CN103147038B - Method of preparing GaAs thin-film material - Google Patents
Method of preparing GaAs thin-film material Download PDFInfo
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- CN103147038B CN103147038B CN201210552365.6A CN201210552365A CN103147038B CN 103147038 B CN103147038 B CN 103147038B CN 201210552365 A CN201210552365 A CN 201210552365A CN 103147038 B CN103147038 B CN 103147038B
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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 being 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, belongs to direct transition type energy band structure with indium phosphide (InP).Gallium arsenide is gray solid darkly, 1238 DEG C of fusing points.It, can existence stable in the air below 600 DEG C, and is 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 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 used 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, GaAs circuit can be used in the aspects such as mobile telephone, satellite communication, the point-to-point line of microwave, radar system.GaAs was once 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 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.
According to the prediction of Silicon Valley Strategies company of the U.S., within 2000, the global wireless communication devices market requirement 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 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 is also 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.1970 time, 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 more than 32% efficiency, and may operate in the light under 2,000 suns.This solar cell was once used in surveys areographic robot: spirit ramber (spirit rover) and chance ramber (opportunity rover).And a lot of solar cells are all the arrays making of GaAs.
Because the lattice parameter of GaAs and AlAs is almost the same, so conventionally can utilize molecular beam epitaxy (molecular beam epitaxy, or metal organic vapor metal-organic vapor phase epitaxy MBE), MOVPE), also be called Metalorganic Chemical Vapor Deposition (metal-organic chemical vapor deposition, MOCVD), on GaAs, form heterojunction structure, 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 people to regard semi-insulator with the GaAs that vertical pulling method (Czochralski method) is appeared ultra-high purity.
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 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 expensive metal organic compound liquid state (or gaseous state) trimethyl-gallium of gallium and the deadly poisonous compound of 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 GaAs thin-film material of prior art and method.
For achieving the above object, the present invention adopts following technical scheme to realize:
Prepare a method for 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, be pressed into the sheet material that thickness is 1～10mm with the pressure of 10～15MPa, then be positioned in reactor corundum crucible, vacuumize with high pure nitrogen, displacement is ppm level to oxygen concentration, and then vacuumize and replace 1～2 time with mixed gas, be evacuated to 7～13Pa, control heat-up rate within the scope of 5～10 DEG C/min, reaction zone is heated within the scope of 1200 DEG C～1250 DEG C, sedimentary province is heated within the scope of 600 DEG C～800 DEG C, constant temperature 3～4h, keep be not less than-0.08MPa of vacuum tightness therebetween, when reaction zone temperature reaches after preset temperature, be naturally 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.
Adopt the preparation GaAs aimed thin film material that technical scheme of the present invention can be fairly large, once prepare multi-disc film, and preparation cycle is short, strong to substrate (substrate) adaptability for materials, do not need its substrate (substrate) to process especially.
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, and environmentally safe, can be prepared without security threat on a large scale to operator.
Brief description of the drawings
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, be pressed into the disk that thickness is 3mm with the pressure of 10MPa, be then positioned in reactor corundum crucible, vacuumizing displacement with high pure nitrogen is 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 DEG C/min, start to be heated to 1200 DEG C of reaction zones, 600 DEG C of sedimentary provinces, constant temperature 3～4h, keeps be not less than-0.08MPa of vacuum tightness therebetween; When reaction zone temperature reaches after preset temperature, open substrate swivel arrangement to reaction and finish, be then naturally cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened 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 thing phase of highly purified pure phase GaAs, and 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, being pressed into thickness with the pressure of 15MPa is 10mm square piece, is then positioned in reactor, vacuumizing displacement with high pure nitrogen is 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 1mmHg left and right, heat-up rate is controlled at 5～10 DEG C/min, start electrically heated and be warming up to 1300 DEG C of reaction zones, 800 DEG C of sedimentary provinces, when reaction zone temperature reaches after preset temperature, open substrate swivel arrangement and finish to reaction, 5 revs/min of rotating speeds, constant temperature 3～4h, keeps be not less than-0.08MPa of vacuum tightness therebetween; Then be naturally cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened tail gas valve to normal pressure, then opens reactor, takes out deposition substrate, obtains 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, be pressed into the disk that thickness is 8mm with the pressure of 12MPa, be then positioned in reactor, vacuumizing displacement with high pure nitrogen is 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 7Pa left and right, heat-up rate is controlled at 8 DEG C/min, start to be heated to 1210 DEG C of reaction zones, sedimentary province temperature is controlled at 700 DEG C, when reaction zone temperature reaches after preset temperature, opening substrate swivel arrangement to reaction finishes, 5 revs/min of rotating speeds, constant temperature 3～4h, keeps be not less than-0.08MPa of vacuum tightness therebetween, then be naturally cooled to room temperature, be filled with high-purity Ar+H
2mixed gas is opened 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, reduce purifying 5h, obtain GaAs film.
Detect and analyze through Rigaku D/max XRD, film is to have highly crystalline, single pure phase GaAs.
Embodiment 4
If the thing of product is mutually impure or purity is not high enough, can adopt high-purity hydrogen (H
2) carry out purification process.The GaAs film preparing is positioned on the swinging strut in reactor to sealed reactor.Then vacuumizing displacement with high pure nitrogen is 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 tail gas valve, heat-up rate is controlled at 8 DEG C/min, starts to be heated to 1240 DEG C of reaction zones, and sedimentary province temperature is controlled at 750 DEG C, when reaction zone temperature reaches after preset temperature, open substrate swivel arrangement, 5 revs/min 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, is cooled to room temperature naturally, opens tail gas valve, then open reactor to normal pressure, takes out deposition substrate, obtains GaAs film.
If purity is not high, can again adopt high-purity hydrogen to carry out purification process, until reach needed purity.
Claims (2)
1. a method of preparing 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, be pressed into the sheet material that thickness is 1～10mm with the pressure of 10～15MPa, then be positioned in reactor corundum crucible, vacuumize with high pure nitrogen, displacement is ppm level to oxygen concentration, and then with Ar and H
2mixed gas vacuumize displacement 1～2 time, described H
2volume accounts for 10%～30% of mixed gas cumulative volume, be evacuated to 7～13Pa, control heat-up rate within the scope of 5～10 DEG C/min, reaction zone is heated within the scope of 1200 DEG C～1250 DEG C, sedimentary province is heated within the scope of 600 DEG C～800 DEG C, constant temperature 3～4h, keeps be not less than-0.08MPa of vacuum tightness therebetween; When reaction zone temperature reaches after preset temperature, be naturally cooled to room temperature, be filled with mixed gas to normal pressure, obtain the GaAs film of grey black.
2. a kind of method of preparing GaAs thin-film material according to claim 1, is characterized in that: meter: Ga in molar ratio
2o
3︰ As
2o
3︰ C is 1.0 ︰ (1.0～1.5) ︰ (3.0～8.0).
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| 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 |
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 (2)
| Title |
|---|
| "非晶态砷化镓薄膜的研制";吴汝麟 等;《半导体学报》;19850731;第6卷(第4期);第355-361页 * |
| 吴汝麟 等."非晶态砷化镓薄膜的研制".《半导体学报》.1985,第6卷(第4期),第355-361页. |
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