JP4048316B2 - Manufacturing method and manufacturing apparatus of zinc oxide single crystal film on single crystal silicon substrate and laminated structure - Google Patents
Manufacturing method and manufacturing apparatus of zinc oxide single crystal film on single crystal silicon substrate and laminated structure Download PDFInfo
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- JP4048316B2 JP4048316B2 JP2001361242A JP2001361242A JP4048316B2 JP 4048316 B2 JP4048316 B2 JP 4048316B2 JP 2001361242 A JP2001361242 A JP 2001361242A JP 2001361242 A JP2001361242 A JP 2001361242A JP 4048316 B2 JP4048316 B2 JP 4048316B2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 203
- 239000013078 crystal Substances 0.000 title claims description 139
- 239000011787 zinc oxide Substances 0.000 title claims description 99
- 239000000758 substrate Substances 0.000 title claims description 88
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000010408 film Substances 0.000 claims description 108
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 88
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 80
- 239000010409 thin film Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 6
- 238000005424 photoluminescence Methods 0.000 claims description 5
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 238000000608 laser ablation Methods 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 36
- 229910052710 silicon Inorganic materials 0.000 description 36
- 239000010703 silicon Substances 0.000 description 36
- 239000004065 semiconductor Substances 0.000 description 15
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002524 electron diffraction data Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000097 high energy electron diffraction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003071 parasitic effect Effects 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
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は単結晶シリコン基板上に単結晶酸化亜鉛膜をエピタキシャル成長する方法及びこの方法を実施する装置並びに積層構造に関する。
【０００２】
【従来の技術】
従来、多結晶酸化亜鉛（ＺｎＯ）は、その誘電的性質、可視光透過性等の多機能性を利用して、表面弾性波素子、焦電素子、圧電素子、ガスセンサー、バリスター、あるいは透明導電膜等に用いられてきた。
酸化亜鉛は、可視光の短波長端に相当する禁制帯幅を持った直接遷移型の半導体であるので、結晶完全性の高い酸化亜鉛単結晶が成長できれば、高耐圧電子デバイス用半導体、発光受光デバイス用半導体としても使用可能である。
したがって、結晶完全性の高い酸化亜鉛単結晶膜が成長できれば、半導体電子デバイス、発光受光デバイス、誘電的性質を利用した種々のデバイスを酸化亜鉛単結晶チップに集積した高機能デバイスを製造することが可能になる。
【０００３】
このため近年、酸化亜鉛単結晶の成長方法の研究が種々行われている。
例えば、サファイヤ基板上に、分子線エピタキシー法により酸素（Ｏ）ラジカルと亜鉛（Ｚｎ）分子線を用いて酸化亜鉛単結晶膜をエピタキシャル成長した報告（岩田 他、セラミックデータブック２０００別冊ｐ１９０−１９４参照）がされている。
この方法は、サファイヤ基板面と酸化亜鉛（０００１）面のマッチングが良いことを利用してエピタキシャル成長するものであり、基板面の垂直方向にｃ軸配向した酸化亜鉛単結晶膜が得られる。
しかしながら、サファイヤ基板はコストが高く、また加工が難しいことから、実用化には、他のコストが低くかつ加工性に優れた基板にエピタキシャル成長する方法が求められている。酸化亜鉛単結晶基板上に成長することも可能であるがさらにコストが高い。
【０００４】
【発明が解決しようとする課題】
また、シリコン（１１１）面基板上にシリコン窒化膜を形成し、シリコン窒化膜上に上記の例と同様な方法で酸化亜鉛単結晶膜をエピタキシャル成長する方法が開示されている（特開２００１−４４４９９号公報参照）。
この方法は、シリコン（１１１）面と酸化亜鉛（０００１）面のマッチングが良いことを利用してエピタキシャル成長するものであるが、酸素ラジカルがシリコン基板表面を酸化してシリコン基板表面をアモルファス化すると単結晶成長できないので、シリコン表面に極薄いシリコン窒化膜を形成して保護してからエピタキシャル成長するものである。
【０００５】
この方法によれば、コストが低く、かつ加工性に優れたシリコン基板を用いることができ、多機能にわたる酸化亜鉛半導体デバイスとシリコン集積回路技術を融合することができ非常に有益である。しかしながらこの方法で得られた酸化亜鉛単結晶膜は、基板面に垂直方向には良好なｃ軸配向を示すが、膜面内では結晶ドメインが回転しており、結晶ドメイン界面でキャリアが散乱されてキャリア移動度が小さい、ドメイン界面の再結合中心のために発光効率が悪いといった課題がある。
またこの方法は、シリコン窒化膜の膜厚が極めて重要であり、厚すぎるとシリコン基板表面に非晶質シリコン窒化膜が厚く形成されて規則正しい原子配列が得られず、薄すぎるとシリコン基板表面の酸化を防止できない。最適膜厚は１０ｎｍ程度であり、この厚さを再現性良く基板表面全面に亘って形成するのは極めて難しく、このため、シリコン窒化膜の膜厚制御に多大の工数を必要とし、生産性が上がらないといった課題がある。
また、半導体電子デバイス、発光受光デバイス、あるいはこれらの集積回路を形成する場合には、寄生容量やリーク電流の減少、あるいは素子分離のためにシリコン基板と酸化亜鉛単結晶膜は電気的に分離されていることが好ましい。しかしながら、この方法では、シリコン窒化膜が極めて薄くなければならないので、シリコン基板と酸化亜鉛単結晶膜を電気的に分離できないといった課題がある。
【０００６】
本発明は上記課題に鑑み、低コストかつ加工性に優れたシリコン基板上に成長することができ、基板面に垂直方向及び面内で結晶完全性が高く、かつ、シリコン基板と電気的に絶縁することができる単結晶シリコン基板上の酸化亜鉛単結晶膜の製造方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
上記課題を解決するために、本発明の単結晶シリコン基板上の酸化亜鉛単結晶膜の製造方法は、単結晶シリコン基板上にフッ化カルシウム単結晶薄膜をエピタキシャル成長し、フッ化カルシウム単結晶薄膜上に酸化亜鉛単結晶膜をエピタキシャル成長することで、フッ化カルシウム単結晶薄膜表面に垂直方向にｃ軸配向し、かつ、Ｘ線回折による極点図形が６回対称となり、面内で結晶ドメインが回転していない酸化亜鉛単結晶膜を得ることを特徴とする。
この構成によれば、シリコン（１１１）面とフッ化カルシウム（１１１）面と酸化亜鉛（０００１）面との格子整合性が良いので、シリコン基板上に結晶完全性の高いフッ化カルシウム単結晶薄膜をエピタキシャル成長することができ、結晶完全性の高いフッ化カルシウム単結晶薄膜上に酸化亜鉛をエピタキシャル成長するので、基板面に垂直方向にｃ軸配向しかつ単結晶膜の面内で回転ドメインのない結晶完全性の良好な酸化亜鉛単結晶膜が得られる。また、シリコン基板を使用するので低コストで酸化亜鉛単結晶膜が得られる。また、フッ化カルシウムは絶縁物であり、かつ、厚く積層することができるのでシリコン基板と酸化亜鉛単結晶膜とを電気的に絶縁分離できる。そして、フッ化カルシウムは可視域を含む幅広い波長範囲の光に対して透明であるため、酸化亜鉛単結晶膜を透過する可視光を単結晶シリコン基板に到達させることができる。
このため、例えば、基板としてシリコン太陽電池を用い、その上にフッ化カルシウム単結晶薄膜を介して酸化亜鉛単結晶膜を用いた紫外光センサーを形成すれば、太陽電池の電力を電源とする、センサー・電源一体型紫外線センサーを作製することも可能である。
本発明によるエピタキシャル成長方法は、分子線エピタキシャル法、電子ビーム蒸着法、レーザーアブレーション法等のいずれのエピタキシャル法でも良く、また、これらの組み合わせであっても良い。
ここで、フッ化カルシウム単結晶薄膜の厚さを１５ｎｍ以上にすれば結晶完全性の高い酸化亜鉛単結晶膜が得られ、１００ｎｍ以上の厚さにすれば、シリコン基板と酸化亜鉛単結晶膜とを、半導体電子デバイス、発光受光デバイスにとって十分な程度に電気的に絶縁分離することができる。さらに、フッ化カルシウム単結晶薄膜の厚さを１５ｎｍ以上１００ｎｍ以下程度にすれば、シリコン基板にｐ型を用い、フッ化カルシウム単結晶薄膜を絶縁膜として、酸化亜鉛単結晶膜をｎ型半導体としたｐｉｎ型のダイオードを形成することができる。
【０００８】
本発明の単結晶シリコン基板上の酸化亜鉛単結晶膜の製造装置は、超高真空槽内に、少なくとも単結晶シリコン基板を保持し加熱する基板加熱装置と、フッ化カルシウムを入れた坩堝からなりフッ化カルシウム分子線を発生させるフッ化カルシウム分子線源と、亜鉛を入れた坩堝からなり亜鉛分子線を発生させる亜鉛分子線源と、高周波放電ガンを用いて酸素ラジカルを発生させる酸素ラジカル源と、が設けられている。この製造装置を用いて本発明の方法を実施すれば、基板面に垂直方向にｃ軸配向しかつ単結晶膜の面内で回転ドメインのない結晶完全性の良好な酸化亜鉛単結晶膜が得られる。
【０００９】
本発明の積層構造は、単結晶シリコン基板と、単結晶シリコン基板上のフッ化カルシウム単結晶薄膜と、フッ化カルシウム単結晶薄膜上の酸化亜鉛単結晶膜と、からなり、酸化亜鉛単結晶膜は、フッ化カルシウム単結晶薄膜表面に垂直方向にｃ軸配向しており、かつ、Ｘ線回折による極点図形が６回対称であり、該酸化亜鉛単結晶膜の面内で結晶ドメインが回転していないことを特徴とする。
上記構成において、単結晶シリコン基板は、好ましくは、（１１１）面基板である。フッ化カルシウム単結晶薄膜の厚さは、好ましくは、１５ｎｍ以上である。フッ化カルシウム単結晶薄膜の厚さが１００ｎｍ程度で、単結晶シリコン基板と酸化亜鉛単結晶膜とが電気的に絶縁されることができる。
酸化亜鉛単結晶膜の室温でのフォトルミネッセンスにおいて、好ましくは、欠陥に基づく１．５〜２．５ｅＶの深い準位からの発光が観測されない。
このように、本発明の方法を用いれば、低コストで、従来にない結晶完全性を有し、かつ、基板と絶縁分離された、あるいは基板と電気的に接続できる酸化亜鉛単結晶膜を製造することが可能である。
【００１０】
【発明の実施の形態】
以下、図面に基づいて本発明の実施の形態を詳細に説明する。
本発明の単結晶シリコン基板上の酸化亜鉛単結晶膜の製造方法は、単結晶シリコン基板上にフッ化カルシウム単結晶薄膜をエピタキシャル成長し、フッ化カルシウム単結晶薄膜上に酸化亜鉛単結晶膜をエピタキシャル成長することを特徴としている。
図１は、本発明の方法によって形成される、単結晶シリコン基板とフッ化カルシウム単結晶薄膜と酸化亜鉛単結晶膜との積層構造を示す図である。図２は、図１の積層構造を形成するための装置の一例である分子線エピタキシャル装置を模式的に示す図である。
以下、図１及び図２を用いて本発明の実施の形態を説明する。
シリコン（１１１）面単結晶基板１上にフッ化カルシウム単結晶薄膜２をエピタキシャル成長し、フッ化カルシウム単結晶薄膜２上に酸化亜鉛単結晶膜３をエピタキシャル成長する。フッ化カルシウム単結晶薄膜２を１５ｎｍ以上の厚さに積層すれば結晶完全性の高い酸化亜鉛単結晶膜３が得られ、１００ｎｍ以上積層すればシリコン基板１と酸化亜鉛単結晶膜３を電気的に絶縁することができる。
【００１１】
エピタキシャル成長方法は、例えば、図２に示した分子線エピタキシャル装置を用いることができる。図２に示すように、超高真空槽４内において、基板加熱装置５に設置されたＳｉ基板１の表面に、フッ化カルシウムを入れた坩堝６を加熱してフッ化カルシウム分子線を照射して所望の厚さのフッ化カルシウム単結晶薄膜２をエピタキシャル成長する。酸化亜鉛単結晶膜３は、フッ化カルシウム単結晶薄膜２上に、亜鉛を入れた坩堝７を加熱して亜鉛分子線を照射すると共に、高周波放電ガンを使用した酸素ラジカル源８から酸素ラジカルを照射してエピタキシャル成長する。なお、図２において、９は排気系を示し、１０，１１はそれぞれ、ＲＨＥＥＤ（高エネルギー電子線回折装置）の電子銃及びスクリーンを示している。
【００１２】
上記説明では分子線エピタキシャル装置を例にとったが、他のエピタキシャル成長方法、例えば、電子ビーム蒸着法、またはフッ化カルシウムターゲットと酸化亜鉛ターゲットを用いたレーザーアブレーション法でも良く、またこれらのエピタキシャル成長法の組み合わせでも良い。また、坩堝の加熱方法は、抵抗加熱でも電子ビーム加熱でも良い。
なお、上述した酸素ラジカル源は、高周波放電ガンを使用した酸素ラジカル源を例にとって説明したが，電子サイクロトロン共鳴ガンを使用した酸素ラジカル源でも良い。
【００１３】
上記方法によれば、シリコン（１１１）面とフッ化カルシウム（１１１）面と酸化亜鉛（０００１）面とのマッチングが良いので、シリコン基板上に結晶完全性の高いフッ化カルシウム単結晶薄膜をエピタキシャル成長することができ、結晶完全性の高いフッ化カルシウム単結晶薄膜上に酸化亜鉛をエピタキシャル成長するので、基板面に垂直方向にｃ軸配向しかつ面内で結晶ドメインの回転のない結晶完全性の良好な酸化亜鉛単結晶膜が得られる。また、シリコン基板を使用するので低コストで酸化亜鉛単結晶膜が得られる。
【００１４】
ここで、フッ化カルシウム単結晶薄膜の厚さを１５ｎｍ以上にすれば結晶完全性の高い酸化亜鉛単結晶膜が得られ、１００ｎｍ以上の厚さにすれば、シリコン基板と酸化亜鉛単結晶膜とを、半導体電子デバイス、発光受光デバイスにとって十分な程度に電気的に絶縁分離することができる。さらに、フッ化カルシウム単結晶薄膜の厚さを１５ｎｍ以上、１００ｎｍ以下程度にすれば、シリコン基板にｐ型を用い、フッ化カルシウム単結晶薄膜を絶縁膜として、酸化亜鉛単結晶膜をｎ型半導体としたｐｉｎ型のダイオードを形成することができる。
【００１５】
次に，本発明の実施例を説明する。
結晶成長装置として、高周波放電ガンを用いた酸素ラジカル源と亜鉛坩堝およびフッ化カルシウム坩堝を備えた図２の分子線エピタキシャル装置を用いた。高周波放電ガンへ供給される酸素ガス流量は０．３ｃｃｍで，高周波放電電力は３５０Ｗとした。基板としてシリコン（１１１）面単結晶基板を用いた。
シリコン単結晶基板を有機溶媒で洗浄後，フッ酸を用いた標準的なエッチングによって最表面を水素原子で終端して分子線エピタキシャル装置に装着した。この基板を１×１０-7Ｐａの真空中で８００℃に昇温して５分保つと、超構造７×７の反射電子線回折パターンを示す清浄表面が得られた。
この清浄表面を持った基板を６５０℃に降温してフッ化カルシウム坩堝からフッ化カルシウム分子線を照射した。フッ化カルシウム膜の成長速度は１．０ｎｍ／ｍｉｎとした。フッ化カルシウムとシリコンの格子定数がほぼ等しいため、成長開始に伴う電子線回折パターンの変化はストリーク・ツー・ストリークで、堆積の第１層目から平坦な単結晶フッ化カルシウム膜が得られた。厚さ３ｎｍから１００ｎｍの範囲のフッ化カルシウム薄膜を成長して比較した。
原子間力顕微鏡で測定したこれら薄膜の２乗平均表面粗さは、０．４ｎｍ程度で、以降の酸化亜鉛膜の堆積にとって十分に平坦であった。
【００１６】
次に、この基板の温度を２５０℃に下げ，先ず酸素ラジカルを、その後に亜鉛坩堝から亜鉛分子線を追加照射して酸化亜鉛膜の成長を開始した。酸化亜鉛膜の成長速度は３．３ｎｍ／ｍｉｎとした。厚さ１０ｎｍの酸化亜鉛膜を成長してから酸素ラジカルの照射を停止して一旦成長を中断した。その後、亜鉛分子線のみを照射しながら７５０℃まで昇温して１０分間保って熱処理を施し、次いで５００℃に降温した。この熱処理の間に、酸化亜鉛膜の表面からの電子線回折パターンはスポットライクからブロードなストリークに変化した。この変化は、凹凸に成長した酸化亜鉛の表面がほぼ平坦になったことを示している。
その後、再び酸素ラジカルの照射を追加して厚さ６００ｎｍの酸化亜鉛膜を再成長した。このときの成長速度は６．７ｎｍ／ｍｉｎとした。再成長の開始に伴いブロードなストリークであった電子線回折パターンは徐々にシャープなストリークに変化し、高品質な単結晶酸化亜鉛膜がエピタキシャル成長していることが判った。
【００１７】
図３はこのようにして作製した面積が２ｃｍ2 の酸化亜鉛膜における、｛１０−１１｝を極点としたＸ線回折の極点図である。比較のために、シリコン基板に直接、酸化亜鉛膜をエピタキシャル成長した場合、すなわち、フッ化カルシウム薄膜を挿入しない試料についても示した。別途測定したθ−２θ法のＸ線回折では、いずれの酸化亜鉛膜からも（０００１）面による反射ピークのみが観測された。しかし、フッ化カルシウム薄膜を挿入しない場合には、図３の極点図形における回折ピーク分布がリング状になっている。このことは、酸化亜鉛膜の結晶構造が膜面内の回転ドメインを含むｃ軸配向膜になっていることを意味し、従来技術による報告結果と一致している。一方、フッ化カルシウム薄膜を挿入した場合は、フッ化カルシウム薄膜の厚さの増加とともに極点図形が６回対称に近づき、厚さが１５ｎｍを超えたあたりでほぼ完全に６回対称スポットのみになった。このことは、フッ化カルシウム薄膜の挿入によって酸化亜鉛膜中の回転ドメインの発生を防止できること、その効果はフッ化カルシウム薄膜の厚さが１５ｎｍ以上となった場合に十分発揮されることを示している。
【００１８】
図４は、これらの酸化亜鉛膜における（０００１）面Ｘ線回折ピークのロッキングカーブの半値幅とフッ化カルシウム膜厚の関係を示す図である。半値幅の減少は、酸化亜鉛膜におけるモザイク結晶の減少に対応しており、図３からの情報と一致して、厚さ１５ｎｍ以上のフッ化カルシウム薄膜の挿入が単結晶の酸化亜鉛膜をエピタキシャル成長させるために重要であることを示している。
【００１９】
図５及び図６は、厚さ３０ｎｍのフッ化カルシウム薄膜を挿入した試料における、酸化亜鉛単結晶膜からのフォトルミネッセンスを示す図であり、図５は発光エネルギーが３．２〜３．５ｅＶにおけるスペクトルの温度変化を示し、図６は発光エネルギーが２．０〜３．５ｅＶの幅広い領域における３００Ｋのスペクトルを示している。
図５に示すように、２０Ｋの低温から６０Ｋまでバンド端近傍の束縛励起子発光のみが観測され、それ以上の温度では自由励起子発光のみが観測されている。また、図６からわかるように、室温でも欠陥に基づく深い準位からの発光は観測されていない。この結果はフッ化カルシウム薄膜を挿入した酸化亜鉛膜には欠陥が少なく、半導体電子デバイスおよび発光受光デバイスの材料として使用できる高品質膜であることを示している。一方、フッ化カルシウム薄膜を挿入しなかった場合には、従来技術で製造された結晶について報告された結果と同様に１．５〜２．５ｅＶに欠陥からの発光が強く観測され、図５のいずれの温度においてもバンド端近傍の発光は微弱であった。この結果は、フッ化カルシウム薄膜を挿入しなかった酸化亜鉛膜は多量の欠陥準位を含んでおり半導体電子デバイスおよび発光受光デバイスの材料としては十分な品質を有していないことを示している。
【００２０】
図７は、フッ化カルシウム薄膜の厚さを変えた試料における酸化亜鉛膜とシリコン基板（ｐ型で抵抗率は０．０１Ωｃｍ、接合面積は２０ｍｍ2 ）との間の電流−電圧特性を示す図であり、この特性は電気絶縁層となるフッ化カルシウム薄膜を挟んだｐ型シリコンとｎ型酸化亜鉛が形成するｐｉｎ構造に基づくダイオード特性を示しており、また、フッ化カルシウム膜厚の増加とともに電気的絶縁性が顕著になることがわかる。フッ化カルシウム薄膜の厚さを１００ｎｍ以上にすると、順方向、逆方向ともに漏れ電流がほとんど観測されず、接合面の全域にわたって良好に電気的に絶縁分離されていることが観測され、シリコン基板と酸化亜鉛単結晶膜とを、半導体電子デバイス、発光受光デバイスにとって十分な程度に電気的に絶縁分離することができることがわかる。このことから、単結晶シリコン基板と酸化亜鉛膜を電気的に絶縁する上で必要なフッ化カルシウム薄膜の厚さは１００ｎｍ程度で十分であると結論できる。
【００２１】
【発明の効果】
上記説明から理解されるように本発明によれば、低コストかつ加工性に優れたシリコン基板上に成長することができ、基板面に垂直方向及び膜面内で結晶完全性が高く、かつ、シリコン基板と電気的に絶縁された酸化亜鉛単結晶膜を提供することができる。
したがって、本発明によれば、酸化亜鉛を使った半導体電子デバイス、発光受光デバイス、誘電的性質を利用した種々のデバイスをシリコン半導体による集積回路とワンチップに集積した高機能デバイス用材料として用いれば、極めて有用である。
【図面の簡単な説明】
【図１】本発明の方法によって形成される、単結晶シリコン基板とフッ化カルシウム単結晶薄膜と酸化亜鉛単結晶膜との積層構造を示す図である。
【図２】図１の積層構造を形成するための装置の一例である分子線エピタキシャル成長装置を模式的に示す図である。
【図３】本発明の方法によって形成された酸化亜鉛単結晶膜の｛１０−１１｝を極点としたＸ線回折の極点図であり、ｄはフッ化カルシウムの膜厚である。
【図４】本発明の方法によって形成された酸化亜鉛単結晶膜の（０００１）面Ｘ線回折ピークのロッキングカーブの半値幅とフッ化カルシウム膜厚ｄの関係を示す図である。
【図５】厚さ３０ｎｍのフッ化カルシウム薄膜を挿入した試料における、酸化亜鉛単結晶膜からのフォトルミネッセンスを示すグラフで、測定温度は２０Ｋから３００Ｋである。
【図６】厚さ３０ｎｍのフッ化カルシウム薄膜を挿入した試料における、酸化亜鉛単結晶膜からのフォトルミネッセンスを示すグラフで、測定温度は３００Ｋである。
【図７】フッ化カルシウム薄膜の厚さｄを変えた試料における酸化亜鉛膜とシリコン基板（ｐ型で抵抗率は０．０１Ωｃｍ、接合面積は２０ｍｍ2 ）との間の電流−電圧特性を示す図である。
【符号の説明】
１ 単結晶シリコン基板
２ フッ化カルシウム単結晶薄膜
３ 酸化亜鉛単結晶膜
４ 超高真空槽
５ 基板加熱装置
６ フッ化カルシウム坩堝
７ 亜鉛坩堝
８ 酸素ラジカル源
９ 排気系
１０ 電子銃
１１ スクリーン[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for epitaxially growing a single crystal zinc oxide film on a single crystal silicon substrate, an apparatus for performing this method, and a laminated structure .
[0002]
[Prior art]
Conventionally, polycrystalline zinc oxide (ZnO) has a surface acoustic wave element, a pyroelectric element, a piezoelectric element, a gas sensor, a varistor, or a transparent element utilizing its multifunctional properties such as dielectric properties and visible light transmission properties. It has been used for conductive films and the like.
Zinc oxide is a direct-transition type semiconductor with a forbidden band corresponding to the short wavelength end of visible light, so if a zinc oxide single crystal with high crystal integrity can be grown, it will be a semiconductor for high voltage electronic devices, emitting light It can also be used as a semiconductor for devices.
Therefore, if a zinc oxide single crystal film with high crystal integrity can be grown, it is possible to manufacture a semiconductor electronic device, a light emitting / receiving device, and a high-performance device in which various devices utilizing dielectric properties are integrated on a zinc oxide single crystal chip. It becomes possible.
[0003]
For this reason, various researches on the growth method of zinc oxide single crystals have been conducted in recent years.
For example, a report of epitaxial growth of a zinc oxide single crystal film on a sapphire substrate using an oxygen (O) radical and zinc (Zn) molecular beam by molecular beam epitaxy (see Iwata et al., Ceramic Data Book 2000, separate volume p190-194) Has been.
This method is an epitaxial growth utilizing the good matching between the sapphire substrate surface and the zinc oxide (0001) surface, and a zinc oxide single crystal film having a c-axis orientation in the direction perpendicular to the substrate surface is obtained.
However, since a sapphire substrate is expensive and difficult to process, a method for epitaxial growth on a substrate having a low cost and excellent workability is required for practical use. Although it is possible to grow on a zinc oxide single crystal substrate, the cost is higher.
[0004]
[Problems to be solved by the invention]
Also disclosed is a method in which a silicon nitride film is formed on a silicon (111) plane substrate, and a zinc oxide single crystal film is epitaxially grown on the silicon nitride film by the same method as in the above example (Japanese Patent Laid-Open No. 2001-44499). No. publication).
This method is an epitaxial growth utilizing the good matching between the silicon (111) plane and the zinc oxide (0001) plane. However, when oxygen radicals oxidize the silicon substrate surface to make the silicon substrate surface amorphous, it is simple. Since crystal growth cannot be performed, epitaxial growth is performed after forming and protecting an extremely thin silicon nitride film on the silicon surface.
[0005]
According to this method, it is possible to use a silicon substrate that is low in cost and excellent in workability, and is very useful because it can fuse a multifunctional zinc oxide semiconductor device and silicon integrated circuit technology. However, the zinc oxide single crystal film obtained by this method shows good c-axis orientation in the direction perpendicular to the substrate surface, but the crystal domain is rotated in the film surface, and carriers are scattered at the crystal domain interface. Thus, there are problems such as low carrier mobility and poor luminous efficiency due to recombination centers at the domain interface.
In this method, the film thickness of the silicon nitride film is extremely important. If the film is too thick, an amorphous silicon nitride film is formed thick on the surface of the silicon substrate and a regular atomic arrangement cannot be obtained. It cannot prevent oxidation. The optimum film thickness is about 10 nm, and it is extremely difficult to form this thickness over the entire surface of the substrate with good reproducibility. For this reason, it takes a great deal of man-hours to control the film thickness of the silicon nitride film, and the productivity is high. There is a problem of not going up.
In addition, when forming a semiconductor electronic device, a light emitting / receiving device, or an integrated circuit thereof, the silicon substrate and the zinc oxide single crystal film are electrically separated to reduce parasitic capacitance and leakage current, or to separate elements. It is preferable. However, this method has a problem that the silicon substrate and the zinc oxide single crystal film cannot be electrically separated because the silicon nitride film must be extremely thin.
[0006]
In view of the above problems, the present invention can grow on a silicon substrate having low cost and excellent workability, has high crystal integrity in a direction perpendicular to the substrate surface and in the plane, and is electrically insulated from the silicon substrate. It is an object of the present invention to provide a method for manufacturing a zinc oxide single crystal film on a single crystal silicon substrate.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, a method for producing a zinc oxide single crystal film on a single crystal silicon substrate according to the present invention comprises epitaxially growing a calcium fluoride single crystal thin film on the single crystal silicon substrate, By epitaxially growing a zinc oxide single crystal film, the c-axis orientation is perpendicular to the surface of the calcium fluoride single crystal thin film, and the pole figure by X-ray diffraction becomes 6-fold symmetric, and the crystal domain rotates in the plane. It is characterized in that an unobtained zinc oxide single crystal film is obtained.
According to this configuration, since the lattice matching between the silicon (111) plane, the calcium fluoride (111) plane, and the zinc oxide (0001) plane is good, the calcium fluoride single crystal thin film having high crystal integrity on the silicon substrate. Since zinc oxide is epitaxially grown on a calcium fluoride single crystal thin film with high crystal integrity, a crystal having a c-axis orientation perpendicular to the substrate surface and having no rotation domain in the plane of the single crystal film A zinc oxide single crystal film having good integrity can be obtained. In addition, since a silicon substrate is used, a zinc oxide single crystal film can be obtained at low cost. In addition, since calcium fluoride is an insulator and can be laminated thickly, the silicon substrate and the zinc oxide single crystal film can be electrically insulated and separated. Since calcium fluoride is transparent to light in a wide wavelength range including the visible range, visible light that passes through the zinc oxide single crystal film can reach the single crystal silicon substrate.
For this reason, for example, if a silicon solar cell is used as a substrate and an ultraviolet light sensor using a zinc oxide single crystal film is formed thereon via a calcium fluoride single crystal thin film, the power of the solar cell is used as a power source. It is also possible to produce a sensor / power source integrated UV sensor.
The epitaxial growth method according to the present invention may be any epitaxial method such as a molecular beam epitaxial method, an electron beam evaporation method, a laser ablation method, or a combination thereof.
Here, if the thickness of the calcium fluoride single crystal thin film is 15 nm or more, a zinc oxide single crystal film having high crystal integrity can be obtained. If the thickness is 100 nm or more, the silicon substrate, the zinc oxide single crystal film, Can be electrically insulated and separated to a degree sufficient for a semiconductor electronic device and a light emitting / receiving device. Furthermore, if the thickness of the calcium fluoride single crystal thin film is about 15 nm or more and 100 nm or less, a p-type silicon substrate is used, the calcium fluoride single crystal thin film is used as an insulating film, and the zinc oxide single crystal film is used as an n-type semiconductor. A pin-type diode can be formed.
[0008]
The apparatus for producing a zinc oxide single crystal film on a single crystal silicon substrate of the present invention comprises a substrate heating device for holding and heating at least a single crystal silicon substrate in an ultra-high vacuum chamber, and a crucible containing calcium fluoride. A calcium fluoride molecular beam source for generating a calcium fluoride molecular beam; a zinc molecular beam source for generating a zinc molecular beam comprising a crucible containing zinc; an oxygen radical source for generating an oxygen radical using a high-frequency discharge gun; , Is provided. When the method of the present invention is carried out using this manufacturing apparatus, a zinc oxide single crystal film having a c-axis orientation in the direction perpendicular to the substrate surface and having no crystallographic domain in the plane of the single crystal film is obtained. It is done.
[0009]
The laminated structure of the present invention comprises a single crystal silicon substrate, a calcium fluoride single crystal thin film on the single crystal silicon substrate, and a zinc oxide single crystal film on the calcium fluoride single crystal thin film. Has a c-axis orientation perpendicular to the surface of the calcium fluoride single crystal thin film, and the pole figure by X-ray diffraction is 6-fold symmetric, and the crystal domain rotates in the plane of the zinc oxide single crystal film. It is characterized by not.
In the above structure, the single crystal silicon substrate is preferably a (111) plane substrate. The thickness of the calcium fluoride single crystal thin film is preferably 15 nm or more. In the 100nm thickness of about calcium fluoride single crystal thin film, a single crystal silicon substrate and the zinc oxide single crystal film is electrically insulated can Rukoto.
In the photoluminescence of the zinc oxide single crystal film at room temperature, it is preferable that light emission from a deep level of 1.5 to 2.5 eV based on defects is not observed.
Thus, by using the method of the present invention, it is possible to produce a zinc oxide single crystal film that is low in cost, has unprecedented crystal integrity, is insulated from the substrate, or can be electrically connected to the substrate. Is possible.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The method for producing a zinc oxide single crystal film on a single crystal silicon substrate according to the present invention comprises epitaxially growing a calcium fluoride single crystal thin film on the single crystal silicon substrate and epitaxially growing a zinc oxide single crystal film on the calcium fluoride single crystal thin film. It is characterized by doing.
FIG. 1 is a view showing a laminated structure of a single crystal silicon substrate, a calcium fluoride single crystal thin film, and a zinc oxide single crystal film formed by the method of the present invention. FIG. 2 is a diagram schematically showing a molecular beam epitaxial apparatus which is an example of an apparatus for forming the laminated structure of FIG.
Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 and 2.
A calcium fluoride single crystal
[0011]
As the epitaxial growth method, for example, the molecular beam epitaxial apparatus shown in FIG. 2 can be used. As shown in FIG. 2, in the
[0012]
In the above description, the molecular beam epitaxial apparatus is taken as an example, but other epitaxial growth methods such as an electron beam evaporation method or a laser ablation method using a calcium fluoride target and a zinc oxide target may be used. A combination may be used. The method for heating the crucible may be resistance heating or electron beam heating.
The oxygen radical source described above has been described by taking an oxygen radical source using a high-frequency discharge gun as an example, but an oxygen radical source using an electron cyclotron resonance gun may be used.
[0013]
According to the above method, since the matching of the silicon (111) plane, the calcium fluoride (111) plane, and the zinc oxide (0001) plane is good, a calcium fluoride single crystal thin film with high crystal integrity is epitaxially grown on the silicon substrate. Since zinc oxide is epitaxially grown on a calcium fluoride single crystal thin film with high crystal integrity, the crystal integrity is excellent in the c-axis orientation in the direction perpendicular to the substrate surface and without rotation of crystal domains in the plane. A zinc oxide single crystal film can be obtained. In addition, since a silicon substrate is used, a zinc oxide single crystal film can be obtained at low cost.
[0014]
Here, if the thickness of the calcium fluoride single crystal thin film is 15 nm or more, a zinc oxide single crystal film having high crystal integrity can be obtained. If the thickness is 100 nm or more, the silicon substrate, the zinc oxide single crystal film, Can be electrically insulated and separated to a degree sufficient for a semiconductor electronic device and a light emitting / receiving device. Furthermore, if the thickness of the calcium fluoride single crystal thin film is about 15 nm or more and 100 nm or less, a p-type silicon substrate is used, the calcium fluoride single crystal thin film is used as an insulating film, and the zinc oxide single crystal film is used as an n-type semiconductor. A pin type diode can be formed.
[0015]
Next, examples of the present invention will be described.
As the crystal growth apparatus, the molecular beam epitaxial apparatus of FIG. 2 provided with an oxygen radical source using a high-frequency discharge gun, a zinc crucible and a calcium fluoride crucible was used. The flow rate of oxygen gas supplied to the high frequency discharge gun was 0.3 ccm, and the high frequency discharge power was 350 W. A silicon (111) plane single crystal substrate was used as the substrate.
After cleaning the silicon single crystal substrate with an organic solvent, the outermost surface was terminated with hydrogen atoms by standard etching using hydrofluoric acid and mounted on a molecular beam epitaxial apparatus. When this substrate was heated to 800 ° C. in a vacuum of 1 × 10 −7 Pa and kept for 5 minutes, a clean surface showing a reflected electron beam diffraction pattern of
The substrate having the clean surface was cooled to 650 ° C. and irradiated with a calcium fluoride molecular beam from a calcium fluoride crucible. The growth rate of the calcium fluoride film was 1.0 nm / min. Since the lattice constants of calcium fluoride and silicon are almost equal, the change in the electron diffraction pattern at the start of growth is streak-to-streaks, and a flat single-crystal calcium fluoride film was obtained from the first layer of deposition. . A calcium fluoride thin film having a thickness of 3 nm to 100 nm was grown and compared.
The mean square surface roughness of these thin films measured with an atomic force microscope was about 0.4 nm and was sufficiently flat for subsequent deposition of the zinc oxide film.
[0016]
Next, the temperature of the substrate was lowered to 250 ° C., and oxygen radicals were first irradiated, and then a zinc molecular beam was additionally irradiated from a zinc crucible to start growth of a zinc oxide film. The growth rate of the zinc oxide film was 3.3 nm / min. After a 10 nm thick zinc oxide film was grown, the oxygen radical irradiation was stopped and the growth was temporarily interrupted. Thereafter, while irradiating only the zinc molecular beam, the temperature was raised to 750 ° C. and kept for 10 minutes, followed by heat treatment, and then lowered to 500 ° C. During this heat treatment, the electron diffraction pattern from the surface of the zinc oxide film changed from spot-like to broad streak. This change indicates that the surface of the zinc oxide grown on the unevenness is almost flat.
Thereafter, oxygen radical irradiation was added again to re-grow a zinc oxide film having a thickness of 600 nm. The growth rate at this time was 6.7 nm / min. As the regrowth started, the electron diffraction pattern, which was a broad streak, gradually changed to a sharp streak, indicating that a high-quality single crystal zinc oxide film was epitaxially grown.
[0017]
FIG. 3 is a pole figure of X-ray diffraction with {10-11} as a pole in the zinc oxide film having an area of 2 cm 2 produced in this way. For comparison, a sample in which a zinc oxide film is epitaxially grown directly on a silicon substrate, that is, a sample in which a calcium fluoride thin film is not inserted is also shown. In the X-ray diffraction of the θ-2θ method separately measured, only the reflection peak due to the (0001) plane was observed from any zinc oxide film. However, when the calcium fluoride thin film is not inserted, the diffraction peak distribution in the pole figure of FIG. 3 has a ring shape. This means that the crystal structure of the zinc oxide film is a c-axis oriented film including a rotation domain in the film plane, which is consistent with the results reported by the prior art. On the other hand, when a calcium fluoride thin film is inserted, as the thickness of the calcium fluoride thin film increases, the pole figure approaches 6-fold symmetry, and when the thickness exceeds 15 nm, there is almost only a 6-fold symmetry spot. It was. This indicates that the insertion of the calcium fluoride thin film can prevent the generation of rotational domains in the zinc oxide film, and that the effect is sufficiently exerted when the thickness of the calcium fluoride thin film exceeds 15 nm. Yes.
[0018]
FIG. 4 is a diagram showing the relationship between the full width at half maximum of the rocking curve of the (0001) plane X-ray diffraction peak and the calcium fluoride film thickness in these zinc oxide films. The decrease in the half width corresponds to the decrease in the mosaic crystal in the zinc oxide film. In accordance with the information from FIG. 3, the insertion of a calcium fluoride thin film having a thickness of 15 nm or more epitaxially grows a single crystal zinc oxide film. It is important to make it happen.
[0019]
5 and 6 are diagrams showing photoluminescence from a zinc oxide single crystal film in a sample in which a calcium fluoride thin film having a thickness of 30 nm is inserted, and FIG. 5 shows a case where emission energy is 3.2 to 3.5 eV. The temperature change of the spectrum is shown, and FIG. 6 shows the spectrum of 300K in a wide region where the emission energy is 2.0 to 3.5 eV.
As shown in FIG. 5, only bound exciton luminescence near the band edge is observed from a low temperature of 20K to 60K, and only free exciton luminescence is observed at a temperature higher than that. Further, as can be seen from FIG. 6, light emission from a deep level based on defects is not observed even at room temperature. This result shows that the zinc oxide film with the calcium fluoride thin film inserted has few defects and is a high quality film that can be used as a material for semiconductor electronic devices and light-emitting / receiving devices. On the other hand, when the calcium fluoride thin film was not inserted, emission from defects was observed strongly at 1.5 to 2.5 eV, similar to the results reported for the crystals produced by the prior art. At any temperature, the light emission in the vicinity of the band edge was weak. This result indicates that the zinc oxide film into which the calcium fluoride thin film is not inserted contains a large amount of defect levels and does not have sufficient quality as a material for semiconductor electronic devices and light-emitting / receiving devices. .
[0020]
FIG. 7 is a diagram showing current-voltage characteristics between a zinc oxide film and a silicon substrate (p-type, resistivity is 0.01 Ωcm, junction area is 20 mm 2 ) in a sample in which the thickness of the calcium fluoride thin film is changed. This characteristic shows a diode characteristic based on a pin structure formed by p-type silicon and n-type zinc oxide sandwiching a calcium fluoride thin film serving as an electrical insulating layer, and as the calcium fluoride film thickness increases It can be seen that the electrical insulation becomes remarkable. When the thickness of the calcium fluoride thin film is set to 100 nm or more, almost no leakage current is observed in both the forward direction and the reverse direction, and it is observed that electrical insulation is well separated over the entire bonding surface. It can be seen that the zinc oxide single crystal film can be electrically insulated and separated to a degree sufficient for a semiconductor electronic device and a light emitting / receiving device. From this, it can be concluded that the thickness of the calcium fluoride thin film necessary for electrically insulating the single crystal silicon substrate and the zinc oxide film is about 100 nm.
[0021]
【The invention's effect】
As understood from the above description, according to the present invention, it is possible to grow on a silicon substrate having low cost and excellent workability, high crystal integrity in a direction perpendicular to the substrate surface and in the film surface, and A zinc oxide single crystal film that is electrically insulated from a silicon substrate can be provided.
Therefore, according to the present invention, if a semiconductor electronic device using zinc oxide, a light emitting / receiving device, and various devices utilizing dielectric properties are used as a material for a high-functional device integrated on an integrated circuit made of silicon semiconductor and one chip. Is extremely useful.
[Brief description of the drawings]
FIG. 1 is a view showing a laminated structure of a single crystal silicon substrate, a calcium fluoride single crystal thin film, and a zinc oxide single crystal film formed by the method of the present invention.
2 is a view schematically showing a molecular beam epitaxial growth apparatus which is an example of an apparatus for forming the stacked structure of FIG. 1;
FIG. 3 is an X-ray diffraction pole figure of {10-11} of a zinc oxide single crystal film formed by the method of the present invention, and d is the thickness of calcium fluoride.
FIG. 4 is a diagram showing a relationship between a half-value width of a rocking curve of a (0001) plane X-ray diffraction peak and a calcium fluoride film thickness d of a zinc oxide single crystal film formed by the method of the present invention.
FIG. 5 is a graph showing photoluminescence from a zinc oxide single crystal film in a sample in which a calcium fluoride thin film having a thickness of 30 nm is inserted, and the measurement temperature is 20K to 300K.
FIG. 6 is a graph showing photoluminescence from a zinc oxide single crystal film in a sample in which a calcium fluoride thin film having a thickness of 30 nm is inserted, and the measurement temperature is 300K.
FIG. 7 shows current-voltage characteristics between a zinc oxide film and a silicon substrate (p type, resistivity is 0.01 Ωcm, junction area is 20 mm 2 ) in a sample with a different thickness d of the calcium fluoride thin film. FIG.
[Explanation of symbols]
DESCRIPTION OF
Claims (11)
上記フッ化カルシウム単結晶薄膜表面に垂直方向にｃ軸配向し、かつ、Ｘ線回折による極点図形が６回対称となり、面内で結晶ドメインが回転していない上記酸化亜鉛単結晶膜を得ることを特徴とする、単結晶シリコン基板上の酸化亜鉛単結晶膜の製造方法。By epitaxially growing a calcium fluoride single crystal thin film on a single crystal silicon substrate and epitaxially growing a zinc oxide single crystal film on this calcium fluoride single crystal thin film,
To obtain the zinc oxide single crystal film which is c-axis oriented perpendicularly to the surface of the calcium fluoride single crystal thin film and whose pole figure by X-ray diffraction is 6-fold symmetric and whose crystal domain is not rotated in the plane. A method for producing a zinc oxide single crystal film on a single crystal silicon substrate.
フッ化カルシウムを入れた坩堝からなりフッ化カルシウム分子線を発生させるフッ化カルシウム分子線源と、
亜鉛を入れた坩堝からなり亜鉛分子線を発生させる亜鉛分子線源と、
高周波放電ガンを用いて酸素ラジカルを発生させる酸素ラジカル源と、
が設けられている単結晶シリコン基板上の酸化亜鉛単結晶膜の製造装置であって、
請求項１〜５に記載の方法を実施することを特徴とする、単結晶シリコン基板上の酸化亜鉛単結晶膜の製造装置。A substrate heating device for holding and heating at least a single crystal silicon substrate in an ultra-high vacuum chamber;
A calcium fluoride molecular beam source that is composed of a crucible containing calcium fluoride and generates a calcium fluoride molecular beam;
A zinc molecular beam source that generates a zinc molecular beam consisting of a crucible containing zinc;
An oxygen radical source that generates oxygen radicals using a high-frequency discharge gun;
An apparatus for producing a zinc oxide single crystal film on a single crystal silicon substrate provided with:
An apparatus for producing a zinc oxide single crystal film on a single crystal silicon substrate, wherein the method according to claim 1 is carried out.
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