined temperature; and obtaining a grey black GaAs thin film after filling the reactor corundum crucible with the mixed gas. According to the method of preparing the GaAs thin-film material, used raw materials are simple, low in price, and easy to obtain, and the raw materials are either solid or non-toxic gas, are free from polluting the environment, and do not threat the safety of an operator.
Description
Technical field
The present invention relates to thin-film material and manufacture field, particularly relate to a kind of method of the GaAs of preparation thin-film material.
Background technology
Gallium arsenide (GaAs) is the semiconductor material formed by the element Ga of IIIA family and VA family elements A s chemical combination of synthetic.Molecular formula is GaAs.Under room temperature, energy gap is 1.42eV, and GaAs belongs to lattice of zinc blende type structure, lattice parameter 5.65 * 10
-10m, belong to direct transition type energy band structure with indium phosphide (InP).Gallium arsenide is gray solid darkly, 1238 ℃ of fusing points.It is below 600 ℃, can existence stable in the air, and be not non-oxidizing acid attack.
Gallium arsenide was in semiconductor material, has the material of many-sided advantage concurrently, and gallium arsenide entered the substantive application stage in 1964.Gallium arsenide can be made resistivity and exceed 3 semi-insulating highly resistant materials more than the order of magnitude than silicon, germanium, is used for making unicircuit substrate, infrared eye, γ photon detector etc.Due to its electronic mobility than silicon large 5～6 times, therefore obtaining important application making aspect microwave device and high-speed digital circuit.The advantages such as the semiconducter device made from gallium arsenide has high frequency, high temperature, low-temperature performance is good, noise is little, capability of resistance to radiation is strong.In addition, can also be for making transferring device-bulk effect device.
GaAs has some than the better characteristic electron of Si, makes GaAs can be used in the occasion higher than 250GHz.If, when the GaAs of equivalence and Si element are operating in high frequency, GaAs can produce less noise simultaneously.Simultaneously because GaAs has higher disruptive voltage, so GaAs is more suitable for operating in high-power occasion than same Si element.Due to these characteristics, the GaAs circuit can be used in the aspects such as mobile telephone, satellite communication, the point-to-point line of microwave, radar system.GaAs once was used for making gunn diode, microwave diode and Gunn diode) with launched microwave.Because GaAs is the semiconductor material of direct band gap, so can be used for luminous.And Si is indirect bandgap material, can only launch very faint light.Therefore, GaAs application prospect in LED is extensive.
Gallium arsenide plays an important role in contemporary microelectronics and photoelectronic industry, and its product 50% is applied in military affairs, space flight aspect, and 30% for communication aspects, and all the other are for the network equipment, computer and testing tool aspect.Due to the good high frequency characteristics of gallium arsenide, it is widely used in manufacturing radio communication and optical communication device, and the semi-insulating GaAs monocrystalline has become the main raw of manufacturing HIGH-POWERED MICROWAVES, millimeter wave communication device and unicircuit., yellow led red, orange for optical radiation, solar cell, infrared eye, mobile communication, optical-fibre communications, wire television, satellite communications, car radar, infrared LED, high brightness, semiconductor laser diode, military night vision equipment and space flight high performance solar batteries.
Prediction according to U.S. Silicon Valley Strategies company, within 2000, the wireless communication devices market requirement of the whole world based on GaAs material is 1,700,000,000 dollars, wherein the demand of gallium arsenide polished section and epitaxial wafer is 600,000,000 dollars, and will reach 2,500,000,000 dollars in 2005, and annual growth reaches 30%.
Because gallium arsenide can be processed photooptical data on the same chip simultaneously, thereby be widely used in many optoelectronic areas such as remote control, mobile phone, DVD computer peripheral equipment, illumination.In addition, because its electronic mobility is higher 6 times than silicon, gallium arsenide becomes the requisite of ultra-high speed, ultra-high frequency device and unicircuit.It also is widely used in military field, is the important materials of laser-guided bomb.
The very important application of another of GaAs is high efficiency solar cell.In the time of 1970, Zhores Alferov and his team make the solar cell of first GaAs heterojunction structure in the Soviet Union.The three interface solar cells made from GaAs, Ge and tri-kinds of materials of InGaP, have the efficiency more than 32%, and may operate in the light under 2,000 suns.This solar cell once was used in surveys areographic robot: spirit ramber (spirit rover) and chance ramber (opportunity rover).And a lot of solar cells are all the arrays of making of GaAs.
Because the lattice parameter of GaAs and AlAs is almost the same, so usually can utilize molecular beam epitaxy (molecular beam epitaxy, MBE) or metal organic vapor metal-organic vapor phase epitaxy, MOVPE), also be called Metalorganic Chemical Vapor Deposition (metal-organic chemical vapor deposition, MOCVD), form heterojunction structure on GaAs, as growth aluminium arsenide (AlAs) or aluminum gallium arsenide (Al
xga
1-xas) alloy.Because become longer ply stress very little, so almost can grow up to thickness arbitrarily.
Utilize horizontal Bridgman (Horizontal Bridgeman, HB) technology can produce the monocrystalline of GaAs, because the mechanical characteristic of GaAs, so vertical pulling method (Czochralski method) is to be difficult to be used in the preparation of GaAs material.But once there is the people to be by vertical pulling method (Czochralski method) GaAs that appears ultra-high purity and regarded semi-insulator.
The common preparation method of III-V compounds of group N-type semiconductorN GaAs thin-film material is except above-mentioned traditional method and modernism, the expensive harsh physical method of main or employing and the MOCVD method of complex and expensive, the former adopts high pure metal Ga and high-purity nonmetal As reaction to obtain GaAs, as reaction formula (1).Physical method is such as the plasma sputtering method, molecular beam epitaxy (MBE), electron-beam vapor deposition method (EBE), pulsed laser deposition (PLD), magnetron sputtering methods (MSD) etc., the latter adopts the deadly poisonous compound of liquid (or gaseous state) trimethyl-gallium of the expensive metal organic compound of gallium and As (as gaseous state arsine AsH
3) reaction prepare GaAs, as reaction formula (2).Their principle and chemical reaction are as follows respectively:
Ga+As→GaAs→GaAs (1)
Ga(CH
3)
3+AsH
3→GaAs+3CH
4 (2)
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of simplified equipment, method and starting material and preparation technology will obviously be better than the method for preparing the GaAs thin-film material of prior art and method.
For achieving the above object, the present invention adopts following technical scheme to realize:
A kind of method for preparing the GaAs thin-film material, with Ga
2o
3, As
2o
3and gac C is raw material, add the dehydrated alcohol suitable with solid material quality 50%～100%, after grinding evenly, with the pressure of 10～15MPa, it is pressed into to the sheet material that thickness is 1～10mm, then it is positioned in the reactor corundum crucible, with high pure nitrogen, vacuumize, displacement is the ppm level to oxygen concentration, and then vacuumize displacement 1～2 time with mixed gas, be evacuated to 7～13Pa, control heat-up rate in 5～10 ℃/min scope, reaction zone is heated in 1200 ℃～1250 ℃ scopes, sedimentary province is heated in 600 ℃～800 ℃ scopes, constant temperature 3～4h, keep be not less than-0.08MPa of vacuum tightness therebetween, after reaction zone temperature reaches preset temperature, naturally be cooled to room temperature, be filled with mixed gas to normal pressure, obtain the GaAs film of grey black.
Described mixed gas is Ar and H
2mixed gas, described H
2volume accounts for 10%～30% of mixed gas cumulative volume.
Principle of the present invention and chemical reaction are as shown in reaction formula (1), (2):
Ga
2O
3+As
2O
3+6H
2→2GaAs+6H
2O (1)
Ga
2O
3+As
2O
3+6C→2GaAs+6CO (2)
In above-mentioned reaction, generate CO and H
2o discharges and gets final product.
Adopt the preparation GaAs aimed thin film material that technical scheme of the present invention can be fairly large, once prepare the multi-disc film, and preparation cycle is short, strong to substrate (substrate) adaptability for materials, do not need to process its substrate (substrate) is special.
The preparation method of patent of the present invention and main technologic parameters traditional or existing GaAs preparation method are compared as follows shown in table 1.
The main technologic parameters comparison sheet of table 1 tradition or existing method and patented method of the present invention
Beneficial effect of the present invention is: the raw material of use is simple, cheap and easy to get, and is solid or nontoxic gas, to operator, without security threat, can prepare on a large scale by environmentally safe.
The accompanying drawing explanation
Fig. 1 is GaAs XRD diffraction spectrogram.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Accurately take Ga with ten thousand/electronic balance
2o
3, As
2o
3gac C, the even mixed grinding of the ratio of Ga/As/C=1.0/1.2/6.0 in molar ratio, because As easily distils, the ratio of As is excessive a little, add the dehydrated alcohol suitable with solid material quality 50%, after carefully grinding evenly, with the pressure of 10MPa, it is pressed into to the disk that thickness is 3mm, then it is positioned in the reactor corundum crucible, vacuumizing displacement with high pure nitrogen is the ppm level to oxygen concentration, and then uses Ar+H
2mixed gas is (containing H
2volume percent is 10%) vacuumize and replace 1 time, deposit required substrate and be positioned in advance after treatment specified location in reactor, then be evacuated to 7Pa, heat-up rate is controlled at 5 ℃/min, start to be heated to 1200 ℃ of reaction zones, 600 ℃ of sedimentary provinces, constant temperature 3～4h, keep be not less than-0.08MPa of vacuum tightness therebetween; After reaction zone temperature reaches preset temperature, open substrate swivel arrangement to reaction and finish, then naturally be cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened the tail gas valve to normal pressure, then opens reactor, takes out deposition substrate, obtains the GaAs film of grey black.
Film detects and analyzes through Rigaku D/max XRD, and film is for having higher crystallinity, the single phase of highly purified pure phase GaAs, and the XRD diffraction spectrogram is shown in accompanying drawing 1.
Embodiment 2
Accurately take Ga with ten thousand/electronic balance
2o
3, As
2o
3gac C, the even mixed grinding of the ratio of Ga/As/C=1.0/1.0/6.0 in molar ratio, add the dehydrated alcohol suitable with solid material quality 100%, after carefully grinding evenly, with the pressure of 15MPa, it being pressed into to thickness is the 10mm square piece, then it is positioned in reactor, vacuumizing displacement with high pure nitrogen is the ppm level to oxygen concentration, and then uses Ar+H
2mixed gas is (containing H
2volume percent is 30%) vacuumize displacement 2 times, deposit required substrate and be positioned in advance after treatment specified location in reactor.Then be evacuated to the 1mmHg left and right, heat-up rate is controlled at 5～10 ℃/min, start electrically heated and be warming up to 1300 ℃ of reaction zones, 800 ℃ of sedimentary provinces, after reaction zone temperature reaches preset temperature, open the substrate swivel arrangement and finish to reaction, 5 rev/mins of rotating speeds, constant temperature 3～4h, keep be not less than-0.08MPa of vacuum tightness therebetween; Then naturally be cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened the tail gas valve to normal pressure, then opens reactor, takes out deposition substrate, obtains the GaAs film.
Detect and analyze through Rigaku D/max XRD, the pure phase GaAs that film is highly crystalline.
Embodiment 3
Accurately take Ga with ten thousand/electronic analytical balance
2o
3, As
2o
3or As
2o
5gac C, the even mixed grinding of the ratio of Ga/As/C=1.0/1.2/8.0 in molar ratio, add the dehydrated alcohol suitable with solid material quality 65%, after carefully grinding evenly, with the pressure of 12MPa, it is pressed into to the disk that thickness is 8mm, then it is positioned in reactor, vacuumizing displacement with high pure nitrogen is the ppm level to oxygen concentration, and then uses Ar+H
2mixed gas is (containing H
2volume percent is 25%) vacuumize and replace 2 times, deposit required substrate and be positioned in advance after treatment specified location in reactor, then be evacuated to the 7Pa left and right, heat-up rate is controlled at 8 ℃/min, start to be heated to 1210 ℃ of reaction zones, the sedimentary province temperature is controlled at 700 ℃, after reaction zone temperature reaches preset temperature, opening substrate swivel arrangement to reaction finishes, 5 rev/mins of rotating speeds, constant temperature 3～4h, keep be not less than-0.08MPa of vacuum tightness therebetween, then naturally be cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened the tail gas valve to normal pressure, then opens reactor, takes out deposition substrate, and then at mobile pure hydrogen or high-purity Ar+H
2under mixed-gas atmosphere, reduction purifying 5h, obtain the GaAs film.
Detect and analyze through Rigaku D/max XRD, film is to have highly crystalline, single pure phase GaAs.
Embodiment 4
If the phase of product is impure or purity is not high enough, can adopt high-purity hydrogen (H
2) carry out purification process.The GaAs film prepared is positioned on the swinging strut in reactor to sealed reactor.Then vacuumizing displacement with high pure nitrogen is the ppm level to oxygen concentration in reactor, and then uses Ar+H
2mixed gas is (containing H
2volume percent is 15%) vacuumize displacement 1 time, deposit required substrate and be positioned in advance after treatment specified location in reactor.Then continue to pass into high-purity Ar+H
2mixed gas is to normal pressure, open the tail gas valve, heat-up rate is controlled at 8 ℃/min, starts to be heated to 1240 ℃ of reaction zones, and the sedimentary province temperature is controlled at 750 ℃, after reaction zone temperature reaches preset temperature, open the substrate swivel arrangement, 5 rev/mins of rotating speeds, constant temperature 4h, keep therebetween flowing atmosphere to small malleation, then continue to be filled with high-purity Ar+H
2mixed gas, be cooled to room temperature naturally, opens the tail gas valve to normal pressure, then open reactor, takes out deposition substrate, obtains the GaAs film.
If purity is not high, can again adopt high-purity hydrogen to carry out purification process, until reach needed purity.
Claims (3)
1. a method for preparing the GaAs thin-film material, is characterized in that: with Ga
2o
3, As
2o
3and gac C is raw material, add the dehydrated alcohol suitable with solid material quality 50% ~ 100%, after grinding evenly, with the pressure of 10 ~ 15MPa, it is pressed into to the sheet material that thickness is 1 ~ 10mm, then it is positioned in the reactor corundum crucible, with high pure nitrogen, vacuumize, displacement is the ppm level to oxygen concentration, and then vacuumize displacement 1 ~ 2 time with mixed gas, be evacuated to 7 ~ 13Pa, control heat-up rate in 5 ~ 10 ℃/min scope, reaction zone is heated in 1200 ℃ ~ 1250 ℃ scopes, sedimentary province is heated in 600 ℃ ~ 800 ℃ scopes, constant temperature 3 ~ 4h, keep be not less than-0.08MPa of vacuum tightness therebetween, after reaction zone temperature reaches preset temperature, naturally be cooled to room temperature, be filled with mixed gas to normal pressure, obtain the GaAs film of grey black.
2. a kind of method for preparing the GaAs thin-film material according to claim 1, is characterized in that: count in molar ratio: Ga
2o
3︰ As
2o
3︰ C is 1.0 ︰ (1.0 ~ 1.5) ︰ (3.0 ~ 8.0).
3. a kind of method for preparing the GaAs thin-film material according to claim 1, it is characterized in that: described mixed gas is Ar and H
2mixed gas, described H
2volume accounts for 10% ~ 30% of mixed gas cumulative volume.
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|---|---|---|---|
| CN201210552365.6A CN103147038B (en) | 2012-12-19 | 2012-12-19 | Method of preparing GaAs thin-film material |
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|---|---|---|---|
| CN201210552365.6A CN103147038B (en) | 2012-12-19 | 2012-12-19 | Method of preparing GaAs thin-film material |
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| CN103147038A true CN103147038A (en) | 2013-06-12 |
| CN103147038B CN103147038B (en) | 2014-10-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820771A (en) * | 2013-12-31 | 2014-05-28 | 电子科技大学 | Method for preparing GaAs film material |
| CN103866379A (en) * | 2013-12-31 | 2014-06-18 | 电子科技大学 | Method of preparing GaP film material |
| CN104498896A (en) * | 2014-12-26 | 2015-04-08 | 电子科技大学 | Preparation method of film material for compound semiconductor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0201933A2 (en) * | 1985-05-16 | 1986-11-20 | The Furukawa Electric Co., Ltd. | Vapor deposition method for the GaAs thin film |
| US4876218A (en) * | 1987-09-29 | 1989-10-24 | Oy Nokia Ab | Method of growing GaAs films on Si or GaAs substrates using ale |
| CN101372760A (en) * | 2008-09-10 | 2009-02-25 | 太原理工大学 | Preparation of glowing oxygen doped gallium arsenide polycrystalline film |
-
2012
- 2012-12-19 CN CN201210552365.6A patent/CN103147038B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0201933A2 (en) * | 1985-05-16 | 1986-11-20 | The Furukawa Electric Co., Ltd. | Vapor deposition method for the GaAs thin film |
| US4876218A (en) * | 1987-09-29 | 1989-10-24 | Oy Nokia Ab | Method of growing GaAs films on Si or GaAs substrates using ale |
| CN101372760A (en) * | 2008-09-10 | 2009-02-25 | 太原理工大学 | Preparation of glowing oxygen doped gallium arsenide polycrystalline film |
Non-Patent Citations (1)
| Title |
|---|
| 吴汝麟 等: ""非晶态砷化镓薄膜的研制"", 《半导体学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820771A (en) * | 2013-12-31 | 2014-05-28 | 电子科技大学 | Method for preparing GaAs film material |
| CN103866379A (en) * | 2013-12-31 | 2014-06-18 | 电子科技大学 | Method of preparing GaP film material |
| CN103820771B (en) * | 2013-12-31 | 2016-05-18 | 电子科技大学 | A kind of method of preparing GaAs thin-film material |
| CN103866379B (en) * | 2013-12-31 | 2016-08-17 | 电子科技大学 | A kind of method preparing GaP thin-film material |
| CN104498896A (en) * | 2014-12-26 | 2015-04-08 | 电子科技大学 | Preparation method of film material for compound semiconductor |
| WO2016101388A1 (en) * | 2014-12-26 | 2016-06-30 | 电子科技大学 | Preparation method of compound semiconductor thin-film material |
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| Publication number | Publication date |
|---|---|
| CN103147038B (en) | 2014-10-29 |
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Address after: 213022 Changzhou, Jiangsu new North District, Tianmu Lake Road, No. 1 Patentee after: Changzhou Xinghai Electronic Limited by Share Ltd Address before: 213022 Tianmu Lake, Changzhou, Jiangsu New District, No. 1 Patentee before: Changzhou Star Sea Electronics Co., Ltd. |