JP5076094B2 - Group III nitride single crystal manufacturing method, base crystal substrate having metal nitride layer, and multilayer structure wafer - Google Patents
Group III nitride single crystal manufacturing method, base crystal substrate having metal nitride layer, and multilayer structure wafer Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims description 144
- 150000004767 nitrides Chemical class 0.000 title claims description 121
- 239000000758 substrate Substances 0.000 title claims description 87
- 229910052751 metal Inorganic materials 0.000 title claims description 59
- 239000002184 metal Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 claims description 23
- 238000005121 nitriding Methods 0.000 claims description 15
- 229910052594 sapphire Inorganic materials 0.000 claims description 15
- 239000010980 sapphire Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000003486 chemical etching Methods 0.000 claims description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 35
- 229910002601 GaN Inorganic materials 0.000 description 31
- 239000007789 gas Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 3
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910015363 Au—Sn Inorganic materials 0.000 description 1
- MHYQBXJRURFKIN-UHFFFAOYSA-N C1(C=CC=C1)[Mg] Chemical compound C1(C=CC=C1)[Mg] MHYQBXJRURFKIN-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- -1 InN Chemical compound 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Chemical Vapour Deposition (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
Description
本発明は、III族窒化物単結晶の製造方法、該製造方法により製造されるIII族窒化物単結晶、該製造方法に用いる金属窒化物層を有する下地結晶基板、およびそれにIII族窒化物単結晶層を形成した多層構造ウエハに関する。 The present invention relates to a method for producing a group III nitride single crystal, a group III nitride single crystal produced by the production method, a base crystal substrate having a metal nitride layer used in the production method, and a group III nitride single crystal The present invention relates to a multilayer structure wafer in which a crystal layer is formed.
窒化ガリウム（ＧａＮ）に代表されるIII族窒化物単結晶は、発光ダイオード及びレーザーダイオード等の発光デバイスやＨＥＭＴ及びＨＢＴ等の高周波及び高出力の電子デバイスに適用される物質として有用である。このため、結晶性の高いＧａＮ等のIII族窒化物単結晶を効率よく製造することが必要とされている。 A group III nitride single crystal typified by gallium nitride (GaN) is useful as a material applied to light-emitting devices such as light-emitting diodes and laser diodes and high-frequency and high-power electronic devices such as HEMT and HBT. For this reason, it is necessary to efficiently produce a group III nitride single crystal such as GaN having high crystallinity.
例えばＧａＮ結晶の成長に用いることができる最も理想的な基板はＧａＮ基板である。しかし、ＧａＮは窒素の平衡蒸気圧がＧａに比べて極端に高いために、従来の引き上げ法などを利用してバルク結晶を成長させることが困難である。そのため、ＧａＮとは異なる材料からなる基板すなわち異種材料からなる基板（例えばサファイア基板、ＳｉＣ基板、Ｓｉ基板、ＧａＡｓ基板等）上にＧａＮ結晶を成長させた後、異種基板を除去することにより、ＧａＮを作製する方法がとられている（特許文献１〜３参照）。
しかしながら、成長させた結晶を異種基板から除去する工程は必ずしも簡便ではない。また、簡便な方法を採用しようとするとIII族窒化物単結晶の結晶性が低下してしまう問題もあった。
そこで本発明者らは、このような従来技術の課題を解決するために、高品質なIII族窒化物単結晶を簡便に製造する方法を提供することを目的として設定した。また、その製造方法に用いる基板を提供することも目的として設定した。
However, the process of removing the grown crystal from the different substrate is not always simple. Further, there is a problem that the crystallinity of the group III nitride single crystal is lowered when a simple method is adopted.
Therefore, the present inventors have set up for the purpose of providing a method for easily producing a high-quality group III nitride single crystal in order to solve such problems of the conventional art. Moreover, it set also as the objective to provide the board | substrate used for the manufacturing method.
本発明者らは鋭意検討を重ねた結果、下地基板として低次の面に対するオフ角度を有する結晶を用いることにより従来技術の課題を解決しうることを見出した。すなわち、課題を解決する手段として、以下の本発明を提供するに至った。 As a result of intensive studies, the present inventors have found that the problems of the prior art can be solved by using a crystal having an off angle with respect to a low-order plane as a base substrate. That is, the following present invention has been provided as means for solving the problems.
［１］ 低次の面に対するオフ角度が０．１５〜０．４０°である主面を有する下地結晶基板の該主面上に金属層を形成する金属層形成工程と、該金属層を窒化して金属窒化物層とする窒化工程と、該金属窒化物層の上にIII族窒化物単結晶を成長するIII族窒化物層成長工程とを含むことを特徴とするIII族窒化物単結晶の製造方法。
［２］ 前記下地結晶基板が六方晶系の結晶構造を有しており、（０００１）面に対するオフ角度が０．１０°以上である面を主面とすることを特徴とする［１］に記載のIII族窒化物単結晶の製造方法。
［３］ 前記下地結晶基板がサファイアであることを特徴とする［１］または［２］に記載のIII族窒化物単結晶の製造方法。
［４］ 前記窒化工程をアンモニアを含むガスを用いて行うことを特徴とする［１］〜［３］のいずれか一項に記載のIII族窒化物単結晶の製造方法。
［５］ 前記III族窒化物がＧａＮであることを特徴とする［１］〜［４］のいずれか一項に記載のIII族窒化物単結晶の製造方法。
［６］ 前記III族窒化物層成長工程の後に、III族窒化物単結晶を分離する工程をさらに含むことを特徴とする［１］〜［５］のいずれか一項に記載のIII族窒化物単結晶の製造方法。
［７］ 前記金属窒化物層の選択的化学エッチングによりIII族窒化物単結晶を分離することを特徴とする［６］に記載のIII族窒化物単結晶の製造方法。
[1] A metal layer forming step of forming a metal layer on the main surface of the base crystal substrate having a main surface with an off angle of 0.15 to 0.40 ° with respect to the lower-order surface, and nitriding the metal layer A group III nitride single crystal comprising: a nitriding step for forming a metal nitride layer, and a group III nitride layer growing step for growing a group III nitride single crystal on the metal nitride layer. Manufacturing method.
[2] In the above [1], the base crystal substrate has a hexagonal crystal structure, and a main surface is a plane having an off angle of 0.10 ° or more with respect to the (0001) plane. The manufacturing method of the group III nitride single crystal of description.
[3] The method for producing a group III nitride single crystal according to [1] or [2], wherein the base crystal substrate is sapphire.
[ 4 ] The method for producing a group III nitride single crystal according to any one of [1] to [ 3 ], wherein the nitriding step is performed using a gas containing ammonia.
[ 5 ] The method for producing a group III nitride single crystal according to any one of [1] to [ 4 ], wherein the group III nitride is GaN.
[ 6 ] The group III nitride according to any one of [1] to [ 5 ], further including a step of separating the group III nitride single crystal after the group III nitride layer growth step. A method for producing a single crystal.
[ 7 ] The method for producing a group III nitride single crystal according to [ 6 ], wherein the group III nitride single crystal is separated by selective chemical etching of the metal nitride layer.
［８］ ［６］または［７］に記載の製造方法により製造したIII族窒化物単結晶。
［９］ 前記III族窒化物がＧａＮであることを特徴とする［８］に記載のIII族窒化物単結晶。
[ 8 ] A group III nitride single crystal produced by the production method according to [ 6 ] or [ 7 ].
[ 9 ] The group III nitride single crystal according to [ 8 ], wherein the group III nitride is GaN.
［１０］ 低次の面に対するオフ角度が０．１５〜０．４０°である主面を有する下地結晶基板の該主面上に金属窒化物層を有することを特徴とする金属窒化物層を有する下地結晶基板。
［１１］ 前記金属窒化物がＣｒＮであることを特徴とする［１０］に記載の金属窒化物層を有する下地結晶基板。
［１２］ 前記下地結晶基板がサファイアであることを特徴とする［１０］または［１１］に記載の金属窒化物層を有する下地結晶基板。
[ 10 ] A metal nitride layer comprising a metal nitride layer on the main surface of a base crystal substrate having a main surface with an off angle of 0.15 to 0.40 ° with respect to a lower-order surface. An underlying crystal substrate.
[ 11 ] The underlying crystal substrate having a metal nitride layer according to [ 10 ], wherein the metal nitride is CrN.
[ 12 ] The base crystal substrate having a metal nitride layer according to [10] or [11] , wherein the base crystal substrate is sapphire.
［１３］ ［１０］〜［１２］のいずれか一項に記載の金属窒化物層を有する下地結晶基板からなることを特徴とする、III族窒化物単結晶の成長用基板。
［１４］ ［１０］〜［１３］のいずれか一項に記載の金属窒化物層を有する下地結晶基板の金属窒化物層上にさらにIII族窒化物単結晶層を有することを特徴とする多層構造ウエハ。
［１５］ ［１４］に記載の多層構造ウエハを含むことを特徴とする半導体素子。
[ 13 ] A group III nitride single crystal growth substrate comprising a base crystal substrate having the metal nitride layer according to any one of [ 13 ] [ 10 ] to [ 12 ].
[ 14 ] A multilayer having a group III nitride single crystal layer further on the metal nitride layer of the underlying crystal substrate having the metal nitride layer according to any one of [ 10 ] to [ 13 ] Structure wafer.
[ 15 ] A semiconductor element comprising the multilayer structure wafer according to [ 14 ].
本発明のIII族窒化物単結晶の製造方法によれば、高品質なIII族窒化物単結晶を簡便に製造することができる。本発明の金属窒化物層を有する下地結晶基板は、高品質なIII族窒化物単結晶を成長させるための基板として有用である。 According to the method for producing a group III nitride single crystal of the present invention, a high-quality group III nitride single crystal can be easily produced. The base crystal substrate having the metal nitride layer of the present invention is useful as a substrate for growing a high-quality group III nitride single crystal.
以下において、本発明のIII族窒化物単結晶の製造方法などについて詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the production method of the group III nitride single crystal of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
［III族窒化物単結晶の製造方法］
（特徴）
本発明のIII族窒化物単結晶の製造方法は、低次の面に対するオフ角度が０．１０°以上である主面を有する下地結晶基板の該主面上に金属層を形成する金属層形成工程と、該金属層を窒化して金属窒化物層とする窒化工程と、該金属窒化物層の上にIII族窒化物単結晶を成長するIII族窒化物層成長工程とを含むことを特徴とする。
[Production Method of Group III Nitride Single Crystal]
(Feature)
The method for producing a group III nitride single crystal of the present invention is a method for forming a metal layer on a main surface of a base crystal substrate having a main surface having an off angle of 0.10 ° or more with respect to a lower-order surface. Nitriding the metal layer to form a metal nitride layer, and a group III nitride layer growing step of growing a group III nitride single crystal on the metal nitride layer. And
（下地結晶基板）
本発明の製造方法では、低次の面に対するオフ角度が０．１０°以上である主面を有する下地結晶基板を用いる。
ここで低次の面とは、面方位をミラー指数（ｈｋｌｍ）で表した場合、それぞれの指数の絶対値が２以下（｜ｈ｜≦２，｜ｋ｜≦２，｜ｌ｜≦２，｜ｍ｜≦２）であり、かつそれぞれの指数の絶対値の和が６以下（｜ｈ｜＋｜ｋ｜＋｜ｌ｜＋｜ｍ｜≦６）である面をいう。例えば、六方晶系の結晶構造を有する下地結晶基板を用いる場合は、低次の面として（０００１）面およびそれと結晶学的に等価な面、（１−１００）面およびそれと結晶学的に等価な面、（１１−２０）面およびそれと結晶学的に等価な面、（１−１０２）面およびそれと結晶学的に等価な面などを挙げることができ、好ましい低次の面は（０００１）面である。
(Underlying crystal substrate)
In the manufacturing method of the present invention, an underlying crystal substrate having a main surface with an off angle of 0.10 ° or more with respect to a low-order surface is used.
Here, the low-order plane means that when the plane orientation is expressed by the Miller index (hklm), the absolute value of each index is 2 or less (| h | ≦ 2, | k | ≦ 2, | l | ≦ 2, | M | ≦ 2) and the sum of the absolute values of the indices is 6 or less (| h | + | k | + | l | + | m | ≦ 6). For example, when an underlying crystal substrate having a hexagonal crystal structure is used, the (0001) plane and the crystallographically equivalent plane as the lower order plane, the (1-100) plane and the crystallographically equivalent plane Plane, (11-20) plane and plane crystallographically equivalent to it, (1-102) plane and plane crystallographically equivalent to it, and preferred low-order planes are (0001) Surface.
オフ角度は０．１０°以上である。本発明の製造方法にしたがって望ましいIII族窒化物単結晶（例えばＧａＮ）を成長する観点からは、オフ角度は０．１５°〜０．５０°が好ましく、０．１６°〜０．４７°がより好ましく、０．１７°〜０．４０°がさらに好ましく、０．１８°〜０．３５°がさらにより好ましく、０．２０°〜０．３０°が特に好ましい。また、本発明の製造方法にしたがって、望ましい金属窒化物層（例えばＣｒＮ層）を形成する観点からは、オフ角度は０．１５°〜０．５０°が好ましく、０．１６°〜０．４５°がより好ましく、０．１７°〜０．４０°がさらに好ましく、０．１８°〜０．３０°が特に好ましい。例えば、いったん金属窒化物層を形成した時点で製造物を取り出し、それをIII族窒化物単結晶の成長用基板として用いる場合は、金属窒化物層を形成する観点から好ましいオフ角度を採用することが望ましい。 The off angle is 0.10 ° or more. From the viewpoint of growing a desired group III nitride single crystal (for example, GaN) according to the production method of the present invention, the off angle is preferably 0.15 ° to 0.50 °, and preferably 0.16 ° to 0.47 °. More preferably, 0.17 ° to 0.40 ° is more preferable, 0.18 ° to 0.35 ° is even more preferable, and 0.20 ° to 0.30 ° is particularly preferable. Further, from the viewpoint of forming a desirable metal nitride layer (for example, a CrN layer) according to the production method of the present invention, the off angle is preferably 0.15 ° to 0.50 °, and 0.16 ° to 0.45. Is more preferable, 0.17 ° to 0.40 ° is more preferable, and 0.18 ° to 0.30 ° is particularly preferable. For example, when a product is taken out once a metal nitride layer is formed and used as a substrate for growth of a group III nitride single crystal, a preferred off-angle is adopted from the viewpoint of forming the metal nitride layer. Is desirable.
下地結晶基板としては、六方晶系の結晶構造を有する結晶を用いることが好ましい。特に、（０００１）面に対するｍ軸方向のオフ角度が上記の範囲内にある面を主面とする結晶が好ましい。ここで、六方晶系の結晶構造におけるｍ軸とは、Ｍ面である（１−１００）面およびそれに結晶学的に等価な面に垂直な方向を意味する。また、ここでいうｍ軸方向とは、必ずしも厳密にｍ軸の方向である必要はなく、ｍ軸の方向の±３０°以内の方向を含み、±５°以内が好ましく、±１°以内がさらに好ましく、±０．５°以内がさらにより好ましく、±０．１°以内が特に好ましい。 As the base crystal substrate, a crystal having a hexagonal crystal structure is preferably used. In particular, a crystal whose principal surface is a plane in which the off angle in the m-axis direction with respect to the (0001) plane is within the above range is preferable. Here, the m-axis in the hexagonal crystal structure means a direction perpendicular to the (1-100) plane that is the M plane and a crystallographically equivalent plane. The m-axis direction here does not necessarily need to be strictly the m-axis direction, includes a direction within ± 30 ° of the m-axis direction, preferably within ± 5 °, preferably within ± 1 °. More preferably, within ± 0.5 ° is even more preferable, and within ± 0.1 ° is particularly preferable.
下地結晶基板のサイズや形状は特に制限されないが、一般に１辺が１０ｍｍ以上の角型または直径が１０ｍｍ以上の丸型で、かつ厚さ１００μｍ以上であるものを採用することが可能であり、直径２インチ以上の丸型で、かつ厚さ３００μｍ以上であるものを用いることが好ましい。
下地結晶基板の表面は特に制限されないが、一般に表面を鏡面研磨仕上げした研磨基板、その研磨基板の表面をドライエッチング法やウエットエッチング法等により加工して凹凸を形成した加工基板、その研磨基板の表面に誘電体膜等でストライプ状や格子状のパターンを形成したパターン付き基板等を用いることができる。
The size and shape of the underlying crystal substrate are not particularly limited, but it is generally possible to adopt a square shape with a side of 10 mm or more or a round shape with a diameter of 10 mm or more and a thickness of 100 μm or more. It is preferable to use a round shape of 2 inches or more and a thickness of 300 μm or more.
The surface of the underlying crystal substrate is not particularly limited, but in general, a polished substrate whose surface is mirror-polished, a processed substrate in which irregularities are formed by processing the surface of the polished substrate by a dry etching method or a wet etching method, and the like A substrate with a pattern in which a stripe or lattice pattern is formed on the surface with a dielectric film or the like can be used.
（金属層形成工程）
金属層形成工程は、上記の下地結晶基板上に金属層を形成する工程である。
金属層を構成する金属は、窒化物を形成しうるものの中から選択する。具体的には、Ｇａ、Ｃｏ、Ｍｎ、Ｚｎ、Ｓｎ、Ｇｅ、Ｍｇ、Ｂｅ、Ｃａ、Ｓｒ、Ｂａ、Ｎｂ、Ｖ、Ｔａ、Ｚｒ、Ｈｆ、Ｓｃ、Ｔｉ、Ａｌ、Ｃｒ、Ｍｏ、Ｗ、Ｃｕ、Ｆｅ、Ｃなどを挙げることができる。これらの中で、好ましいのはＣｒ、Ｓｃ、Ｔｉ、Ａｌ、Ｍｏ、Ｗ、Ｃｕであり、より好ましいのはＣｒ、Ｓｃ、Ｔｉ、Ｃｕである。
(Metal layer forming process)
The metal layer forming step is a step of forming a metal layer on the base crystal substrate.
The metal constituting the metal layer is selected from those capable of forming a nitride. Specifically, Ga, Co, Mn, Zn, Sn, Ge, Mg, Be, Ca, Sr, Ba, Nb, V, Ta, Zr, Hf, Sc, Ti, Al, Cr, Mo, W, Cu , Fe, C and the like. Among these, Cr, Sc, Ti, Al, Mo, W, and Cu are preferable, and Cr, Sc, Ti, and Cu are more preferable.
金属層の形成方法は特に制限されないが、例えばスパッタ法、真空蒸着法、ＭＢＥ法などを挙げることができ、好ましいのはスパッタ法である。 The method for forming the metal layer is not particularly limited, and examples thereof include a sputtering method, a vacuum evaporation method, and an MBE method, and the sputtering method is preferable.
金属層形成工程において形成する金属層の厚みは、１ｎｍ〜５００ｎｍが好ましく、２ｎｍ〜１００ｎｍがより好ましく、５ｎｍ〜５０ｎｍがさらに好ましい。 The thickness of the metal layer formed in the metal layer forming step is preferably 1 nm to 500 nm, more preferably 2 nm to 100 nm, and further preferably 5 nm to 50 nm.
（窒化工程）
窒化工程は、上で形成した金属層を窒化して金属窒化物層とする工程である。
金属層を形成した下地結晶基板を、例えばＨＶＰＥ装置内にて６００℃以上のアンモニア雰囲気中に置くことにより、窒化を行うことができる。キャリアガスとしては窒素などを用いることができる。
本発明の窒化工程によって、少なくとも金属層の表面が窒化物となる。本発明の窒化工程では、金属層全体が窒化していなくても少なくとも表面が窒化していればよい。
(Nitriding process)
The nitriding step is a step of nitriding the metal layer formed above to form a metal nitride layer.
Nitriding can be performed by placing the base crystal substrate on which the metal layer is formed in an ammonia atmosphere at 600 ° C. or higher, for example, in an HVPE apparatus. Nitrogen or the like can be used as the carrier gas.
By the nitriding step of the present invention, at least the surface of the metal layer becomes a nitride. In the nitriding step of the present invention, it is sufficient that at least the surface is nitrided even if the entire metal layer is not nitrided.
（III族窒化物層成長工程）
III族窒化物層成長工程は、上で形成した金属窒化物層の上にIII族窒化物単結晶を成長する工程である。
このとき、上で形成した金属窒化物層の上に直接III族窒化物単結晶を成長してもよいが、バッファ層を形成してからIII族窒化物単結晶を成長することが好ましい。例えば、成長させようとしているIII族窒化物単結晶と同じ単結晶を比較的低い温度で成長させることができる。具体的には、ＧａＮであれば、６００〜１０００℃で数ｎｍから数十μｍ形成することができる。
(Group III nitride layer growth process)
The group III nitride layer growth step is a step of growing a group III nitride single crystal on the metal nitride layer formed above.
At this time, the group III nitride single crystal may be grown directly on the metal nitride layer formed above, but it is preferable to grow the group III nitride single crystal after forming the buffer layer. For example, the same single crystal as the group III nitride single crystal to be grown can be grown at a relatively low temperature. Specifically, in the case of GaN, it can be formed from 600 nm to 1000 ° C. from several nm to several tens of μm.
バッファ層を形成した後、好ましくは連続してIII族窒化物単結晶を成長させる。具体的には、バッファ層形成温度よりも高い温度で単結晶を成長させる。ＧａＮであれば、通常１０００℃以上に設定する。成長させるIII族窒化物単結晶の厚みは、目的や用途に応じて適宜調整することができる。例えば、数ｎｍから数十μｍ成長させることが可能であるが、１００μｍ以上の厚膜を形成して、III族窒化物単結晶の自立基板を得ることも可能である。
III族窒化物単結晶の成長法としては、ＨＶＰＥ法、ＭＯＣＶＤ法などを採用することが可能であり、ＨＶＰＥ法を採用することが好ましい。図１に本発明で用いることができるＨＶＰＥ装置の一例を挙げる。リアクター１００内のサセプタ１０７上にサンプルを載せ、矢印の方向に回転させながらIII族原料と窒素原料をそれぞれ配管１０３，１０４から供給し、キャリアガスを配管１０１，１０２から供給する。温度はヒーター１０６により調整しつつIII族窒化物単結晶を成長させる。
After forming the buffer layer, a group III nitride single crystal is preferably grown continuously. Specifically, the single crystal is grown at a temperature higher than the buffer layer formation temperature. In the case of GaN, it is usually set to 1000 ° C. or higher. The thickness of the group III nitride single crystal to be grown can be appropriately adjusted according to the purpose and application. For example, it is possible to grow several nanometers to several tens of micrometers, but it is also possible to form a group III nitride single crystal free-standing substrate by forming a thick film of 100 micrometers or more.
As a method for growing a group III nitride single crystal, an HVPE method, an MOCVD method, or the like can be employed, and the HVPE method is preferably employed. FIG. 1 shows an example of an HVPE apparatus that can be used in the present invention. A sample is placed on the susceptor 107 in the reactor 100, and the group III material and the nitrogen material are supplied from the pipes 103 and 104, respectively, while rotating in the direction of the arrow, and the carrier gas is supplied from the pipes 101 and 102. The group III nitride single crystal is grown while the temperature is adjusted by the heater 106.
成長させるIII族窒化物の種類は特に制限されない。例えばＧａＮ、ＩｎＮ、ＡｌＮ、ＩｎＧａＮ、ＡｌＧａＮ、ＡｌＩｎＧａＮなどを挙げることができる。好ましいのはＧａＮ、ＡｌＮ、ＡｌＧａＮであり、より好ましいのはＧａＮである。 The type of group III nitride to be grown is not particularly limited. For example, GaN, InN, AlN, InGaN, AlGaN, AlInGaN, etc. can be mentioned. Preferred is GaN, AlN, AlGaN, and more preferred is GaN.
（分離工程）
本発明の製造方法により成長させたIII族窒化物単結晶は、下地結晶基板などから分離することができる。分離法として、金属窒化物層を化学エッチング法により除去することが好ましい。化学エッチング法に用いるエッチング剤としては、金属窒化物層が化学エッチングできるものであれば特に制限はない。金属窒化物層がＣｒＮの場合、エッチング剤としては、水（Ｈ2Ｏ）＋過塩素酸（ＨＣｌＯ4）＋硝酸ニアンモニウムセリウム（Ｃｅ（ＮＨ4）2（ＮＯ3）6）などを挙げることができる。
本発明の製造方法により厚膜のIII族窒化物単結晶を成長した場合は、分離工程を行うことによって、自立性のあるIII族窒化物単結晶を得ることができ、自立基板等として有効に利用することができる。
(Separation process)
The group III nitride single crystal grown by the production method of the present invention can be separated from the underlying crystal substrate or the like. As a separation method, the metal nitride layer is preferably removed by a chemical etching method. The etchant used in the chemical etching method is not particularly limited as long as the metal nitride layer can be chemically etched. When the metal nitride layer is CrN, examples of the etchant include water (H 2 O) + perchloric acid (HClO 4 ) + diammonium cerium nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ). Can do.
When a thick group III nitride single crystal is grown by the production method of the present invention, a self-supporting group III nitride single crystal can be obtained by performing the separation step, and is effective as a freestanding substrate or the like. Can be used.
［III族窒化物単結晶の成長用基板］
上記の本発明の製造方法の製造過程において、金属窒化物層を有する下地結晶基板が得られる。この金属窒化物層を有する下地結晶基板は、金属窒化物層上に高品質なIII族窒化物単結晶を成長させて多層構造ウエハを得ることができることから、III族窒化物単結晶の成長用基板として有用である。取得したいIII族窒化物単結晶の形状やサイズに応じて、成長用基板の形状やサイズを適宜調整することができる。
[Group III nitride single crystal growth substrate]
In the manufacturing process of the manufacturing method of the present invention, a base crystal substrate having a metal nitride layer is obtained. The underlying crystal substrate having the metal nitride layer can be used for growing a group III nitride single crystal because a high-quality group III nitride single crystal can be grown on the metal nitride layer to obtain a multilayer structure wafer. Useful as a substrate. The shape and size of the growth substrate can be adjusted as appropriate according to the shape and size of the group III nitride single crystal to be obtained.
［III族窒化物単結晶］
本発明の製造方法により得られるIII族窒化物単結晶は、低次の面に対するオフ角度が０．１０°以上である主面を有する下地結晶基板を用いて成長させているため、品質が高いという特徴を有する。オフ角度を有しない下地結晶基板の面に成長させたときに比べて、結晶性が優れている。また、このような高品質な結晶は、厚膜形成したときにも変わらずに得られる。
本発明のIII族窒化物単結晶やそれを含む多層構造ウエハは、高品質であることから様々な用途に利用することができる。例えば、ＬＥＤなどの半導体発光素子、半導体レーザ、電子デバイスなどの半導体素子形成に有効に用いられる。
[Group III nitride single crystal]
The group III nitride single crystal obtained by the production method of the present invention has high quality because it is grown using a base crystal substrate having a main surface with an off angle of 0.10 ° or more with respect to a low-order surface. It has the characteristics. The crystallinity is excellent as compared with the case of growing on the surface of the base crystal substrate having no off-angle. Moreover, such a high quality crystal can be obtained without change even when a thick film is formed.
The group III nitride single crystal of the present invention and the multilayer structure wafer including the same can be used for various applications because of high quality. For example, it is effectively used for forming semiconductor elements such as semiconductor light emitting elements such as LEDs, semiconductor lasers, and electronic devices.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
本実施例において行った試験方法は以下のとおりである。なお、以下の実施例では、図１に示すＨＶＰＥ装置を用いて行った。
The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
The test methods performed in this example are as follows. In the following examples, the HVPE apparatus shown in FIG. 1 was used.
（１）下地結晶基板の作製と評価
下地結晶基板として、（０００１）面に対するｍ軸方向のオフ角度が０．１５°である主面を有する厚さ４３０μｍ、直径２インチのサファイア基板を用意した。その後スパッタ法により、下地結晶基板の上に厚さ２０ｎｍの下地Ｃｒ層を堆積した。次いで、基板をＨＶＰＥ装置のリアクター１００内に配置して、１０８０℃まで昇温した後、Ｎ2のみからなるキャリアガスＧ２とＮＨ3ガスＧ４を供給しながら３０分間窒化しＣｒＮ膜を得た。この窒化工程において、成長圧力を１．０１×１０5Ｐａとし、Ｎ2ガスＧ２の分圧を７．７６×１０4Ｐａとし、ＮＨ3ガスＧ４の分圧を２．３４×１０4Ｐａとした。窒化工程が終了後に室温まで降温して、図２に示すような下地結晶基板上に堆積されたＣｒＮ膜を得た（実施例１）。
サファイア基板のオフ角度が０．２０°、０．３０°、０．５０°、０．７０°、０°である下地結晶基板を用いた点を変更し、その他は上記と同じ方法により下地結晶基板上にＣｒＮ膜を形成した（順に実施例２および３、参考例１および２、比較例１）。
(1) Fabrication and Evaluation of Underlying Crystal Substrate A sapphire substrate with a thickness of 430 μm and a diameter of 2 inches having a main surface with an off-angle in the m-axis direction of 0.15 ° with respect to the (0001) plane was prepared as the underlying crystal substrate. . Thereafter, a base Cr layer having a thickness of 20 nm was deposited on the base crystal substrate by sputtering. Next, the substrate was placed in the reactor 100 of the HVPE apparatus, heated to 1080 ° C., and then nitrided for 30 minutes while supplying the carrier gas G2 and NH 3 gas G4 consisting only of N 2 to obtain a CrN film. In this nitriding step, the growth pressure is 1.01 × 10 5 Pa, the partial pressure of the N 2 gas G2 is 7.76 × 10 4 Pa, and the partial pressure of the NH 3 gas G4 is 2.34 × 10 4 Pa. did. After completion of the nitriding step, the temperature was lowered to room temperature, and a CrN film deposited on the underlying crystal substrate as shown in FIG. 2 was obtained (Example 1).
Change the point using the base crystal substrate whose off-angle of the sapphire substrate is 0.20 °, 0.30 °, 0.50 °, 0.70 °, 0 °, otherwise the base crystal by the same method as above A CrN film was formed on the substrate (Examples 2 and 3, Reference Examples 1 and 2 , and Comparative Example 1 in this order).
得られた６種類のＣｒＮ膜について、（１１１）Ｘ線ロッキングカーブの半値幅を測定した。下地サファイア基板のオフ角度を横軸にとり、得られたＣｒＮ膜の（１１１）Ｘ線ロッキングカーブの半値幅の値を縦軸にとったグラフを図３に示す。ＣｒＮ膜の結晶性を示す（１１１）Ｘ線ロッキングカーブの半値幅は小さいほど良好であることを示す。グラフは０．２°付近で極小値をとり、低オフ角度側は急激に半値幅が増大し、高オフ角度側はなだらかに半値幅が上昇する結果となった。 With respect to the obtained six types of CrN films, the half width of the (111) X-ray rocking curve was measured. FIG. 3 shows a graph in which the off-angle of the underlying sapphire substrate is taken on the horizontal axis, and the half-value width of the (111) X-ray rocking curve of the obtained CrN film is taken on the vertical axis. The smaller the half width of the (111) X-ray rocking curve indicating the crystallinity of the CrN film, the better. The graph showed a minimum value near 0.2 °, and the half-value width increased abruptly on the low off-angle side, and the half-value width gradually increased on the high off-angle side.
（２）窒化物単結晶の成長と評価
（１）のＣｒ層堆積工程と窒化工程を実施して６種類のＣｒＮ膜付き下地結晶基板を作製した。窒化工程終了後に９００℃まで降温して、実質的にＨ2のみからなるキャリアガスＧ１と、ＧａとＨＣｌの反応生成物であるＧａＣｌガスＧ３と、ＮＨ3ガスＧ４とを供給しながら、ＧａＮバッファー層を約５分間成長させた。このバッファー層成長工程において、成長圧力を１．０１×１０5Ｐａとし、ＧａＣｌガスＧ３の分圧を５．３９×１０2Ｐａとし、ＮＨ3ガスＧ４の分圧を６．７３×１０3Ｐａとした。
次いで、再び反応室の温度を１０４０℃まで上げ、ＧａＮ単結晶膜を成長させた。この単結晶成長工程においては成長圧力を１．０１×１０5Ｐａとし、ＧａＣｌガスＧ３の分圧を２．６９×１０2Ｐａとし、ＮＨ3ガスＧ４の分圧を６．７３×１０3Ｐａとした。
単結晶成長工程が終了後、室温まで降温し、下地結晶基板上にＣｒＮ膜、ＧａＮバッファー層を介して厚さが約２０μｍのＧａＮ単結晶膜を得た（図４）。
(2) Growth and Evaluation of Nitride Single Crystal The Cr layer deposition step and the nitridation step (1) were carried out to produce six types of base crystal substrates with CrN films. After the nitridation step, the temperature is lowered to 900 ° C., and a GaN buffer is supplied while supplying a carrier gas G1 consisting essentially of H 2 , a GaCl gas G3 that is a reaction product of Ga and HCl, and an NH 3 gas G4. The layer was grown for about 5 minutes. In this buffer layer growth step, the growth pressure is 1.01 × 10 5 Pa, the partial pressure of the GaCl gas G3 is 5.39 × 10 2 Pa, and the partial pressure of the NH 3 gas G4 is 6.73 × 10 3 Pa. It was.
Next, the temperature of the reaction chamber was raised again to 1040 ° C. to grow a GaN single crystal film. In this single crystal growth step, the growth pressure is 1.01 × 10 5 Pa, the partial pressure of GaCl gas G3 is 2.69 × 10 2 Pa, and the partial pressure of NH 3 gas G4 is 6.73 × 10 3 Pa. It was.
After completion of the single crystal growth step, the temperature was lowered to room temperature, and a GaN single crystal film having a thickness of about 20 μm was obtained on the underlying crystal substrate via a CrN film and a GaN buffer layer (FIG. 4).
得られた各ＧａＮ単結晶膜について、（００２）Ｘ線ロッキングカーブの半値幅と（１０２）Ｘ線ロッキングカーブの半値幅をそれぞれ測定した。下地サファイア基板のオフ角度を横軸にとり、得られたＧａＮ単結晶膜の（００２）Ｘ線ロッキングカーブの半値幅及び（１０２）Ｘ線ロッキングカーブの半値幅をそれぞれ縦軸にとったグラフを図５に示す。ＧａＮ単結晶膜のチルト成分の結晶性を示す（００２）Ｘ線ロッキングカーブの半値幅及び、ツイスト成分の結晶性を示す（１０２）Ｘ線ロッキングカーブの半値幅は、小さいほど良好であることを示す。共に０．２５°付近で半値幅の極小値が得られた。 About each obtained GaN single crystal film, the half value width of the (002) X-ray rocking curve and the half value width of the (102) X-ray rocking curve were measured, respectively. A graph in which the off-angle of the underlying sapphire substrate is taken on the horizontal axis, and the half width of the (002) X-ray rocking curve and the half width of the (102) X-ray rocking curve of the obtained GaN single crystal film are taken on the vertical axis, respectively. As shown in FIG. The smaller the FWHM of the (002) X-ray rocking curve indicating the crystallinity of the tilt component of the GaN single crystal film and the (102) X-ray rocking curve indicating the crystallinity of the twist component, the better the smaller. Show. In both cases, the minimum value of the half width was obtained around 0.25 °.
（３）ＬＥＤの作製と評価
下地結晶基板として、（０００１）ジャスト面を主面とする厚さ４３０μｍ、直径２インチのサファイア基板、および（０００１）面に対するｍ軸方向のオフ角度が０．２０°である主面を有する厚さ４３０μｍ、直径２インチのサファイア基板を用意した。（２）と同様な方法で下地結晶基板上にＣｒＮ膜、ＧａＮバッファー層を介して厚さが約２０μｍのＧａＮ単結晶膜を得た。
上記下地結晶上のＧａＮ単結晶膜を、ＭＯＣＶＤ装置内でアンモニア雰囲気中で１０５０℃まで昇温した。１０５０℃になった段階でＴＭＧ（トリメチルガリウム）を供給して、アンドープＧａＮ層を約２μｍ成長させた。次に適宜ＴＭＧ、ＴＭＡ（トリメチルアルミニウム）、アンモニア、シラン、Ｃｐ2Ｍｇ（シクロペンタジエニルマグネシウム）等を用いることにより、ｎ型Ａｌ0.2ＧａＮ0.8Ｎクラッド層、ＩｎＡｌＧａＮ ＭＱＷ活性層、ｐ型Ａｌ0.2Ｇａ0.8Ｎクラッド層、ｐ型ＧａＮコンタクト層からなる多層膜を形成した。各々の膜厚はおおよそ２００ｎｍ、１０ｎｍ、１００ｎｍ、２０ｎｍであった。その後酸素を含む雰囲気中で６００℃でアニーリングを行い、ｐ型層の低抵抗化を行った。次にｐ型コンタクト層の上にｐ電極を形成し、オーミックコンタクトするためのアニールを６００℃でおこなった。またｐ電極以外の露出面は絶縁性のＳｉＯ2保護膜を形成した。次に導電性のＳｉ基板上に上記ｐ電極面をＡｕ−Ｓｎの半田を用い加温およびプレス加圧することにより接合固着させた。
(3) Production and Evaluation of LED As a base crystal substrate, a sapphire substrate having a thickness of 430 μm and a diameter of 2 inches having a (0001) just surface as a main surface, and an off angle in the m-axis direction with respect to the (0001) surface is 0.20. A sapphire substrate having a thickness of 430 μm and a diameter of 2 inches having a principal surface at 0 ° was prepared. A GaN single crystal film having a thickness of about 20 μm was obtained on the underlying crystal substrate through a CrN film and a GaN buffer layer by the same method as in (2).
The GaN single crystal film on the base crystal was heated to 1050 ° C. in an ammonia atmosphere in an MOCVD apparatus. When the temperature reached 1050 ° C., TMG (trimethylgallium) was supplied to grow an undoped GaN layer by about 2 μm. Next, by appropriately using TMG, TMA (trimethylaluminum), ammonia, silane, Cp 2 Mg (cyclopentadienylmagnesium), etc., an n-type Al 0.2 GaN 0.8 N cladding layer, an InAlGaN MQW active layer, a p-type Al 0.2 A multilayer film composed of a Ga 0.8 N cladding layer and a p-type GaN contact layer was formed. Each film thickness was approximately 200 nm, 10 nm, 100 nm, and 20 nm. Thereafter, annealing was performed at 600 ° C. in an oxygen-containing atmosphere to reduce the resistance of the p-type layer. Next, a p-electrode was formed on the p-type contact layer, and annealing for ohmic contact was performed at 600 ° C. Further, an insulating SiO 2 protective film was formed on the exposed surface other than the p-electrode. Next, the p-electrode surface was bonded and fixed on a conductive Si substrate by heating and pressurizing using Au—Sn solder.
次に上記固着したウエハを、水（Ｈ2Ｏ）５００ｍｌ、６０％過塩素酸（ＨＣｌＯ4）２０ｍｌ、硝酸ニアンモニウムセリウム（Ｃｅ（ＮＨ4）2（ＮＯ3）6）８０ｇからなる温度８０℃の薬液に浸漬させ、ＣｒＮのエッチングを行いサファイア基板を剥離した。次に露出したＨＶＰＥ厚膜層をエッチング、研磨することによりｎ型クラッド層を露出させた。次にｎ型クラッド層上にｎ電極を、Ｓｉ基板裏面にｎパッド電極を形成し、最後にダイシングで素子分離して電流を基板に対して垂直に流し、ｎ電極側から光を取り出す構造のＬＥＤを作製した。 Next, the fixed wafer was heated at 80 ° C. composed of 500 ml of water (H 2 O), 20 ml of 60% perchloric acid (HClO 4 ) and 80 g of diammonium cerium nitrate (Ce (NH 4 ) 2 (NO 3 ) 6 ). Then, the sapphire substrate was peeled off by etching with CrN. Next, the n-type cladding layer was exposed by etching and polishing the exposed HVPE thick film layer. Next, an n-electrode is formed on the n-type clad layer, an n-pad electrode is formed on the back surface of the Si substrate, and finally the element is separated by dicing, and a current is made to flow perpendicularly to the substrate to extract light from the n-electrode side. LED was produced.
（０００１）ジャストのサファイア基板上に作製したＬＥＤ（実施例４）と、（０００１）面に対するｍ軸方向のオフ角度が０．２０°である主面を有するサファイア基板上に作製したＬＥＤ（比較例２）の外部光出力を比較したところ、後者が２．３倍大きい値であった。 An LED fabricated on a (0001) just sapphire substrate (Example 4 ) and an LED fabricated on a sapphire substrate having a main surface with an off angle of 0.20 ° in the m-axis direction with respect to the (0001) plane (comparison) When the external light output of Example 2) was compared, the latter was 2.3 times larger.
本発明のIII族窒化物単結晶の製造方法によれば、高品質なIII族窒化物単結晶を簡便に製造することができる。本発明の金属窒化物層を有する下地結晶基板は、高品質なIII族窒化物単結晶を成長させるための基板として有用である。本発明のIII族窒化物単結晶は、半導体発光素子、半導体レーザ、電子デバイスなどの半導体素子形成に用いられる。したがって、本発明は産業上の利用可能性が高い。 According to the method for producing a group III nitride single crystal of the present invention, a high-quality group III nitride single crystal can be easily produced. The base crystal substrate having the metal nitride layer of the present invention is useful as a substrate for growing a high-quality group III nitride single crystal. The group III nitride single crystal of the present invention is used for forming semiconductor elements such as semiconductor light emitting elements, semiconductor lasers, and electronic devices. Therefore, the present invention has high industrial applicability.
１００ リアクター
１０１ Ｈ2キャリアガス用配管
１０２ Ｎ2キャリアガス用配管
１０３ III族原料用配管
１０４ 窒素原料用配管
１０５ III族原料用リザーバー
１０６ ヒーター
１０７ サセプター
１０８ 排気管
２００ 表面にオフ角度を持った下地サファイア基板
２０１ ＣｒＮ膜
４００ 表面にオフ角度を持った下地サファイア基板
４０１ ＣｒＮ膜
４０２ ＧａＮバッファー膜
４０３ ＧａＮ単結晶膜
Ｇ１ Ｈ2キャリアガス
Ｇ２ Ｎ2キャリアガス
Ｇ３ III族原料ガス
Ｇ４ Ｖ族原料ガス
100 Reactor 101 H 2 Carrier Gas Pipe 102 N 2 Carrier Gas Pipe 103 Group III Material Pipe 104 Nitrogen Material Pipe 105 Group III Material Reservoir 106 Heater 107 Susceptor 108 Exhaust Pipe 200 Ground Sapphire with an Off Angle on the Surface Substrate 201 CrN film 400 Base sapphire substrate having an off angle on the surface 401 CrN film 402 GaN buffer film 403 GaN single crystal film G1 H 2 carrier gas G2 N 2 carrier gas G3 Group III source gas G4 Group V source gas
Claims (12)
A semiconductor device comprising the multilayer structure wafer according to claim 11 .
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