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CN1389904A - Transverse epitaxial growth process of high-quality gallium nitride film - Google Patents

Transverse epitaxial growth process of high-quality gallium nitride film Download PDF

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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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gan
film
hvpe
dislocation density
mocvd
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CN1174470C (en
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张�荣
修向前
顾书林
卢佃清
毕朝霞
沈波
江若琏
施毅
朱顺明
韩平
胡立群
郑有炓
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Nanjing University
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Nanjing University
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Abstract

横向外延生长高质量氮化镓薄膜的方法,用MOCVD、MBE或其他方法生长GaN籽晶层;在GaN籽晶层上沉积SiO2、Si3N4、W等薄膜,利用光刻方法蚀刻出一定的图形,对于平行长条状,掩摸区宽度2-20μm,GaN窗口区宽度0.2-20μm,平行长条状的开口方向是沿GaN的[1100]取向;对于正六边形的开口,使GaN的[1100]取向垂直于正六边形的边,然后用MOCVD或HVPE方法外延生长GaN,直至掩模层被GaN铺满,继续生长得到低位错密度氮化镓薄膜。HVPE生长速率很快。由于在远离界面处位错密度比较低,所以在横向外延薄膜上HVPE厚膜外延,可得到位错密度更低的GaN薄膜。The method of lateral epitaxial growth of high-quality gallium nitride film, using MOCVD, MBE or other methods to grow the GaN seed layer; depositing SiO 2 , Si 3 N 4 , W and other thin films on the GaN seed layer, etched out by photolithography For a certain pattern, for parallel strips, the width of the mask area is 2-20 μm, and the width of the GaN window area is 0.2-20 μm. The opening direction of the parallel strips is along the [1100] orientation of GaN; for regular hexagonal openings, make The [1100] orientation of GaN is perpendicular to the sides of the regular hexagon, and then epitaxially grow GaN by MOCVD or HVPE until the mask layer is covered by GaN, and continue to grow to obtain a low dislocation density gallium nitride film. The growth rate of HVPE is very fast. Because the dislocation density is relatively low far away from the interface, the GaN film with lower dislocation density can be obtained by HVPE thick film epitaxy on the lateral epitaxial film.

Description

The method of transversal epitaxial growth high-quality gallium nitride film
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、横向外延生长高质量氮化镓薄膜的方法,其特征是用MOCVD、MBE或其他方法生长GaN籽晶层;在GaN籽晶层上沉积SiO2、Si3N4、W等薄膜,利用光刻方法蚀刻出一定的图形,对于平行长条状,掩摸区宽度2-20μm,GaN窗口区宽度0.2-20μm,平行长条状的开口方向是沿GaN的[1ī00]取向;对于正六边形的开口,使GaN的[1ī00]取向垂直于正六边形的边,然后用MOCVD或HVPE方法外延生长GaN,直至掩模层被GaN铺满,继续生长得到低位错密度氮化镓薄膜。1. A method for growing high-quality gallium nitride films by lateral epitaxy, which is characterized by growing a GaN seed layer by MOCVD, MBE or other methods; depositing SiO 2 , Si 3 N 4 , W and other films on the GaN seed layer, using A certain pattern is etched by photolithography. For parallel strips, the width of the mask area is 2-20 μm, and the width of the GaN window area is 0.2-20 μm. The opening direction of parallel strips is along the [1ī00] orientation of GaN; Shaped openings, so that the [1ī00] orientation of GaN is perpendicular to the sides of the regular hexagon, and then epitaxially grow GaN by MOCVD or HVPE until the mask layer is covered with GaN, and continue to grow to obtain a low dislocation density GaN film. 2、由权利要求1所述的横向外延生长高质量氮化镓薄膜的方法,其特征是V价N原子与III价Ga原子比33~83∶1。2. The method for growing high-quality GaN thin films by lateral epitaxy according to claim 1, characterized in that the ratio of V-valent N atoms to III-valent Ga atoms is 33-83:1.
CNB021130841A 2002-05-31 2002-05-31 Method for growing high-quality GaN thin films by lateral epitaxial growth Expired - Fee Related CN1174470C (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
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

Cited By (16)

* Cited by examiner, † Cited by third party
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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