CN1389904A - Transverse epitaxial growth process of high-quality gallium nitride film - Google Patents
Transverse epitaxial growth process of high-quality gallium nitride film Download PDFInfo
- Publication number
- CN1389904A CN1389904A CN02113084.1A CN02113084A CN1389904A CN 1389904 A CN1389904 A CN 1389904A CN 02113084 A CN02113084 A CN 02113084A CN 1389904 A CN1389904 A CN 1389904A
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- gallium nitride
- nitride film
- growth
- film
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- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 61
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims abstract description 16
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 238000000407 epitaxy Methods 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001657 homoepitaxy Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
The invention relates to the method of growth of gallium nitride film in high quality by the technique of extension in the lateral direction. GaN crystal seed layer is grown by use of the MOCVD, MBE or other method. The SiO2, Si3N4W etc. films are deposited on the GaN crystal seed layer with sertain graph being etched by etching method. The direction of the parallel strip opening is along the direction of GaN [1100]. The width of the mask area is 2-20 microns. The width of the GaN window area is 0.2-20 microns. Then the MOCVD or HVPE method is accepted to grow GaN in epitaxial growth till the mask layer is overspreader by the GaN. Continuing growth obtains the gallium nitride film with low dislocation density. Since HVPE providing quick growth rare, to the HVPE thick film extension can obtain GaN film even lower dislocation density.
Description
One, technical field
The present invention relates to the method and the technology of horizontal extension technology and bond organics gaseous phase extended (MOCVD), hydride gas-phase epitaxy thin film technique growing gallium nitride (GaN) films such as (HVPE), the method for the low dislocation density GaN film of especially growing.
Two, background technology
III-V group nitride material (claiming the GaN sill again) based on GaN and InGaN, AlGaN alloy material is the novel semiconductor material of extremely paying attention in the world in recent years, the direct band gap of its 1.9-6.2eV continuous variable, excellent physics, chemical stability, high saturated electron drift velocity, superior functions such as high disruptive field intensity and high heat conductance make it become the most preferably material of short wavelength's semiconductor photoelectronic device and high frequency, high pressure, the preparation of high temperature microelectronic component.
Because the restriction of the physical property of GaN own, the growth of GaN body monocrystalline has very big difficulty, as yet practicability not.Yet, carry out homoepitaxy with the GaN substrate and obtain III group-III nitride thin-film material and but demonstrated extremely superior performance, therefore with the low-dislocation-density substrate carry out GaN homoepitaxy be improve III nitride epitaxial layers quality than good method.Early stage people mainly adopt hydride gas-phase epitaxy (HVPE) method direct growth GaN on Sapphire Substrate, are separated again, obtain the GaN backing material.The outstanding shortcoming of this method is that dislocation density is very high in the GaN epitaxial loayer, generally reaches 10
10Cm
-2About.The key technology that reduces dislocation density at present is to adopt horizontal extension (Epitaxial-Lateral-Overgrown, method ELO).Dislocation density can reduce by 4～5 magnitudes.
GaN horizontal extension technology is meant that the deposit masking material is (as SiO on the GaN planar materials that has obtained
2, Si
3N
4, W etc.) and carve specific graphical window, carry out the secondary epitaxy of GaN more thereon.Employing horizontal extension technology can reduce the dislocation density in the epitaxial loayer significantly, and improves epitaxial layer quality, reduces the involuntary doping electron concentration of epitaxial loayer, thereby reduces P type doping difficulty etc.
In the present invention, we adopt the horizontal extension method in conjunction with MOCVD, the HVPE film growth techniques low dislocation density GaN film of growing on Sapphire Substrate, and dislocation density is lower than 10
6/ cm
2
Three, summary of the invention
The present invention seeks to: the horizontal extension method is in conjunction with MOCVD, the HVPE film growth techniques low dislocation density GaN film of growing on Sapphire Substrate.
Technical solution of the present invention:
At first use MOCVD, MBE or additive method growing GaN inculating crystal layer; On the GaN inculating crystal layer, deposit SiO
2, Si
3N
4, film such as W, utilize photoetching method to etch certain figure (as strip, hexagon etc.); With MOCVD or the epitaxial growth of HVPE method, be paved with by GaN until mask layer then, continued growth obtains thick film.Zhi Bei GaN thin film dislocation density is lower like this (is lower than 10
6/ cm
2), be of high quality.
Mechanism of the present invention and technical characterstic are:
In GaN horizontal extension technology, because selective epitaxy, only in the epitaxial growth of GaN window portion energy GaN ability, and SiO
2Partly be difficult to nucleation Deng mask layer.When the GaN that goes out when extension in the GaN window region surpasses mask layer thickness, when grow with vertical direction, the generation cross growth.After acquiring a certain degree, cross growth just can be carried out the GaN epitaxial loayer of lid entirely.This growth is " accurate free " growth conditions because meet, and the direction of growth is perpendicular to the direction of climbing of former GaN dislocation, thereby very high quality is arranged, and dislocation density is lower more than direct growth.The HVPE growth rate is very fast, can reach youngster ten even hundreds of μ m/ hour.Because away from dislocation density is lower at the interface, thus on the horizontal extension film HVPE thick film extension, can obtain the lower GaN film of dislocation density.
Four, description of drawings
Fig. 1 is the GaN film sectional view of horizontal extension of the present invention and HVPE technology growth, and dislocation density is lower than 10
6/ cm
2
Growth conditions: 1100 ℃, [NH
3]: [HCl]=0.076: 0.0023.
Fig. 2 is the GaN film AFM surface topography map of horizontal extension of the present invention and HVPE technology growth.Among the figure, GaN
GaN in window region and the mask district combines.Growth conditions: 1100oC,
[NH
3]∶[HCl]＝0.076∶0.0023。
Five, embodiment
The transversal epitaxial growth technology that the present invention adopts comprises following a few step:
1, adopts MOCVD, MBE or additive method growing GaN inculating crystal layer on Sapphire Substrate.
2, deposit SiO on the GaN inculating crystal layer
2, Si
3N
4, film such as W makes mask layer, thickness is 100nm.
3, obtain certain figure with the photoetching method etch mask layer, the mask district is generally all greater than window region.Graphics shape
Mainly contain parallel long strip and orthohexagonal.For the parallel long strip, mask sector width 2-20 μ m, GaN
Window region width 0.2-20 μ m, the opening direction of parallel long strip is orientated along GaN [1 ī 00].Positive six
The opening of limit shape, [the 1 ī 00] orientation that makes GaN is perpendicular to orthohexagonal limit.
4, control V valency N atom and III valency Ga atomic ratio (33～83: 1), growth temperature (1030～1100 ℃),
The selection of window and mask regions is compared etc., under different conditions, and HVPE on above-mentioned figure GaN inculating crystal layer
Extension GaN thick film.On the figure inculating crystal layer, also can directly carry out horizontal extension and thick film life with MOCVD
Long, just the time is long more than HVPE.
5, in addition, above-mentioned steps 4 also can be carried out like this: elder generation's MOCVD growing GaN on figure GaN, when
After film covers with whole mask layer, adopt the HVPE growing technology acquisition thick film of growing fast again.
The GaN film that obtains of growth like this, dislocation density can be lower than 10
6/ cm
2
Claims (2)
1, the method for transversal epitaxial growth high-quality gallium nitride film is characterized in that with MOCVD, MBE or additive method growing GaN inculating crystal layer; On the GaN inculating crystal layer, deposit SiO
2, Si
3N
4, film such as W, utilize photoetching method to etch certain figure, for the parallel long strip, mask sector width 2-20 μ m, GaN window region width 0.2-20 μ m, the opening direction of parallel long strip are orientated along GaN [1 ī 00]; For orthohexagonal opening, [1 ī 00] orientation of GaN with MOCVD or HVPE method epitaxial growth GaN, is paved with by GaN until mask layer then perpendicular to orthohexagonal limit, continued growth obtains the low-dislocation-density gallium nitride film.
2,, it is characterized in that V valency N atom and III valency Ga atomic ratio 33～83: 1 by the method for the described transversal epitaxial growth high-quality gallium nitride film of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021130841A CN1174470C (en) | 2002-05-31 | 2002-05-31 | Transverse epitaxial growth process of high-quality gallium nitride film |
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|---|---|---|---|
| CNB021130841A CN1174470C (en) | 2002-05-31 | 2002-05-31 | Transverse epitaxial growth process of high-quality gallium nitride film |
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| Publication Number | Publication Date |
|---|---|
| CN1389904A true CN1389904A (en) | 2003-01-08 |
| CN1174470C CN1174470C (en) | 2004-11-03 |
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|---|---|---|---|
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300387C (en) * | 2004-11-12 | 2007-02-14 | 南京大学 | Process for non-mask transverse epitaxial growth of high quality gallium nitride |
| CN1309013C (en) * | 2004-03-05 | 2007-04-04 | 长春理工大学 | Method of growing low dislocation gallium nitride on silicon substrate |
| CN1318661C (en) * | 2003-05-08 | 2007-05-30 | 住友电气工业株式会社 | III-v compound semiconductor crystal and method for production thereof |
| CN1329955C (en) * | 2004-07-21 | 2007-08-01 | 南京大学 | Method of preparing high quality non-polar GaN self-support substrate |
| CN100478491C (en) * | 2005-07-29 | 2009-04-15 | 中国科学院上海微系统与信息技术研究所 | Metal inserting layer in hydride gas phase epitaxial growth gallium nitride film and process for preparing the same |
| CN101245491B (en) * | 2007-02-14 | 2011-06-15 | 中国科学院半导体研究所 | Method for growing unsupported gallium nitride nanocrystalline on zinc oxide of nano-stick |
| CN1734247B (en) * | 2004-08-10 | 2011-07-20 | 日立电线株式会社 | III-V group nitride system semiconductor substrate, method of making the same and III-V group nitride system semiconductor |
| CN102828240A (en) * | 2012-08-31 | 2012-12-19 | 南京大学 | Method for preparing GaN film material |
| WO2014032467A1 (en) * | 2012-08-31 | 2014-03-06 | 南京大学 | Method for preparing low-stress gan film |
| CN104818526A (en) * | 2015-01-27 | 2015-08-05 | 夏洋 | Preparation method for vapor grown two-dimensional material |
| CN105448651A (en) * | 2014-08-15 | 2016-03-30 | 北大方正集团有限公司 | Epitaxial wafer on substrate and manufacturing method |
| CN106981415A (en) * | 2017-04-19 | 2017-07-25 | 华南理工大学 | The gallium nitride film and its nanometer epitaxial lateral overgrowth method of GaN HEMTs |
| CN109097834A (en) * | 2018-09-03 | 2018-12-28 | 南京大学 | Porous network structure GaN single crystal film, preparation method and application |
| CN112301325A (en) * | 2019-08-01 | 2021-02-02 | 北京飓芯科技有限公司 | 3D laminated mask substrate structure and preparation method and epitaxial growth method thereof |
-
2002
- 2002-05-31 CN CNB021130841A patent/CN1174470C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318661C (en) * | 2003-05-08 | 2007-05-30 | 住友电气工业株式会社 | III-v compound semiconductor crystal and method for production thereof |
| CN1309013C (en) * | 2004-03-05 | 2007-04-04 | 长春理工大学 | Method of growing low dislocation gallium nitride on silicon substrate |
| CN1329955C (en) * | 2004-07-21 | 2007-08-01 | 南京大学 | Method of preparing high quality non-polar GaN self-support substrate |
| CN1734247B (en) * | 2004-08-10 | 2011-07-20 | 日立电线株式会社 | III-V group nitride system semiconductor substrate, method of making the same and III-V group nitride system semiconductor |
| CN1300387C (en) * | 2004-11-12 | 2007-02-14 | 南京大学 | Process for non-mask transverse epitaxial growth of high quality gallium nitride |
| CN100478491C (en) * | 2005-07-29 | 2009-04-15 | 中国科学院上海微系统与信息技术研究所 | Metal inserting layer in hydride gas phase epitaxial growth gallium nitride film and process for preparing the same |
| CN101245491B (en) * | 2007-02-14 | 2011-06-15 | 中国科学院半导体研究所 | Method for growing unsupported gallium nitride nanocrystalline on zinc oxide of nano-stick |
| WO2014032467A1 (en) * | 2012-08-31 | 2014-03-06 | 南京大学 | Method for preparing low-stress gan film |
| CN102828240A (en) * | 2012-08-31 | 2012-12-19 | 南京大学 | Method for preparing GaN film material |
| CN102828240B (en) * | 2012-08-31 | 2015-11-25 | 南京大学 | A kind of method preparing GaN film material |
| CN105448651A (en) * | 2014-08-15 | 2016-03-30 | 北大方正集团有限公司 | Epitaxial wafer on substrate and manufacturing method |
| CN105448651B (en) * | 2014-08-15 | 2019-03-29 | 北大方正集团有限公司 | A kind of epitaxial wafer and preparation method thereof on substrate |
| CN104818526A (en) * | 2015-01-27 | 2015-08-05 | 夏洋 | Preparation method for vapor grown two-dimensional material |
| CN106981415A (en) * | 2017-04-19 | 2017-07-25 | 华南理工大学 | The gallium nitride film and its nanometer epitaxial lateral overgrowth method of GaN HEMTs |
| CN109097834A (en) * | 2018-09-03 | 2018-12-28 | 南京大学 | Porous network structure GaN single crystal film, preparation method and application |
| CN112301325A (en) * | 2019-08-01 | 2021-02-02 | 北京飓芯科技有限公司 | 3D laminated mask substrate structure and preparation method and epitaxial growth method thereof |
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| CN1174470C (en) | 2004-11-03 |
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