JP2009524251A - 有機金属化学気相成長を介して半極性(Al,In,Ga,B)Nの成長を促進させるための方法 - Google Patents
有機金属化学気相成長を介して半極性(Al,In,Ga,B)Nの成長を促進させるための方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 50
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 10
- 230000001737 promoting effect Effects 0.000 title claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 67
- 230000006911 nucleation Effects 0.000 claims abstract description 54
- 238000010899 nucleation Methods 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000004065 semiconductor Substances 0.000 claims abstract description 36
- 239000010409 thin film Substances 0.000 claims abstract description 35
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 13
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 45
- 229910052594 sapphire Inorganic materials 0.000 claims description 18
- 239000010980 sapphire Substances 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002601 GaN Inorganic materials 0.000 description 52
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 52
- 230000010287 polarization Effects 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 230000005693 optoelectronics Effects 0.000 description 8
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 7
- 230000002269 spontaneous effect Effects 0.000 description 7
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 6
- 238000000879 optical micrograph Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910002704 AlGaN Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001534 heteroepitaxy Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000005701 quantum confined stark effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
Description
本出願は、以下の同時継続中の同一譲受人の米国特許出願に対し、35 U.S.C.第119(e)節に基づく優先権を主張する:
米国仮特許出願第60/760,628号、2006年1月20日出願、発明者Hitoshi Sato,John Kaeding,Michael Iza,Troy J.Baker,Benjamin A.Haskell,Steven P.DenBaars、Shuji Nakamura、発明の名称「METHOD FOR ENHANCING GROWTH OF SEMIPOLAR (Al,In,Ga,B)N VIA METALORGANIC CHEMICAL VAPOR DEPOSITION」、代理人管理番号第30794.159−US−P1(2006−178);
この出願は、参照により本明細書に援用される。
米国特許出願第11/372,914号、2006年3月10日出願、発明者Troy J.Baker,Benjamin A.Haskell,Paul T.Fini,Steven P.Denbaars,James S.Speck,Shuji Nakamura、発明の名称「TECHNIQUE FOR THE GROWTH OF PLANAR SEMI−POLAR GALLIUM NITRIDE」、代理人管理番号第30794.128−US−US1(2005−471)、この出願は、米国仮特許出願第60/660,283号、2005年3月10日出願、発明者Troy J.Baker,Benjamin A.Haskell,Paul T.Fini,Steven P.Denbaars,James S.Speck,Shuji Nakamura、「TECHNIQUE FOR THE GROWTH OF PLANAR SEMI−POLAR GALLIUM NITRIDE」、代理人管理番号第30794.128−US−P1(2005−471)について35 U.S.C.第119(e)節に基づく優先権を主張する;
米国特許出願第11/444,946号、2006年6月1日出願、発明者Robert M.Farrell,Jr.,Troy J.Baker,Arpan Chakraborty,Benjamin A.Haskell,P.Morgan Pattison,Rajat Sharma,Umesh K.Mishra,Steven P.Denbaars,James S.Speck,Shuji Nakamura、発明の名称「TECHNIQUE FOR THE GROWTH AND FABRICATION OF SEMIPOLAR (Ga,Al,In,B)N THIN FILMS,HETEROSTRUCTURES,AND DEVICES」、代理人管理番号第30794.140−US−US1(2005−668)、この出願は、米国仮特許出願第60/686,244号、2005年6月1日出願、発明者Robert M.Farrell,Jr.,Troy J.Baker,Arpan Chakraborty,Benjamin A.Haskell,P.Morgan Pattison,Rajat Sharma,Umesh K.Mishra,Steven P.Denbaars,James S.Speck,Shuji Nakamura、発明の名称「TECHNIQUE FOR THE GROWTH AND FABRICATION OF SEMIPOLAR (Ga,Al,In,B)N THIN FILMS,HETEROSTRUCTURES,AND DEVICES」、代理人管理番号第30794.140−US−P1(2005−668)について35 U.S.C.第119(e)節に基づく優先権を主張する;
米国特許出願第11/486,224号、2006年7月13日出願、発明者Troy J.Baker,Benjamin A.Haskell,James S.Speck,Shuji Nakamura、発明の名称「LATERAL GROWTH METHOD FOR DEFECT REDUCTION OF SEMIPOLAR NITRIDE FILMS」、代理人管理番号第30794.141−US−US1(2005−672)、この出願は、米国仮特許出願第60/698,749号、2005年7月13日出願、発明者Troy J.Baker,Benjamin A.Haskell,James S.Speck,Shuji Nakamura、発明の名称「LATERAL GROWTH METHOD FOR DEFECT REDUCTION OF SEMIPOLAR NITRIDE FILMS」、代理人管理番号第30794.141−US−P1(2005−672)について35 U.S.C.第119(e)節に基づく優先権を主張する;
米国特許出願第11/517,797号、2006年9月8日出願、発明者Michael Iza,Troy J.Baker,Benjamin A.Haskell,Steven P.Denbaars,Shuji Nakamura、「METHOD FOR ENHANCING GROWTH OF SEMIPOLAR (Al,In,Ga,B)N VIA METALORGANIC CHEMICAL VAPOR DEPOSITION」、代理人管理番号第30794.144−US−US1(2005−772)、この出願は、米国仮特許出願第60/715,491号、2005年9月9日出願、発明者Michael Iza,Troy J.Baker,Benjamin A.Haskell,Steven P.Denbaars,Shuji Nakamura、「METHOD FOR ENHANCING GROWTH OF SEMIPOLAR (Al,In,Ga,B)N VIA METALORGANIC CHEMICAL VAPOR DEPOSITION」、代理人管理番号第30794.144−US−P1(2005−772)について35 U.S.C.第119(e)節に基づく優先権を主張する;
米国特許出願第xx/xxx,xxx、本出願と同日出願、発明者John Kaeding,Dong−Seon Lee,Michael Iza,Troy J.baker,Hitoshi Sato,Benjamin A.Haskell,James S.Speck,Steven P.Denbaars,Shuji Nakamura、発明の名称「METHOD FOR IMPROVED GROWTH OF SEMIPOLAR (Al,In,Ga,B)N」、代理人管理番号第30794.150−US−U1(2006−126)、この出願は、米国仮特許出願第60/760,739号、2006年1月20日出願、発明者John Kaeding,Michael Iza,Troy J.baker,Hitoshi Sato,Benjamin A.Haskell,James S.Speck,Steven P.Denbaars,Shuji Nakamura、発明の名称「METHOD FOR IMPROVED GROWTH OF SEMIPOLAR (Al,In,Ga,B)N」、代理人管理番号第30794.150−US−P1(2006−126)について35 U.S.C.第119(e)節に基づく優先権を主張する;
米国仮特許出願第60/774,467号、2006年2月17日出願、発明者Hong Zhong,John F.Kaeding,Rajat Sharma,James S.Speck,Steven P.Denbaars,Shuji Nakamura、発明の名称「METHOD FOR GROWTH OF SEMIPOLAR(Al,In,ga,B)N OPTOELECTRONICS DEVICES」、代理人管理番号第30794.173−US−P1(2006−422);
米国仮特許出願第60/869,540、2006年12月11日出願、発明者Steven P.Denbaars,mathew C.Schmidt,Kwang Choong Kim,James S.Speck,Shuji Nakamura、「NON−POLAR(M−PLANE) AND SEMI−POLAR EMITTINGDEVICES」、代理人管理番号第30794.213−US−P1(2007−317);
米国仮特許出願第60/869,701号、2006年12月12日出願、発明者Kwang Choon Kim,Mathew C.Schmidt,Feng Wu,Asako Hirai,Melvin B.McLaurin,Steven P.Denbaars,Shuji Nakamura,James S.Speck、発明の名称「CRYSTAL GROWTH OF M−PLANE AND SEMIPOLAR PLANES OF (Al,In,Ga,B)N ON VARIOUS SUBSTRATES」、代理人管理番号第30794.214−US−P1(2007−334);
上記出願の全ては、参照により本明細書に援用される。
本発明は、有機金属化学気相成長法(Metalorganic Chemical Vapor Deposition;MOCVD)により半極性(Al,In,Ga,B)Nの成長を促進するための方法に関する。
(注:本願は、明細書全体において示されるように、括弧の中の1つ以上の参照番号(例えば[x])により、多くの異なる出版物および特許を参照している。これらの参照番号順で示されたこれらの異なる出版物および特許の一覧は、下の「参考文献」という表題の項で参照することができる。これらの出版物および特許はそれぞれ、参照することにより本明細書に援用される。)
可視および紫外光電子デバイス、ならびに高出力電子デバイスの製造において、窒化ガリウム(GaN)、ならびにアルミニウムおよびインジウムを取り入れたその三元および四元化合物(AlGaN、InGaN、AlInGaN等)の有用性が確立されている。これらのデバイスは、典型的には、分子線エピタキシ(Molecular Beam Epitaxy;MBE)、有機金属化学気相成長法(Metalorganic Chemical Vapor Deposition;MOCVD)、および水素化物気相エピタキシ(Hydride Vapor Phase Epitaxy;HVPE)等の成長技術を用いてエピタキシャルに成長される。
本発明は、少なくともある程度のインジウムを含む(Al,In,Ga)N核形成層を使用したMOCVDによる、デバイス品質平面半極性(例えば
図1は、本発明は、典型的には50Å〜1000Åの厚さの、デバイス品質平面半極性窒化物半導体薄膜の成長を促進するための方法であって、半極性窒化物半導体薄膜を、少なくともある程度のインジウムを含む(Al,In,Ga)N核形成層またはバッファ層上に堆積させるステップを含む方法を示すフローチャートである。
本発明の範囲に含まれるのは、上述の具体例だけではない。この考えは、あらゆる半極性面のすべての窒化物に関連する。例えば、ミスカット
現在実践されているのは、基板と平行なc面を有するGaNの成長である。この面は、ともに膜と垂直な自発分極および圧電分極を有し、これはデバイス性能に有害である。c面窒化物膜に勝る半極性膜の利点は、あるデバイスにおける分極の低減とそれに関連した内部量子効率の増加である。
以下の参考文献は、参照することにより本明細書に援用される。
[1]Nishizuka, K., Applied Physics Letters, Vol. 85 Number 15, 11 October 2004.この論文は、ELO材料の
[2]H. Amano, N. Sawaki, I. Akasaki and Y. Toyoda, Applied Physics Letters Vol. 48 (1986) pp. 353.この論文は、GaN結晶品質改善のためのAlNバッファ層の使用について述べている。
[3]S. Nakamura, Japanese Journal of Applied Physics Vol. 30, No. 10A, October, 1991, pp. L1705−L1707.この論文は、GaN結晶品質改善のためのGaNバッファ層の使用について述べている。
[4]D. D. Koleske, M. E. Coltrin, K. C. Cross, C. C. Mitchell, A. A. Allernan, Journal of Crystal Growth Vol. 273 (2004) pp. 86−99.この論文は、サファイア基板上でのGaNバッファ層の形態発達の効果について述べている。
[5]B. Moran, F. Wu, A. E. Romanov, U. K. Mishra, S. P. Denbaars, J. S. Speck, Journal of Crystal Growth Vol. 273 (2004) pp. 38−47.この論文は、炭化ケイ素基板上でのAlNバッファ層の形態発達の効果について述べている。
[6]米国特許第4,855,249号、1989年8月8日Akasakiらに対し発行、名称「Process for growing III−V compound semiconductors on sapphire using a buffer layer」
[7]米国特許第5,741,724号、1998年4月21日Ramdaniらに対し発行、名称「Method of growing gallium nitride on a spinel substrate」
(結び)
これで、本発明の好適な実施形態の説明を終わる。本発明の1つ以上の実施形態の前述の説明は、例示および説明を目的として提示されている。網羅的であること、または開示される正確な形態に本発明を限定することを意図しない。上述の教示に照らして、多くの修正または変形が可能である。本発明の範囲はこの詳細な説明によって限定されるのではなく、添付の請求項により限定されることが意図される。
Claims (14)
- デバイス品質の平面状の半極性窒化物半導体薄膜の成長を促進するための方法であって、
(a)少なくともある程度のインジウムを含む(Al,In,Ga)N核形成層またはバッファ層上に、半極性窒化物半導体薄膜を堆積させること
を含む、方法。 - 前記(Al,In,Ga)N核形成層またはバッファ層は、InxGa1−xN核形成層(x>0)を含む、請求項1に記載の方法。
- 前記(Al,In,Ga)N核形成層またはバッファ層は、InxGa1−xN核形成層(x=0.1)を含む、請求項1に記載の方法。
- 前記半極性窒化物半導体薄膜は、式GanAlxInyBzN(0≦n≦1、0≦x≦1、0≦y≦1、0≦z≦1、およびn+x+y+z=1)を有する(Ga,Al,In,B)N半導体の合金組成物を含む、請求項1に記載の方法。
- 前記半極性窒化物半導体薄膜の幅10ミクロンより大きい領域は、(Al,In,Ga)N核形成層またはバッファ層が成長される基板表面に実質的に平行である、請求項1に記載の方法。
- 前記半極性窒化物半導体薄膜は、有機金属化学気相成長法(MOCVD)により成長される、請求項1に記載の方法。
- 前記半極性窒化物半導体薄膜は、(Al,In,Ga)N核形成層またはバッファ層なしでの堆積と比較して、平面膜表面、より少ない表面凹凸、および低減された結晶学的欠陥数を含む、最新の窒化物半極性電子デバイスに必要な表面形態を有する、請求項1に記載の方法。
- 請求項1に記載の方法を使用して製造されるデバイス。
- デバイス品質の平面状の半極性窒化物半導体薄膜を成長させるための方法であって、
(a)反応容器に基板を装填することと、
(b)窒素、水素、およびアンモニアのうちの少なくとも1つを含むフロー中で前記基板を加熱することと、
(c)前記加熱された基板上にInxGa1−xN核形成層を堆積させることと、
(d)前記InxGa1−xN核形成層上に半極性窒化物半導体薄膜を堆積させることと、
(e)窒素過圧下で前記基板を冷却することと
を含む、方法。 - 請求項12に記載の方法を使用して製造されるデバイス。
- インジウムを含む核形成層上に堆積された半極性窒化物を含む、平面状の半極性窒化物半導体薄膜。
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