CN1599032A - Growth GaN film on silicon substrate using hydride vapaur phase epitaxial method - Google Patents
Growth GaN film on silicon substrate using hydride vapaur phase epitaxial method Download PDFInfo
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- CN1599032A CN1599032A CN200410041443.1A CN200410041443A CN1599032A CN 1599032 A CN1599032 A CN 1599032A CN 200410041443 A CN200410041443 A CN 200410041443A CN 1599032 A CN1599032 A CN 1599032A
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- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 3
- 229910052710 silicon Inorganic materials 0.000 title description 3
- 239000010703 silicon Substances 0.000 title description 3
- 150000004678 hydrides Chemical class 0.000 title 1
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract 2
- 239000010409 thin film Substances 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 description 6
- 239000010980 sapphire Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
The invention relates to growing the GaN film with high quality on the Si substrate through the hydrid gas phase epitaxial method and low temperature buffer layer technology. In the HVPE growth system or MOCVD system, we chooses the ammonia gas and HCl as the gas source at the relative low temperature of between 400deg.C ad 800deg.C on the Si substrate, grow the GaN and then continue it at the high temperature, such as between 1000deg.C and 1100deg.C. The GaN film grown at the low temperature prevents the nitridation of the ammonia gas to the Si substrate and the reaction between the Si and the HCl at high temperature and thus makes the later GaN have high quality.
Description
Technical Field
The present invention relates to a method and a technique for growing a GaN thin film on a Si substrate by hydride vapor phase epitaxy, and more particularly, to a method for directly growing a GaN thin film.
Technical Field
The III-V nitride material mainly made of GaN, InGaN and AlGaN alloy materials is a novel semiconductor material which is valued internationally in recent years.
The application of GaN-based semiconductor materials in the field of optoelectronics, such as LEDs and LDs, is of great significance. The market value of high-brightness LEDs worldwide is about $ 12 million at present, and the market scale is expected to rapidly increase to $ 30 million by 2005.
The most commonly used substrate material is sapphire (α -Al2O 3). the enormous lattice and thermal mismatch leads to high density dislocations in the GaN epitaxial layers, typically up to 1010/cm2The performance and lifetime of the device are severely affected.
At present, a GaN substrate is generally obtained by vapor-phase growing a GaN thick film on a foreign substrate and then separating the original foreign substrate. Among them, GaN is most commonly grown on sapphire substrates, and has the highest quality. In order to obtain a self-supporting GaN substrate, the sapphire substrate must be removed. Since sapphire is extremely stable, it is difficult to use a chemical etching method. The general method is mechanical grinding, but because sapphire is hard, a large amount of diamond grinding materials are consumed, the cost is high, and the speed is extremely slow. The choice of substrate is therefore also of great importance.
The GaN thin film is mainly grown by Metal Organic Chemical Vapor Deposition (MOCVD), Molecular Beam Epitaxy (MBE), Hydride Vapor Phase Epitaxy (HVPE), and the like. Compared with MOCVD, MBE, HVPE technology has many advantages: the growth rate is high and can reach dozens of even hundreds of micrometers per hour; high transverse-longitudinal growth ratio; no holes and yellow bands; large-area thin films and the like can be grown. Combined with the ELO technology, the method can be used for growing high-quality GaN thin films.
The problem of the reaction of the substrate with the source gas needs to be solved by growing GaN on Si by hydride vapor phase epitaxy, the reaction formula is as follows:
the Si is nitrided to form Si3N4The powder and the HCl and silicon present in the reactor react seriously to form SiCl4, which damages and even hinders the subsequent growth of GaN and reduces the crystal quality of the film.
Technical content
The invention aims to: and growing a high-quality GaN film on the si substrate by using a hydride vapor phase epitaxy method and a low-temperature buffer layer technology.
The technical solution of the invention is as follows:
firstly, in an HVPE growth system or an MOCVD system, firstly, under the condition of lower temperature such as 400-3The flow rate is 600sccm and the flow rate of the ammonia carrier gas is600sccm and HCl flow of 10sccm, growing a layer of GaN by HCl carrier gas flow, and then continuously growing GaN at a high temperature such as 1000-.
The mechanism and the technical characteristics of the invention are as follows:
the GaN layer grown at low temperature prevents the nitridation of ammonia gas to the Si substrate and the reaction of Si and HCl at high temperature, so that the subsequently grown GaN has higher quality.
In the invention, a high-quality GaN film is grown on a Si substrate by a hydride vapor phase epitaxy method. The GaN film grown on the Si substrate has the following advantages: 1) at present, most semiconductor devices are based on Si substrates, and the integration of GaN photoelectronic and microelectronic devices on Si and the existing devices is easy to realize, which is very attractive; 2) since Si-based short wavelength light emitting devices have not been broken through, and GaN-based short wavelength light emitting devices (LEDs, LDs, etc.) have been successful, the GaN device grown on Si can realize the integration of multiple neutral properties such as photoelectromagnetism, etc., and has important application in the fields of quantum computers, etc. in the future; 3) a Si substrate is easily corroded or peeled off, a GaN self-supporting substrate can be easily obtained, and the like. As shown in FIG. 1, the GaN thin films grown under different temperature conditions of 400-800 ℃ have similar structural characteristics.
Drawings
FIG. 1 is an XRD diffraction pattern of GaN thin films grown at different buffer layer temperatures (400-.
FIG. 2 PL spectra of GaN films grown at different buffer layer temperatures (400-
FIG. 3 Raman spectra of GaN thin films grown on different substrates (Si, sapphire)
Detailed Description
The In pre-deposition technology for the substrate surface metal adopted by the invention comprises the following steps:
1. cleaning and processing of Si (111) substrates.
2. After the Si (111) substrate was placed in the reactor, a GaN buffer layer was now grown at low temperature.The temperature is from 400 ℃ to 800 ℃, similar results are obtained under various temperature conditions, and the growth time is 40-90 seconds, such as 60 seconds typically. The gas flow rates are respectively: NH (NH)3The flow rate was 600sccm, the ammonia carrier gas flow rate was 600sccm, the HCl flow rate was 10sccm, the HCl carrier gas flow rate was 20sccm, and the total nitrogen flow rate was 3000 sccm. The GaN/Si sample with the low temperature buffer layer was removed.
3. And (3) raising the temperature to 1040-.
4. Generally, the growth is carried out under the conditions of high temperature of 1000-1050 ℃, and the growth also has the same result in the invention.
Claims (3)
1. A high-quality GaN film is grown on a Si substrate by using a hydride vapor phase epitaxy method and a low-temperature buffer layer technology, and the method is characterized in that in an HVPE growth system or an MOCVD system, a layer of GaN is grown on the Si substrate under the condition of a lower temperature of 400-plus-800 ℃ by using ammonia gas and HCl as gas sources, and then the GaN is continuously grown at a high temperature of, for example, 1000-plus-1100 ℃.
2. The method for growing high quality GaN thin film on Si substrate by hydride vapor phase epitaxy and low temperature buffer layer technique as claimed in claim 1, wherein the growth time is 40-90 seconds at the lower temperature of 400-800 ℃, and the gas flow is: NH (NH)3The flow rate was 600sccm, the ammonia carrier gas flow rate was 600sccm, the HCl flow rate was 10sccm, the HCl carrier gas flow rate was 20sccm, and the total nitrogen flow rate was 3000 sccm.
3. The method as claimed in claim 1, wherein the GaN film is grown on the Si substrate by hydride vapor phase epitaxy and low temperature buffer layer technique at 1040-1080 deg.C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100414431A CN1327486C (en) | 2004-07-21 | 2004-07-21 | Growth GaN film on silicon substrate using hydride vapaur phase epitaxial method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100414431A CN1327486C (en) | 2004-07-21 | 2004-07-21 | Growth GaN film on silicon substrate using hydride vapaur phase epitaxial method |
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| Publication Number | Publication Date |
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| CN1599032A true CN1599032A (en) | 2005-03-23 |
| CN1327486C CN1327486C (en) | 2007-07-18 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431017B (en) * | 2008-12-03 | 2010-06-23 | 南京大学 | Method for improving GaN thick film integrality on sapphire substrate |
| CN101281863B (en) * | 2008-01-11 | 2010-09-15 | 南京大学 | Method for preparing large scale nonpolar surface GaN self-supporting substrate |
| US7825432B2 (en) | 2007-03-09 | 2010-11-02 | Cree, Inc. | Nitride semiconductor structures with interlayer structures |
| CN102492935A (en) * | 2011-12-13 | 2012-06-13 | 中国电子科技集团公司第十三研究所 | Treatment method of silicon substrate for preparing GaN epitaxy material with low dislocation density |
| CN102560676A (en) * | 2012-01-18 | 2012-07-11 | 山东大学 | Method for performing GaN single crystal growth by using thinned and bonded structure |
| US8362503B2 (en) | 2007-03-09 | 2013-01-29 | Cree, Inc. | Thick nitride semiconductor structures with interlayer structures |
| CN103021946A (en) * | 2012-12-05 | 2013-04-03 | 北京大学 | Method of preparing GaN monocrystal substrate in mechanical removal way |
| CN103498193A (en) * | 2013-09-26 | 2014-01-08 | 西安神光皓瑞光电科技有限公司 | Epitaxial growth method for improving crystal quality of material |
| CN108987257A (en) * | 2018-07-12 | 2018-12-11 | 南京南大光电工程研究院有限公司 | Ga is grown on a si substrate using halide vapor phase epitaxy2O3The method of film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3788104B2 (en) * | 1998-05-28 | 2006-06-21 | 住友電気工業株式会社 | Gallium nitride single crystal substrate and manufacturing method thereof |
| US6290774B1 (en) * | 1999-05-07 | 2001-09-18 | Cbl Technology, Inc. | Sequential hydride vapor phase epitaxy |
| JP4524953B2 (en) * | 2001-05-18 | 2010-08-18 | パナソニック株式会社 | Method for manufacturing nitride semiconductor substrate and method for manufacturing nitride semiconductor device |
| US6632725B2 (en) * | 2001-06-29 | 2003-10-14 | Centre National De La Recherche Scientifique (Cnrs) | Process for producing an epitaxial layer of gallium nitride by the HVPE method |
| CN1138025C (en) * | 2001-12-13 | 2004-02-11 | 南京大学 | Process for controlling polarity of GaN |
| CN100428410C (en) * | 2002-01-09 | 2008-10-22 | 南京大学 | Homogeneity improving method and device for hydride gaseous epitaxially groven GaN material |
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2004
- 2004-07-21 CN CNB2004100414431A patent/CN1327486C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8362503B2 (en) | 2007-03-09 | 2013-01-29 | Cree, Inc. | Thick nitride semiconductor structures with interlayer structures |
| US7825432B2 (en) | 2007-03-09 | 2010-11-02 | Cree, Inc. | Nitride semiconductor structures with interlayer structures |
| US9054017B2 (en) | 2007-03-09 | 2015-06-09 | Cree, Inc. | Thick nitride semiconductor structures with interlayer structures and methods of fabricating thick nitride semiconductor structures |
| US8324005B2 (en) | 2007-03-09 | 2012-12-04 | Cree, Inc. | Methods of fabricating nitride semiconductor structures with interlayer structures |
| CN101281863B (en) * | 2008-01-11 | 2010-09-15 | 南京大学 | Method for preparing large scale nonpolar surface GaN self-supporting substrate |
| CN101431017B (en) * | 2008-12-03 | 2010-06-23 | 南京大学 | Method for improving GaN thick film integrality on sapphire substrate |
| CN102492935A (en) * | 2011-12-13 | 2012-06-13 | 中国电子科技集团公司第十三研究所 | Treatment method of silicon substrate for preparing GaN epitaxy material with low dislocation density |
| CN102560676B (en) * | 2012-01-18 | 2014-08-06 | 山东大学 | Method for performing GaN single crystal growth by using thinned and bonded structure |
| CN102560676A (en) * | 2012-01-18 | 2012-07-11 | 山东大学 | Method for performing GaN single crystal growth by using thinned and bonded structure |
| CN103021946A (en) * | 2012-12-05 | 2013-04-03 | 北京大学 | Method of preparing GaN monocrystal substrate in mechanical removal way |
| CN103498193A (en) * | 2013-09-26 | 2014-01-08 | 西安神光皓瑞光电科技有限公司 | Epitaxial growth method for improving crystal quality of material |
| CN103498193B (en) * | 2013-09-26 | 2016-05-18 | 西安神光皓瑞光电科技有限公司 | A kind of epitaxial growth method that improves material crystals quality |
| CN108987257A (en) * | 2018-07-12 | 2018-12-11 | 南京南大光电工程研究院有限公司 | Ga is grown on a si substrate using halide vapor phase epitaxy2O3The method of film |
| CN108987257B (en) * | 2018-07-12 | 2021-03-30 | 南京南大光电工程研究院有限公司 | Growth of Ga on Si substrate by halide vapor phase epitaxy2O3Method for making thin film |
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| CN1327486C (en) | 2007-07-18 |
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