CN102443842A - Preparation method of AlGaN monocrystals - Google Patents
Preparation method of AlGaN monocrystals Download PDFInfo
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- CN102443842A CN102443842A CN2011103509363A CN201110350936A CN102443842A CN 102443842 A CN102443842 A CN 102443842A CN 2011103509363 A CN2011103509363 A CN 2011103509363A CN 201110350936 A CN201110350936 A CN 201110350936A CN 102443842 A CN102443842 A CN 102443842A
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- algan
- single crystal
- gas
- aln
- protective gas
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- 229910002704 AlGaN Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明涉及一种AlGaN单晶的制备方法,本方法所需装置简单，利用金属Ga源和单晶AlN在防止氧化的情况下将Ga扩散进AlN单晶形成AlGaN.通过X射线衍射结果分析所制备的AlGaN单晶体具有高铝组分。所生长的AlGaN单晶有一定使用价值，该AlGaN单晶衬底可供AlGaN等III-N半导体材料薄膜同质外延之需。
The invention relates to a preparation method of AlGaN single crystal. The device required by the method is simple, and the metal Ga source and single crystal AlN are used to diffuse Ga into the AlN single crystal to form AlGaN under the condition of preventing oxidation. According to the analysis of X-ray diffraction results, The prepared AlGaN single crystal has a high aluminum composition. The grown AlGaN single crystal has a certain use value, and the AlGaN single crystal substrate can be used for homoepitaxial growth of III-N semiconductor material thin films such as AlGaN.
Description
Technical field
The present invention relates to a kind of preparation method of AlGaN monocrystalline, belong to technical field of optoelectronic functional materials.
Technical background
The III-N base semiconductor material of broad-band gap has received people's attention day by day in recent years; Reason is III-N material and ternary compound AlGaN thereof; No matter InGaN etc. still electrology characteristic aspect, have premium properties that conventional semiconductors do not possess in optical characteristics.Its energy gap is adjustable, and saturated electrons speed is higher, and voltage breakdown is bigger, chemical property more the stabilization energy better application in LED, ultraviolet detector, laser apparatus and some high frequency efficient rate devices.Yet the epitaxy of III-N sill now is because of the shortage of its substrate matching materials, causes defective in the III-N sill epitaxial process much to influence the performance of device.We can say that optimal extension is exactly an iso-epitaxy, can reduce like this, different with thermal expansivity because the lattice of substrate and epitaxial film does not match.
GaN, the increment study of AlN single crystalline substrate has been carried out decades, and main method has: 1) by the GALLIUM metal pure powder; Aluminium powder and ammonia react under high pressure-temperature or under the solubility promoter effect and generate GaN, and AlN film or little monocrystalline are like S.NaKamura; J.Tietian, Appl. Phys. Lett. 74 (1999) 1687 and Witzke, H-D:Uber das Wachstum von AlN Einkristallen; Description and report that Phys stat sol 2,1109 (1962) carries out.2) utilize GaN, AlN powder subliming method synthetic single crystal.3) the HVPE method is synthetic, like H.P. Maruska, and J.J. Tietjen, Appl.Phys. Lett.15 (1969) 327.And article and the patent etc. of carrying out the preparation of AlGaN monocrystalline rarely have report.Growth AlGaN monocrystalline we can say that the application to promoting III-N base semiconductor material photoelectric device has further help.
Summary of the invention
The purpose of this invention is to provide a kind of AlGaN crystalline preparation method who generates high aluminium component, the AlGaN monocrystalline of said growth can supply the need of III-N semiconductor material thin film extensions such as AlGaN, and technical scheme is following:
A kind of AlGaN crystal preparation method that is used for comprises the steps: GALLIUM metal pure and AlN monocrystalline are mixed; The mixture that obtains is put into heating systems, get rid of Atmospheric components in it; System is slowly heated up, in room temperature to 400
oThe C stage passes to protective gas, at 300-500
oLogical a small amount of reducing gas during the C; The above system is continued to be heated to 800
oC-1300
oC, and constant temperature is more than 1 day, during keep passing to protective gas and keep system's malleation, utilize thermal diffusion effect to make metal Ga mix the AlN monocrystalline and generate AlGaN; Treat that the described system heating schedule of above step finishes and naturally cooling, obtains title product.
Described AlN monocrystalline, metal Ga, its purity is not less than 99.9%;
Described protective gas is nitrogen or argon gas, and described reducing gas is a hydrogen, and these gas purities are more than 99.9%.
Described eliminating in it method of Atmospheric components following: system is evacuated to system gas and forces down in 100 pa, fills then with protective gas to malleation, is evacuated to be lower than 100pa again; Repeat above step 2-6 time.
The content of Al, Ga composition can be regulated through growth temperature and time among the AlGaN of present method preparation.
The present invention is with respect to prior art, and equipment is built simply, and the preparation method is simple.Having must practical value.
Below in conjunction with Figure of description and specific embodiment, technical scheme of the present invention done further describing.
Description of drawings
Fig. 1 is the X powder diffraction figure of AlN monocrystalline;
Fig. 2 is the X powder diffraction figure of the AlGaN monocrystalline of generation;
Fig. 3 is the X-coatings of the AlGaN monocrystalline of AlN monocrystalline and generation, and wherein b is the amplification at a overlapping place.
Embodiment
Embodiment 1: take by weighing high-purity Ga metal of 0.76 g quality, the AlN monocrystalline that fusion envelopes 1 cm * 1 cm * 0.2 cm square is placed in the corundum crucible.Put it in the stove, be evacuated to 20 pa, close pump and stop to bleed, fill with argon gas, be evacuated to 20 pa again, begin slow intensification, room temperature to 400 after repeating 4 times like this to malleation
oPass to 100 sccm argon gas between C and do protection 400
oC-500
oC adds logical 10 sccm hydrogen, 500
oC-1000
oC and constant temperature 1000
oThe 12 day time of C is led to 100 sccm argon gas, after this slowly is cooled to room temperature and takes out crucible.Remove and be used for the X-ray powdery diffractometry behind the surperficial residual metallic Ga and can calculate AlGaN Ga roughly through vegrad law linear rule (
), the content composition of Al is respectively 5.3% and 94.7%.
Embodiment 2: take by weighing high-purity Ga metal of 0.45 g quality, the AlN monocrystalline that fusion envelopes 1 cm * 1 cm * 0.2 cm square is placed in the corundum crucible.Put it in the stove, be evacuated to 20 pa, close pump and stop to bleed, fill with argon gas, be evacuated to 20 pa again, begin slow intensification, room temperature to 400 after repeating 4 times like this to malleation
oPass to 100 sccm argon gas between C and do protection 400
oC-500
oC adds logical 10 sccm hydrogen, 500
oC-900
oC and constant temperature 900
oThe six day time of C is led to the 100sccm argon gas, after this slowly is cooled to room temperature and takes out crucible.Remove and be used for the X-ray powdery diffractometry behind the surperficial residual metallic Ga and can calculate AlGaN Ga roughly through vegrad law linear rule (
), the content composition of Al is respectively 1.2% and 98.8%.
Embodiment 3: take by weighing high-purity Ga metal of 0.85 g quality, the AlN monocrystalline that fusion envelopes 1 cm * 1 cm * 0.2 cm square is placed in the corundum crucible.Put it in the stove, be evacuated to 20 pa, close pump and stop to bleed, fill with argon gas, be evacuated to 20 pa again, begin slow intensification, room temperature to 400 after repeating 4 times like this to malleation
oPass to 100 sccm argon gas between C and do protection 400
oC-500
oC adds logical 10 sccm hydrogen, 500
oC-1100
oC and constant temperature 1100
oThe seven day time of C is led to the 100sccm argon gas, after this slowly is cooled to room temperature and takes out crucible.Remove and be used for the X-ray powdery diffractometry behind the surperficial residual metallic Ga and can calculate AlGaN Ga roughly through vegrad law linear rule (
), the content composition of Al is respectively 3.9% and 96.1%.
Claims (5)
1. one kind is used for AlGaN crystal preparation method, comprises the steps: GALLIUM metal pure and AlN monocrystalline are mixed; The mixture that obtains is put into heating systems, get rid of Atmospheric components in it; System is slowly heated up, in room temperature to 400
oThe C stage passes to protective gas, at 300-500
oLogical a small amount of reducing gas during the C; The above system is continued to be heated to 800
oC-1300
oC, and constant temperature is more than 1 day, during keep passing to protective gas and keep system's malleation, utilize thermal diffusion effect to make metal Ga mix the AlN monocrystalline and generate AlGaN; Treat that the described system heating schedule of above step finishes and naturally cooling, obtains title product.
2. by the described AlGaN method for preparing single crystal of claim 1, it is characterized in that: described AlN monocrystalline, metal Ga, its purity is not less than 99.9%.
3. by the described AlGaN method for preparing single crystal of claim 1, it is characterized in that: described protective gas is nitrogen or argon gas, and described reducing gas is a hydrogen, and these gas purities are more than 99.9%.
4. by the described AlGaN method for preparing single crystal of claim 1, described eliminating in it method of Atmospheric components following: system is evacuated to system gas and forces down in 100 pa, fills then with protective gas to malleation, is evacuated to be lower than 100pa again; Repeat above step 2-6 time.
5. generate the AlGaN crystal that obtains by the wherein arbitrary method of claim 1-4, it is characterized in that: the content of Al, Ga composition can be regulated through growth temperature and time among the AlGaN.
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| CN2011103509363A CN102443842A (en) | 2011-05-05 | 2011-11-08 | Preparation method of AlGaN monocrystals |
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| CN201110115778.3 | 2011-05-05 | ||
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| CN2011103509363A CN102443842A (en) | 2011-05-05 | 2011-11-08 | Preparation method of AlGaN monocrystals |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106270523A (en) * | 2016-09-30 | 2017-01-04 | 中国人民大学 | A kind of large-area ultrathin monocrystalline and method for fast growing thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030226496A1 (en) * | 2001-07-06 | 2003-12-11 | Technologies And Devices International, Inc. | Bulk GaN and AlGaN single crystals |
| WO2006011361A1 (en) * | 2004-07-27 | 2006-02-02 | Sumitomo Electric Industries, Ltd. | Iii group nitride single crystal and method for preparation thereof, and semiconductor device |
| CN1734719A (en) * | 2004-08-04 | 2006-02-15 | 住友电气工业株式会社 | Nitride semiconductor single crystal substrate and its synthesis method |
| WO2006040359A1 (en) * | 2004-10-16 | 2006-04-20 | Azzurro Semiconductors Ag | Method for producing gan or algan crystals |
| CN101351579A (en) * | 2006-03-29 | 2009-01-21 | 住友电气工业株式会社 | Group III nitride single crystal growth method |
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2011
- 2011-11-08 CN CN2011103509363A patent/CN102443842A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030226496A1 (en) * | 2001-07-06 | 2003-12-11 | Technologies And Devices International, Inc. | Bulk GaN and AlGaN single crystals |
| WO2006011361A1 (en) * | 2004-07-27 | 2006-02-02 | Sumitomo Electric Industries, Ltd. | Iii group nitride single crystal and method for preparation thereof, and semiconductor device |
| CN1734719A (en) * | 2004-08-04 | 2006-02-15 | 住友电气工业株式会社 | Nitride semiconductor single crystal substrate and its synthesis method |
| WO2006040359A1 (en) * | 2004-10-16 | 2006-04-20 | Azzurro Semiconductors Ag | Method for producing gan or algan crystals |
| CN101080516A (en) * | 2004-10-16 | 2007-11-28 | 阿祖罗半导体股份公司 | Method for producing gan or algan crystals |
| CN101351579A (en) * | 2006-03-29 | 2009-01-21 | 住友电气工业株式会社 | Group III nitride single crystal growth method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106270523A (en) * | 2016-09-30 | 2017-01-04 | 中国人民大学 | A kind of large-area ultrathin monocrystalline and method for fast growing thereof |
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Application publication date: 20120509 |