JP5046475B2 - 金属・有機化学気相成長によって成長した非極性a平面窒化ガリウム薄膜 - Google Patents
金属・有機化学気相成長によって成長した非極性a平面窒化ガリウム薄膜 Download PDFInfo
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- JP5046475B2 JP5046475B2 JP2003586402A JP2003586402A JP5046475B2 JP 5046475 B2 JP5046475 B2 JP 5046475B2 JP 2003586402 A JP2003586402 A JP 2003586402A JP 2003586402 A JP2003586402 A JP 2003586402A JP 5046475 B2 JP5046475 B2 JP 5046475B2
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- 229910002601 GaN Inorganic materials 0.000 title claims description 92
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims description 80
- 238000005229 chemical vapour deposition Methods 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 title claims 2
- 239000002184 metal Substances 0.000 title claims 2
- 239000010409 thin film Substances 0.000 title description 19
- 229910052594 sapphire Inorganic materials 0.000 claims description 45
- 239000010980 sapphire Substances 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 230000007547 defect Effects 0.000 claims description 15
- 150000004767 nitrides Chemical class 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 27
- 230000010287 polarization Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 230000005684 electric field Effects 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910002704 AlGaN Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- MNKMDLVKGZBOEW-UHFFFAOYSA-M lithium;3,4,5-trihydroxybenzoate Chemical compound [Li+].OC1=CC(C([O-])=O)=CC(O)=C1O MNKMDLVKGZBOEW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 nitride compounds Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000069 prophylactic effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VLCQZHSMCYCDJL-UHFFFAOYSA-N tribenuron methyl Chemical compound COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)N(C)C1=NC(C)=NC(OC)=N1 VLCQZHSMCYCDJL-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 230000005533 two-dimensional electron gas Effects 0.000 description 1
- 230000005428 wave function Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C30B29/406—Gallium nitride
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- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Description
本願は、米国特許法第119条第(e)項のもとで、以下の同時係属中の、同一人に譲渡された米国仮特許出願番号60/372,909(発明の名称「NON−POLAR GALLIUM NITRIDE BASED THIN FILMS AND HETEROSTRUCTURE MATERIALS」、2002年4月15日出願、Michael D.Craven,Stacia Keller,Steven P.DenBaars,Tal Margalith,James S.Speck,Shuji Nakamura,およびUmesh K.Mishra、代理人文書番号30794.95−US−P1)の利益を主張する。この出願は、本明細書中に参考として援用される。
出願番号−−/−−−,−−−、発明の名称「NON−POLAR(AL,B,IN,GA)N QUANTUM WELL AND HETEROSTRUCTURE MATERIALS AND DEVICES」、本願と同日に出願、Michael D.Craven,Stacia Keller,Steven P.DenBaars,Tal Margalith,James S.Speck,Shuji Nakamura,およびUmesh K.Mishra、代理人文書番号30794.101−US−U1);ならびに
出願番号−−/−−−,−−−、発明の名称「DISLOCATION REDUCTION IN NON−POLAR GALLIUM NITRIDE THIN FILMS」、本願と同日に出願、Michael D.Craven,Steven P.DenBaars,およびJames S.Speck、代理人文書番号30794.102−US−U1);
これらの出願の両方が、本明細書中に参考として援用される。
本発明は、半導体材料、方法、およびデバイスに関し、そしてより具体的には、金属・有機化学気相成長(MOCVD)によって成長された、非極性のa平面窒化ガリウム(GaN)薄膜に関する。
(注:本願は、多数の異なる特許、出願および/または刊行物を、1つ以上の参照番号によって、本明細書全体に示されるように参照する。これらの異なる刊行物の、これらの参照番号に従った順序にしたリストは、以下の「参考文献」の表題の節に見出され得る。これらの刊行物の各々は、本明細書中に参考として援用される)。
本発明は、デバイス品質の、非極性のa平面GaN薄膜を、MOCVDを介して、r平面サファイア基板上で成長させるための方法を記載する。本発明は、分極により誘導される効果のない、窒化物ベースのデバイスのための経路を提供する。なぜなら、非極性のa平面GaN薄膜の成長方向は、極性のc軸に対して垂直であるからである。分極により誘導される電場は、存在する場合、非極性のa平面GaN薄膜上で成長する(Al,B,In,Ga)Nデバイス層に対して、最小の影響を有する。
以下の好ましい実施形態の説明において、添付の図面に対して参照がなされる。この図面は、本明細書の一部を形成し、そしてこの図面において、例として、本発明が実施され得る特定の実施形態が説明され得る。本発明の範囲から逸脱することなく、他の実施形態が利用され得、そして構造的変化がなされ得ることが、理解されるべきである。
本発明は、デバイス品質の非極性の
図1は、本発明の好ましい実施形態に従って、非極性の
成長したままのGaNフィルムおよびr平面サファイアの結晶学的配向および構造の質を、4バウンスGe(220)単色Cu Kα放射線および1.2mmのスリットを検出器アームに有する受容スリットモードで作動する、PhilipsTM4サイクル高解像度X線回折計(HR−XRD)を使用して決定した。集束ビーム電子回折(CBED)を使用して、サファイア基板に対するa−GaNフィルムの極性を規定した。ウェッジポリシングおよびイオンミリングによって調製した、透過型電子顕微鏡(TEM)サンプルの平面図および断面図を分析して、a−GaNの欠損構造を決定した。タッピングモードのDigital Instruments D3000 原子力顕微鏡(AFM)は、表面形態学の画像を生じた。
に平行な、サファイア/GaN界面にいて始まる螺旋転位(threadingdislocation)(TD)の大きい密度を明らかにする。平面TEMによって決定されるTD密度は、2.6×1010cm−2であった。TD線の方向が成長方向と平行であるので、純粋な螺旋転位(screw dislocation)は、成長方向
に沿って整列したバーガースベクトルを有し、一方で、純粋な刃状転位は、b=±[0001]を有する。c−GaNに対して減少したa−GaN表面の対称性は、混合した転位の特徴付けを複雑にする。なぜなら、結晶学的に等価な
族として処理され得ないからである。具体的には、混合された転位の可能なバーガースベクトルは、以下の3つの細分:
反射の両方について測定し、a平面GaN結晶の質を特徴付けた。オン軸ピークの全半値幅(FWHM)は、0.29°(1037”)であり、一方で、オフ軸ピークは、0.46°(1659”)のFWHMで間隔を空けた、より大きい配向を示した。大きいFWHM値が予測される。なぜなら、微細構造が、かなりの転位密度を含むからである。Heyingらによって提供された、c−サファイア上のc−GaNフィルムについての分析によれば、オン軸ピーク幅は、螺旋転位および混合転位によって広くされ、一方で、オフ軸幅は、刃状成分TDによって広くされる(TD線がフィルムの法線に平行であると仮定する)。参考文献18を参照のこと。オン軸ピークと比較したオフ軸ピークの幅広化に起因して、比較的大きい刃状転位密度が、r−サファイア上のa−GaNについて予測される。さらなる微細構造分析が、a−GaN TDジオメトリーをロッキングカーブ測定に相関付けるために必要とされる。
以下の参考文献が、本明細書中に参考として援用される:
これは、発明の好ましい実施形態の説明を結論付ける。以下は、本発明を達成するための、いくつかの代替の実施形態を記載する。
図2(b)は、GaNとr−サファイアとの間の面内エピタキシャル関係を決定するために使用される、オフ軸φ走査の編集であり、ここで、傾斜角ψを使用して、各走査について記載されるオフ軸投影に接近した。
図2(c)は、GaNとr平面サファイアとの間のエピタキシャル関係の概略図である。
Claims (9)
- 平滑な平坦な成長表面を有する非極性の窒化ガリウムフィルムを、サファイア基板上で、金属・有機化学蒸着によって成長させる方法であって、以下の工程:
(a)窒化ガリウムからなる緩衝層を、r平面サファイア基板上に、400℃と900℃との間の第1の成長温度および大気圧で堆積させる工程;ならびに
(b)非極性のa平面窒化ガリウムフィルムを、該金属・有機化学蒸着によって、該緩衝層上で、0.2気圧以下の成長圧力で、該第1の成長温度よりも高い第2の成長温度である1100℃で、そしてN/Ga比を1300とした、ガリウムフローおよび窒素フローを用いて成長させる工程であって、ここで、工程(a)および(b)から得られる該非極性のa平面窒化ガリウムフィルムが、
・3.8×105cm−1以下の積層欠損密度を有する該非極性a平面窒化ガリウムフィルムのc軸に垂直に整列された積層欠陥と、
・2.6×1010cm−2以下の螺旋転位密度と、
・該非極性a平面窒化ガリウムフィルムのフィルム法線に対して平行な螺旋転位線方向と、
・平坦な成長表面を有し、
(c)そして工程(b)において形成された前記非極性の窒化ガリウムフィルム上に、1つ以上のデバイス品質の(Al,B,In,Ga)N層であるデバイス層を成長させる工程を、
包含する、方法。 - 前記非極性の窒化ガリウムフィルムの、前記r平面基板に対する面内配向が、
- 前記堆積させる工程(a)の前に、前記基板を1000℃より高温でアニールする工程をさらに包含する、請求項1に記載の方法。
- 前記窒化ガリウムからなる緩衝層が、1〜100ナノメートルの窒化ガリウムを含有する、請求項1に記載の方法。
- 前記成長させる工程(b)が、前記非極性の窒化ガリウムフィルムを、前記窒化ガリウムからなる緩衝層上で、1分間あたり約30μmolのガリウムフロー、および1分間あたり40,000μmolの窒素フローで成長させる工程を包含する、請求項1に記載の方法。
- 前記非極性の窒化ガリウムフィルムが、光学的に反射性の表面により特徴付けられる平滑な平坦な成長表面を有する、請求項1に記載の方法。
- 前記非極性の窒化ガリウムフィルムが、c軸に対して垂直であるわずかな段により特徴付けられる平滑な平坦な成長表面を有する、請求項1に記載の方法。
- 前記基板がミスカット基板である、請求項1に記載の方法。
- 工程(a)および(b)から得られる前記非極性の窒化ガリウムフィルムが、2.6nm以下の表面粗さを有する平滑な平坦な成長表面を有する、請求項1に記載の方法。
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