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CN1381870A - Technology for obtaining large-area high-quality GaN self-supporting substrate - Google Patents

Technology for obtaining large-area high-quality GaN self-supporting substrate Download PDF

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Publication number
CN1381870A
CN1381870A CN02113080.9A CN02113080A CN1381870A CN 1381870 A CN1381870 A CN 1381870A CN 02113080 A CN02113080 A CN 02113080A CN 1381870 A CN1381870 A CN 1381870A
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gan
self
film
sapphire
substrate
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CN1140915C (en
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张�荣
修向前
徐剑
顾书林
卢佃清
毕朝霞
沈波
刘治国
江若琏
施毅
朱顺明
韩平
胡立群
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Nanjing University
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Nanjing University
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Abstract

获得大面积高质量GaN自支撑衬底的方法,首先在蓝宝石衬底上横向外延获得低位错密度GaN薄膜;然后在ELO GaN薄膜上进行氢化物气相外延,获得大面积、低位错密度的GaN厚膜;采用激光扫描辐照剥离技术,将GaN厚膜从蓝宝石衬底上剥离下来,再进行表面抛光处理,就可以获得高质量GaN自支撑衬底。本发明结合了三种不同技术的优点:获得高质量的位错密度的GaN薄膜;可以快速生长大面积GaN厚膜;可以快速地无损伤的将GaN薄膜从蓝宝石衬底上分离开来。The method of obtaining a large-area high-quality GaN self-supporting substrate is first to obtain a low-dislocation density GaN film by lateral epitaxy on a sapphire substrate; High-quality GaN self-supporting substrate can be obtained by peeling off the GaN thick film from the sapphire substrate by using laser scanning irradiation stripping technology, and then performing surface polishing. The invention combines the advantages of three different technologies: high-quality dislocation density GaN film can be obtained; large-area thick GaN film can be grown rapidly; GaN film can be separated from the sapphire substrate quickly and without damage.

Description

Obtain the method for large-area high-quality GaN self-supporting substrate
One, technical field
The present invention relates to the method that horizontal extension technology, hydride gas-phase epitaxy (HVPE) thick film technology and laser lift-off technique prepare large tracts of land self-standing gan (GaN) substrate.
Two, technical background
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, is 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.Owing to lack the body monocrystalline, the acquisition of GaN film is mainly by heteroepitaxy.The most frequently used backing material is sapphire (α-Al2O3).Huge lattice mismatch and thermal mismatching have caused the dislocation of GaN epitaxial loayer middle-high density, typically can reach 10 10/ cm 2, had a strong impact on the performance and the life-span of device.The key technology that reduces dislocation density at present is that (Epitaxial-Lateral-Overgrown, method ELO), dislocation density can reduce by 4~5 more than the magnitude to the employing horizontal extension.Horizontal extension is exactly deposit masking material on the GaN planar materials that has obtained (as SiO2, Si3N4, W etc.) and carves specific graphical window, carries out the secondary epitaxy of GaN more thereon." accurate free " growth conditions owing to meet, and the direction of growth is perpendicular to the direction of climbing of former GaN dislocation, thereby very high quality is arranged.
Large tracts of land GaN substrate all is to go up vapor phase growth GaN thick film in foreign substrate (as sapphire, SiC, Si etc.) usually, obtains after then former foreign substrate being separated.Wherein growing GaN is the most general on Sapphire Substrate, and quality is also the highest.In order to obtain self-supporting GaN substrate, must remove Sapphire Substrate.Because sapphire is extremely stable, is difficult to adopt chemical corrosion method.General method is a mechanical grinding, but because of sapphire is very hard, not only will consume a large amount of diamond abrasives, and cost is very high and speed is extremely slow.Adopt the method for laser irradiation, utilize laser that the boundary zone heating of GaN thick film and substrate is made it fusing, thereby obtain the GaN substrate of self-supporting.Carefully control laser energy density and scan mode, can obtain the GaN substrate of large area, non-gap.Compare with additive method, the advantage of laser-stripping method is that the time is fast, and Sapphire Substrate is recyclable.
The GaN growth for Thin Film mainly contains gas phase epitaxy of metal organic compound (MOCVD), molecular beam epitaxy (MBE), hydride gas-phase epitaxy (HVPE) etc.Compare with MOCVD, MBE, the HVPE technology has lot of advantages: growth rate is very high, per hour can reach tens even the hundreds of micron; High horizontal-longitudinal growth rate ratio; There are not hole and yellowish leukorrhea; Can the growing large-area film etc.In conjunction with the ELO technology, GaN film that can growing high-quality.
Three, summary of the invention
The present invention seeks to: adopt the horizontal extension method in conjunction with HVPE thick film growing technology and laser lift-off technique, obtain large tracts of land low-dislocation-density high-quality GaN self-supporting substrate.
Technical solution of the present invention is: deposition, etching mask layer pattern (SiO on MOCVD, MBE or additive method growing GaN inculating crystal layer 2, Si 3N 4, W etc.); Carry out transversal epitaxial growth with the HVPE method then, obtain the thick film of GaN/ sapphire structures.With the laser scanning irradiation technique Sapphire Substrate is separated with the GaN thick film, obtain high-quality GaN self-supporting substrate.
Low dislocation density GaN growth for Thin Film method such as following: on the GaN inculating crystal layer, deposit SiO 2, Si 3N 4, film such as W, utilize photoetching method to etch certain figure, low dislocation density GaN film, 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].Orthohexagonal opening makes [1 ī 00] orientation of GaN with MOCVD or HVPE method epitaxial growth GaN, be paved with by GaN until mask layer then perpendicular to orthohexagonal limit, and continued growth obtains the low-dislocation-density gallium nitride film.
Adopt excimer laser when laser lift-off prepares the self-standing gan substrate: the pairing energy of optical maser wavelength is less than the sapphire band-gap energy, but band-gap energy greater than GaN, laser irradiation sees through Sapphire Substrate, irradiation sapphire-gallium nitride GaN at the interface, heating or weak acid corrosion then, GaN and sapphire are separated, obtain GaN self-supporting substrate.
Technical characterstic of the present invention is:
The present invention combines the advantage of three kinds of different technologies: the horizontal extension technology can obtain the GaN film of high-quality dislocation density; The hydride gas-phase epitaxy technology is the GaN thick film of tens even hundreds of micron thickness of growing large-area fast; And laser lift-off technique can undamagedly apace be separated the GaN film from Sapphire Substrate.So the employing laser lift-off technique strips down the horizontal extension GaN film of hydride gas phase epitaxial growth from Sapphire Substrate, just can obtain the self-supporting GaN substrate of large-area high-quality.
Four, embodiment
Concrete steps are as follows:
1, obtains MOCVD, MBE or additive method growing GaN inculating crystal layer on Sapphire Substrate.
On the GaN of step 1 inculating crystal layer, carry out transversal epitaxial growth, cover whole mask district, obtain ELO-GaN/ mask layer/GaN/ sapphire thin film structure until the GaN film.Mask layer adopts flexible substrate such as SiO 2, Si 3N 4, film such as W.Mask pattern can adopt parallel long strip and hexagon, and graphics shape mainly contains 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].Orthohexagonal opening, [the 1 ī 00] orientation that makes GaN is perpendicular to orthohexagonal limit.Usually, masked area is all greater than the GaN window region.
2, carry out hydride gas phase epitaxial growth on the ELO GaN film in step 2, until needed thickness.
3, laser lift-off obtains the GaN self-supporting film.Select suitable laser, sapphire is passed in the laser vertical incident that will have certain energy density, and according to certain mode, scanning and irradiation sapphire/GaN interface is separated Sapphire Substrate and GaN thick film.The pairing energy of optical maser wavelength is less than the sapphire band-gap energy, but greater than the band-gap energy of GaN.Laser energy density has the scope of certain suitable use according to the difference that adopts optical maser wavelength.Present embodiment adopts KrF ultraviolet light excimer laser (wavelength 248nm, the wide 38ns of pulse).
4, the GaN self-supporting film that step 4 is obtained carries out processed such as surface finish, just can obtain large tracts of land, low-dislocation-density, self-supporting GaN substrate.

Claims (3)

1、获得大面积高质量GaN自支撑衬底的方法,其特征是首先在蓝宝石衬底上横向外延获得低位错密度GaN薄膜;然后在ELO GaN薄膜上进行氢化物气相外延,获得大面积、低位错密度的GaN厚膜;采用激光扫描辐照剥离技术,将GaN厚膜从蓝宝石衬底上剥离下来,再进行表面抛光处理,就可以获得高质量GaN自支撑衬底。1. The method of obtaining a large-area high-quality GaN self-supporting substrate, which is characterized by first obtaining a low dislocation density GaN film by lateral epitaxy on a sapphire substrate; and then performing hydride vapor phase epitaxy on an ELO GaN film to obtain a large-area, low-position High-quality GaN self-supporting substrate can be obtained by using laser scanning irradiation stripping technology to peel off the GaN thick film from the sapphire substrate, and then perform surface polishing treatment. 2、由权利要求1所述的获得大面积高质量GaN自支撑衬底的方法,其特征是低位错密度GaN薄膜的生长方法如下述:在GaN籽品层上沉积SiO2、Si3N4、W等薄膜,利用光刻方法蚀刻出一定的图形,低位错密度GaN薄膜,图形形状主要有平行长条状和正六方形。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。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。2. The method for obtaining a large-area high-quality GaN self-supporting substrate according to claim 1, characterized in that the growth method of the low dislocation density GaN thin film is as follows: deposit SiO 2 and Si 3 N 4 on the GaN seed layer , W and other thin films are etched with a certain pattern by photolithography, low dislocation density GaN thin film, and the shapes of the patterns mainly include parallel strips and regular hexagons. For the parallel strips, the width of the mask area is 2-20 μm, the width of the GaN window area is 0.2-20 μm, and the opening direction of the parallel strips is along the [1ī00] orientation of GaN. Regular hexagonal openings, so that the [1ī00] orientation of GaN is perpendicular to the sides of the regular hexagonal, and then use MOCVD or HVPE method to epitaxially grow GaN until the mask layer is covered with GaN, and continue to grow to obtain low dislocation density gallium nitride film . 3、由权利要求1所述的获得大面积高质量GaN自支撑衬底的方法,其特征是激光剥离制备自支撑氮化镓衬底时采用准分子激光器:激光波长所对应的能量小于蓝宝石带隙能,但是大于GaN的带隙能,激光辐照透过蓝宝石衬底,辐照蓝宝石-氮化镓界面处的GaN,然后加热或弱酸腐蚀,将GaN和蓝宝石分离开来,得到GaN自支撑衬底。3. The method for obtaining a large-area high-quality GaN self-supporting substrate according to claim 1, characterized in that an excimer laser is used when preparing a self-supporting gallium nitride substrate by laser lift-off: the energy corresponding to the laser wavelength is less than that of a sapphire strip Gap energy, but greater than the bandgap energy of GaN, laser radiation penetrates the sapphire substrate, irradiates the GaN at the sapphire-gallium nitride interface, and then heats or weak acid corrosion to separate GaN and sapphire to obtain GaN self-supporting substrate.
CNB021130809A 2002-05-31 2002-05-31 Method for obtaining large-area high-quality GaN self-supporting substrates Expired - Fee Related CN1140915C (en)

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US7097920B2 (en) * 2002-03-26 2006-08-29 Nec Corporation Group III nitride based semiconductor substrate and process for manufacture thereof
CN1329955C (en) * 2004-07-21 2007-08-01 南京大学 Method of preparing high quality non-polar GaN self-support substrate
CN100433268C (en) * 2004-12-08 2008-11-12 深圳市方大国科光电技术有限公司 Sapphire supporting base grinding method
CN100454490C (en) * 2006-09-30 2009-01-21 中国科学院合肥物质科学研究院 Preparation method of self-exfoliating gallium nitride substrate material
CN100463102C (en) * 2004-11-23 2009-02-18 北京大学 Large-area, low-power laser lift-off method for GaN-based epitaxial layers
CN101680109A (en) * 2008-03-11 2010-03-24 住友电气工业株式会社 Apparatus and method for manufacturing compound semiconductor single crystal
CN101378008B (en) * 2008-09-19 2010-06-02 苏州纳维科技有限公司 Method for separating epitaxial layer and substrate
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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
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CN101680114B (en) * 2007-05-25 2013-02-27 高晶科技有限公司 Method for manufacturing gan-based nitride semiconductor self-supporting substrate
CN103021946A (en) * 2012-12-05 2013-04-03 北京大学 Method of preparing GaN monocrystal substrate in mechanical removal way
CN103367209A (en) * 2013-07-26 2013-10-23 东莞市中镓半导体科技有限公司 Liquid assisted laser lift-off method
CN103367117A (en) * 2013-07-05 2013-10-23 江苏能华微电子科技发展有限公司 GaN (gallium nitride) substrate production method based on HVPE (hydride vapor phase epitaxy) process
CN107134406A (en) * 2017-05-08 2017-09-05 东莞市中镓半导体科技有限公司 A kind of method for preparing nitride self-supported substrate
CN112301422A (en) * 2019-08-01 2021-02-02 北京飓芯科技有限公司 Substrate stripping method based on laminated mask substrate
CN107978659B (en) * 2016-10-21 2021-05-28 三星电子株式会社 Method of manufacturing a gallium nitride substrate

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US7097920B2 (en) * 2002-03-26 2006-08-29 Nec Corporation Group III nitride based semiconductor substrate and process for manufacture thereof
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
CN102174713B (en) * 2004-08-10 2012-07-04 日立电线株式会社 Group iii-v nitride-based semiconductor substrate, its manufacturing method, and group iii-v nitride-based semiconductor
CN100463102C (en) * 2004-11-23 2009-02-18 北京大学 Large-area, low-power laser lift-off method for GaN-based epitaxial layers
CN100433268C (en) * 2004-12-08 2008-11-12 深圳市方大国科光电技术有限公司 Sapphire supporting base grinding method
CN100454490C (en) * 2006-09-30 2009-01-21 中国科学院合肥物质科学研究院 Preparation method of self-exfoliating gallium nitride substrate material
CN101595572B (en) * 2006-12-26 2012-11-28 Qmc株式会社 System and method for deliverying laser beam and laser lift-off method using the same
CN101680114B (en) * 2007-05-25 2013-02-27 高晶科技有限公司 Method for manufacturing gan-based nitride semiconductor self-supporting substrate
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