CN103866379B - A kind of method preparing GaP thin-film material - Google Patents
A kind of method preparing GaP thin-film material Download PDFInfo
- Publication number
- CN103866379B CN103866379B CN201310750279.0A CN201310750279A CN103866379B CN 103866379 B CN103866379 B CN 103866379B CN 201310750279 A CN201310750279 A CN 201310750279A CN 103866379 B CN103866379 B CN 103866379B
- Authority
- CN
- China
- Prior art keywords
- film material
- gap thin
- thin
- method preparing
- ampulla
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides a kind of method preparing GaP thin-film material, with Ga2O3、P2O5For initiation material, by Ga2O3With P2O5Carry out equimolar ratio mixing, be sealed in vacuum ampulla, react under the conditions of 500 DEG C～600 DEG C, generate GaPO4；Then ampulla is smashed, with hydrogen, hydrogen argon gaseous mixture, activated carbon and Hydrocarbon etc. for reduction extraction agent, use the high-temp in-situ solid phase class extractive reaction vapour deposition process from wound, under relatively low vacuum condition, on the various substrates (substrate) such as Si, Ge, rustless steel, electro-conductive glass, conductivity ceramics, be successfully prepared into that thickness is controlled, grey black, there is higher crystallinity, the GaP thin-film material of high-purity single thing phase.The raw material that the present invention uses is simple, cheap and easy to get, is solid or non-toxic gas, and environmentally safe, to operator without security threat；Preparation equipment is simple, and manufacturing cycle is short, and strong to substrate (substrate) adaptability for materials, preparation cost is relatively low, can realize fairly large GaP thin-film material and prepare.
Description
Technical field
The invention belongs to the preparation field of thin-film material, be specifically related to a kind of method preparing GaP thin-film material.
Background technology
GaP is the III-V type semi-conducting material of a kind of synthetic, and high-purity GaP is a kind of transparent salmon
Crystal.The fusing point of gallium phosphide (GaP) monocrystal material is 1467 DEG C, and the crystal of gallium phosphide (GaP) is sphalerite structure, and lattice is normal
Number is 0.5447 ± 0.006nm, and its chemical bond is the mixing key based on covalent bond, and its ionic bond composition is about 20%, 300K
Time band gap (Eg) width be 2.26eV, belong to direct transition type semiconductor.Gallium phosphide (GaP) and other big band gap III-V race's chemical combination
Thing quasiconductor is identical, can by introduce deep centre make fermi level close to mid-gap, as mixed the impurity units such as chromium, ferrum, oxygen
Element can become semi insulating material.Gallium phosphide (GaP) is divided into monocrystal material and epitaxial material.Industrial substrate monocrystal is mixes
Enter sulfur, the N-type semiconductor of sila matter.
GaP monocrystalline is prepared at ambient pressure by liquid phase method in early days, and rear employing liquid covers vertical pulling method to be prepared.Modern semiconductors
Industrial gallium phosphide (GaP) monocrystalline is all in high-pressure synthesis stove, uses directional solidification processes synthesis gallium phosphide polycrystal, enters
Row loads high pressure single crystal growing furnace after suitably processing to carry out crystal-pulling and obtains.Epitaxial material of gallium phosphide is on monocrystal of gallium phosphide substrate
The method being added diffusion growth by liquid phase epitaxy or vapour phase epitaxy is prepared.It is used for manufacturing light emitting diode (LED).Liquid phase epitaxy
Material can manufacture red light, yellow-green light, the light emitting diode of pure green light, and vapour phase epitaxy adds the material of diffusion growth, can make
Make the light emitting diode of sodium yellow, yellow-green light.
The III-V type quasiconductor common preparation method of GaP thin-film material is in addition to above-mentioned traditional method, mainly
Or use expensive harsh physical method or the MOCVD method of complex and expensive.Traditional method uses high pure metal Ga and high-purity
Nonmetal P reaction obtains GaP, its chemical equation such as formula (1)；Physical method is plasma sputtering, molecular beam epitaxy
(MBE), electron-beam vapor deposition method, pulsed laser deposition (PLD), magnetron sputtering method (MSD) etc., MOCVD method uses gallium
The deadly poisonous compound of expensive metal organic compound liquid trimethyl gallium and phosphorus is (such as gaseous state phosphine PH3) reaction prepare GaP,
Its chemical equation such as formula (2).These preparation methoies are all high to equipment requirements, and apparatus expensive, complex process.
The present inventor discloses one in the patent of invention that Publication No. CN103173715A, publication date are 2013.06.26
Plant the method preparing GaP thin-film material.This preparation method uses the present inventor special in the invention of Publication No. CN102517562A
On vertical gradient film of condensate precipitation equipment disclosed in profit, with Ga2O3、P2O5And reduction extraction agent is raw material, reactive deposition obtains
GaP thin film, its chemical reaction such as reaction equation (3), (4).This preparation method uses equipment simple, uses raw material simple, inexpensive easily
?；But its preparation technology haves much room for improvement, it is prepared into GaP thin-film material purity and all needs with degree of crystallinity to be improved further.
Ga+P→GaP→GaP/substrate (1)
Ga(CH3)3+PH3→GaP+3CH4↑ (2)
Ga2O3+P2O5+8H2→2GaP+8H2O (3)
Ga2O3+P2O5+8C→2GaP+8CO (4)
Summary of the invention
It is an object of the invention to provide a kind of method preparing GaP thin-film material, optimize GaP thin-film material system further
Standby technique, improves purity and the degree of crystallinity of GaP thin-film material.
The technical scheme is that a kind of method preparing GaP thin-film material, it is characterised in that comprise the following steps:
Step 1. is by Ga2O3With P2O5Grind after Ga:P=1:1 mixing in molar ratio uniformly, add and solid material quality
The dehydrated alcohol of 50%～100%, regrinding is dried the most afterwards, is pressed into sheet material with the pressure of 10～15MPa, then will
It is sealed in vacuum ampulla, ampulla is positioned in reactor corundum crucible, is heated to 500 DEG C～600 in electric tube furnace
DEG C, constant temperature 2～4h, natural cooling obtains GaPO4；
Vitreosil ampulla is smashed by step 2., places GaPO4Reaction zone in film deposition apparatus, substrate is positioned over thin
Crystallizing field in film deposition apparatus, replacing oxygen concentration with high pure nitrogen evacuation is ppm level, then uses Ar+H2Mixed gas
Evacuation is replaced 1～2 time, is evacuated to 7～13Pa the most again, and controlling programming rate is 5～10 DEG C/min, reaction zone heat temperature raising
To 1200 DEG C～1250 DEG C, crystallizing field is heated to 600 DEG C～800 DEG C, is passed through hydrogen, as reduction extraction agent, constant temperature 3～
4h, keeps vacuum >=-0.08Mpa therebetween；Then it is naturally cooling to room temperature, is filled with high-purity Ar+H2Mixed gas is to normal pressure, base
Sheet surface deposits to obtain GaP thin-film material.
Preferably, described sheet thickness is 1～10mm.Described Ar, H2H in mixed gas2Volume accounts for mixed gas cumulative volume
10%～30%.
Preferably, reduction extraction agent described in step 2 can also use hydrogen-argon-mixed, activated carbon (C) or nytron
Thing.Further, when using activated carbon as reduction extraction agent, solid active charcoal should be positioned over film deposition apparatus reaction
District.
The principle of the present invention and chemical reaction such as reaction equation (5), (6):
Ga2O3+P2O5→2GaPO4 (5)
2GaPO4+8H2→2GaP+8H2O↑ (6)
The present invention provides a kind of method preparing GaP thin-film material, with Ga2O3、P2O5For initiation material, by Ga2O3With P2O5
Carry out equimolar ratio mixing, be sealed in vacuum ampulla, react under the conditions of 500 DEG C～600 DEG C, generate GaPO4；Then smash
Ampulla, with hydrogen, hydrogen-argon gaseous mixture, activated carbon and Hydrocarbon etc. for reduction extraction agent, uses the high temperature from wound former
Position solid phase class extractive reaction vapour deposition process (High-temperature in-situ solid-state extract-like
Vapor deposition method), in vertical gradient film of condensate precipitation equipment, under relatively low vacuum condition, Si,
Successfully be prepared on the various substrates (substrate) such as Ge, rustless steel, electro-conductive glass, conductivity ceramics thickness controlled, grey black, tool
There is the GaP thin-film material of higher crystallinity, high-purity single thing phase.The raw material that the present invention uses is simple, cheap and easy to get, is solid
Body or non-toxic gas, environmentally safe, to operator without security threat；Preparation equipment is simple, and manufacturing cycle is short, to substrate
(substrate) adaptability for materials is strong, and preparation cost is relatively low, can realize fairly large GaP thin-film material and prepare.
The present invention is prepared into that GaP thin-film material purity is higher, degree of crystallinity is more preferable；Preparation technology uses sealing system, keeps away
Exempt from, because raw material distillation causes damage, can stoichiometrically generate GaPO4；Process controllability is high；And preparation temperature is lower, save
Energy consumption.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 step 1 reacts to obtain GaPO4XRD diffraction spectrogram.
Fig. 2 is that embodiment 1 is prepared into GaP thin-film material XRD diffraction spectrogram.
Fig. 3 is that embodiment 2 step 1 reacts to obtain GaPO4XRD diffraction spectrogram.
Fig. 4 is that embodiment 2 is prepared into GaP thin-film material XRD diffraction spectrogram.
Detailed description of the invention
Below in conjunction with specific embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1
The method preparing GaP thin-film material, comprises the following steps:
Step 1. accurately weighs Ga with ten thousand/electronic balance2O3, P2O5, the ratio of Ga/P=1.0/1.0 in molar ratio
Grind uniformly after mixing, add the dehydrated alcohol suitable with solid material quality 50%, after again carefully grinding uniformly, be dried and remove
Remove solvent, be pressed into, with the pressure of 12MPa, disk or the square piece that thickness is 3mm, be then sealed against in vacuum ampulla, will
Ampulla is positioned in reactor corundum crucible, is heated to 500 DEG C in electric tube furnace, and constant temperature 2h obtains GaPO after natural cooling4
Solid material (its XRD diffraction spectrogram is as shown in Figure 1)；
Ampulla is broken by step 2., places GaPO4Reaction zone in vertical gradient film of condensate precipitation equipment, substrate is placed
Specifying position in film deposition apparatus in crystallizing field, replacing oxygen concentration with high pure nitrogen evacuation is ppm level, the most again
Use Ar+H2Mixed gas is (containing H2Percent by volume is 10%～30%) evacuation replaces 2 times, is then evacuated to 1mmHg left
The right side, controlling programming rate is 5 DEG C/min, and reaction zone is heated to 1250 DEG C, and crystallizing field is heated to 800 DEG C；Work as reaction
After district's temperature reaches predetermined temperature, open substrate rotation device, setting speed 5 revs/min；Be passed through hydrogen, as reduction extraction agent,
Constant temperature 4h, keeps vacuum not less than-0.08Mpa therebetween；Finally it is naturally cooling to room temperature, is filled with high-purity Ar+H2Mixed gas
To normal pressure, open tail gas valve, then open precipitation equipment, take out deposition substrate, i.e. obtain orange-red GaP/substrate
Thin film.
It is prepared into GaP thin-film material to analyze through Rigaku D/max XRD detection, its XRD diffraction spectrogram such as Fig. 2 institute
Show.Analyzing display GaP thin-film material is high-crystallinity, highly purified pure phase GaP single thing phase.Thin film is surveyed through step calibrator
Amount is suitable with value of calculation, and error is less, and thickness is about between 2～20 μm.
Embodiment 2
The method preparing GaP thin-film material, comprises the following steps:
Step 1. accurately weighs Ga with ten thousand/electronic balance2O3, P2O5, the ratio of Ga/P=1.0/1.0 in molar ratio
Grind uniformly after mixing, add the dehydrated alcohol suitable with solid material quality 50%, after again carefully grinding uniformly, be dried and remove
Remove solvent, be compressed into, with the pressure of 12MPa, disk or the square piece that thickness is 3mm, be then sealed against in vacuum ampulla,
It is positioned in quartz boat reactor, electric tube furnace is heated to 500 DEG C, constant temperature 2h, obtain GaPO after naturally cooling to room temperature4
Solid material (its XRD diffraction spectrogram is as shown in Figure 3)；
Then ampulla is smashed by step 2., places GaPO4Reaction zone in vertical gradient film of condensate precipitation equipment, substrate
Being positioned over crystallizing field interior appointment position in film deposition apparatus, replacing oxygen concentration with high pure nitrogen evacuation is ppm level, so
After use Ar+H again2Mixed gas is (containing H2Percent by volume is 10%～30%) evacuation replace 2 times, be then evacuated to 1mmHg
Left and right；Controlling programming rate is 10 DEG C/min, and reaction zone is heated to 1250 DEG C, reaction zone, and crystallizing field is heated to 800
℃；After reaction zone, crystallizing field temperature reach predetermined temperature, open substrate rotation device, rotating speed 5 revs/min；It is passed through hydrogen, work
For reduction extraction agent, constant temperature 4h, keep vacuum not less than-0.08Mpa therebetween；Finally it is naturally cooling to room temperature, is filled with high-purity
Ar+H2Mixed gas opens tail gas valve to normal pressure, then opens precipitation equipment, takes out deposition substrate, i.e. obtains orange-red
GaP/substrate thin film.
It is prepared into GaP thin-film material to analyze through Rigaku D/max XRD detection, its XRD diffraction spectrogram such as Fig. 4 institute
Show.Analyzing display GaP thin-film material is high-crystallinity, highly purified pure phase GaP single thing phase.Thin film is surveyed through step calibrator
Amount is suitable with value of calculation, and error is less, and thickness is about between 2～20 μm.Thin film is measured and value of calculation phase through step calibrator
When, error is less, and thickness is about between 2～20 μm.
Claims (4)
1. the method preparing GaP thin-film material, it is characterised in that comprise the following steps:
Step 1. is by Ga2O3With P2O5Grind uniformly after Ga:P=1:1 mixing in molar ratio, add with solid material quality 50%～
The dehydrated alcohol of 100%, regrinding is dried the most afterwards, is pressed into sheet material with the pressure of 10～15MPa, is then sealed against
In vacuum ampulla, ampulla is positioned in reactor corundum crucible, electric tube furnace is heated to 500 DEG C～600 DEG C, constant temperature
2～4h, natural cooling obtains GaPO4；
Vitreosil ampulla is smashed by step 2., places GaPO4Reaction zone in film deposition apparatus, substrate is positioned over thin film and sinks
Crystallizing field in long-pending device, replacing oxygen concentration with high pure nitrogen evacuation is ppm level, then uses Ar+H2Mixed gas is taken out very
Empty substitution 1～2 times, be evacuated to 7～13Pa the most again, and controlling programming rate is 5～10 DEG C/min, and reaction zone is heated to
1200 DEG C～1250 DEG C, crystallizing field is heated to 600 DEG C～800 DEG C, is passed through hydrogen, as reduction extraction agent, constant temperature 3～
4h, keeps vacuum >=-0.08Mpa therebetween；Then it is naturally cooling to room temperature, is filled with high-purity Ar+H2Mixed gas is to normal pressure, base
Sheet surface deposits to obtain GaP thin-film material.
2. a kind of method preparing GaP thin-film material as described in claim 1, it is characterised in that reduction extraction described in step 2
Agent uses hydrogen, hydrogen-argon-mixed, activated carbon or Hydrocarbon.
3. a kind of method preparing GaP thin-film material as described in claim 1, it is characterised in that described sheet thickness be 1～
10mm。
4. a kind of method preparing GaP thin-film material as described in claim 1, it is characterised in that described Ar, H2In mixed gas
H2Volume accounts for the 10%～30% of mixed gas cumulative volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310750279.0A CN103866379B (en) | 2013-12-31 | 2013-12-31 | A kind of method preparing GaP thin-film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310750279.0A CN103866379B (en) | 2013-12-31 | 2013-12-31 | A kind of method preparing GaP thin-film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103866379A CN103866379A (en) | 2014-06-18 |
| CN103866379B true CN103866379B (en) | 2016-08-17 |
Family
ID=50905373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310750279.0A Expired - Fee Related CN103866379B (en) | 2013-12-31 | 2013-12-31 | A kind of method preparing GaP thin-film material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103866379B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498896A (en) * | 2014-12-26 | 2015-04-08 | 电子科技大学 | Preparation method of film material for compound semiconductor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108965A (en) * | 1985-12-20 | 1987-12-09 | 联合碳化公司 | Crystalline gallophosphate compositions |
| CN103147038A (en) * | 2012-12-19 | 2013-06-12 | 常州星海电子有限公司 | Method of preparing GaAs thin-film material |
| CN103159193A (en) * | 2012-12-19 | 2013-06-19 | 常州星海电子有限公司 | Preparation method of InP film material |
| CN103173715A (en) * | 2012-12-19 | 2013-06-26 | 常州星海电子有限公司 | Preparation method of GaP film material |
| CN103352214A (en) * | 2012-12-19 | 2013-10-16 | 常州星海电子有限公司 | Preparation method of In1-xGaxP(x is not lower than 0 and not greater than 1)/Substrate film material |
-
2013
- 2013-12-31 CN CN201310750279.0A patent/CN103866379B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108965A (en) * | 1985-12-20 | 1987-12-09 | 联合碳化公司 | Crystalline gallophosphate compositions |
| CN103147038A (en) * | 2012-12-19 | 2013-06-12 | 常州星海电子有限公司 | Method of preparing GaAs thin-film material |
| CN103159193A (en) * | 2012-12-19 | 2013-06-19 | 常州星海电子有限公司 | Preparation method of InP film material |
| CN103173715A (en) * | 2012-12-19 | 2013-06-26 | 常州星海电子有限公司 | Preparation method of GaP film material |
| CN103352214A (en) * | 2012-12-19 | 2013-10-16 | 常州星海电子有限公司 | Preparation method of In1-xGaxP(x is not lower than 0 and not greater than 1)/Substrate film material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103866379A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Galazka | β-Ga2O3 for wide-bandgap electronics and optoelectronics | |
| Stepanov et al. | Gallium OXIDE: Properties and applica 498 a review | |
| WO2004090202A1 (en) | Zinc oxide single crystal | |
| KR101320708B1 (en) | Method for producing n-type group iii nitride single crystal, n-type group iii nitride single crystal, and crystal substrate | |
| Ashraf et al. | MOCVD of vertically aligned ZnO nanowires using bidentate ether adducts of dimethylzinc | |
| Wang et al. | N-type large single crystal diamond with S doping and BS co-doping grown in FeNi–C system | |
| Santailler et al. | Chemically assisted vapour transport for bulk ZnO crystal growth | |
| CN111455455A (en) | Crystal growth device with online monitoring function | |
| CN107140681A (en) | β‑Ga2O3The preparation method of micro belt | |
| CN108193282B (en) | A kind of synthetic method and its application of high-purity silicon carbide raw material | |
| Liu et al. | The deposition and annealing study of MOCVD ZnMgO | |
| CN108987257A (en) | Ga is grown on a si substrate using halide vapor phase epitaxy2O3The method of film | |
| Zhang et al. | High optical quality ZnO films grown on graphite substrate for transferable optoelectronics devices by ultrasonic spray pyrolysis | |
| CN103173715B (en) | Preparation method of GaP film material | |
| Dierkes et al. | From metals to nitrides-Syntheses and reaction details of binary rare earth systems | |
| CN103866379B (en) | A kind of method preparing GaP thin-film material | |
| CN110203933B (en) | Method for reducing nitrogen impurity content in silicon carbide powder | |
| CN103911600B (en) | A kind of method preparing InP thin-film material | |
| Su et al. | Effect of N2O on high-rate homoepitaxial growth of CVD single crystal diamonds | |
| Chen et al. | Synthesis, structure and properties of Sn-doped ZnO nanobelts | |
| CN103147038B (en) | Method of preparing GaAs thin-film material | |
| Nagata | Indium oxide: In2O3 | |
| CN103820771B (en) | A kind of method of preparing GaAs thin-film material | |
| Krymov et al. | GaN growth on β-Ga 2 O 3 substrates by HVPE | |
| CN104498896A (en) | Preparation method of film material for compound semiconductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20191231 |