JP5122082B2 - Method for forming conductive heterostructure compound film for electronic device - Google Patents
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本発明は電子デバイス用導電性ヘテロ構造化合物膜形成方法に関する。 The present invention relates to a method for forming a conductive heterostructure compound film for electronic devices.
今日、電子材料分野における進歩は著しく、高速電子デバイス、発光デバイスからレーザに至るまで多岐に応用されている。そして、近年、電子デバイスの分野では、ＥｒＰに代表されるランタノイド元素（Ｌｎ）とＶ族元素とからなる化合物を量子井戸とする二重障壁共鳴トンネルダイオードが期待されている。 Today, advances in the field of electronic materials are remarkable and are applied in a wide range of applications from high-speed electronic devices and light-emitting devices to lasers. In recent years, in the field of electronic devices, double barrier resonant tunneling diodes having a quantum well of a compound composed of a lanthanoid element (Ln) typified by ErP and a group V element are expected.
すなわち、Ｇａ（１−ｘ）ＩｎｘＰ／ＬｎＰ／Ｇａ（１−ｘ）ＩｎｘＰの如きのヘテロ構造を作成し、ＬｎＰ層の厚さを厳密に制御してエピタキシャル成長することが出来たならば、半金属と半導体のコントロ−ルが可能となり、種々の超高速電子デバイスを展望することが出来ると考えられる。 That is, if a heterostructure such as Ga (1-x) In x P / LnP / Ga (1-x) In x P can be created and the thickness of the LnP layer can be controlled strictly and epitaxially grown For example, it becomes possible to control semimetals and semiconductors, and it is considered that various ultrafast electronic devices can be prospected.
又、光の分野でも、ＬｎのＧａＡｓやＧａ（１−ｘ）ＩｎｘＰへの添加は通信システムにおける発光デバイスとしての応用が期待されており、特に、発光効率の安定化と発光効率の向上が待たれている。 In addition, in the field of light, addition of Ln to GaAs or Ga (1-x) In x P is expected to be applied as a light emitting device in a communication system, in particular, stabilization of light emission efficiency and improvement of light emission efficiency. Is waiting.
現在、ＧａＡｓに代表される化合物半導体の製造法は、有機金属化学気相成長法（ＭＯＣＶＤ）が主流である。 At present, metal-organic chemical vapor deposition (MOCVD) is the mainstream method for producing compound semiconductors represented by GaAs.
ところで、ランタノイド元素−Ｖ族元素のエピタキシャル成長やランタノイド元素の添加においても、良好なランタノイド有機金属原料が求められる。気化性が有るランタノイド有機金属は、β−ジケトネイトランタノイドが知られているが、このものは、固体であり、安定した蒸気が得られ難く、しかも分解性が悪いことから使用できない。そして、発光効率が良いランタノイド元素を添加した化合物半導体は得られていない。 By the way, a good lanthanoid organometallic raw material is also demanded in the epitaxial growth of a lanthanoid element-group V element and the addition of a lanthanoid element. A lanthanoid organometal having a vaporization property is known to be a β-diketonate lanthanoid, but this is a solid, it is difficult to obtain a stable vapor, and it cannot be used because it has a poor decomposability. Further, a compound semiconductor to which a lanthanoid element with good luminous efficiency is added has not been obtained.
従って、本発明が解決しようとする課題は、高性能な電子移動可能体が得られる技術を提供することである。特に、波長安定性や発光効率が良く、発光波長の環境温度依存性が極めて小さなランタノイド元素を有する電子移動可能体を提供することである。 Therefore, the problem to be solved by the present invention is to provide a technique for obtaining a high-performance electron movable body. In particular, an object of the present invention is to provide an electron-movable body having a lanthanoid element that has good wavelength stability and luminous efficiency and has extremely small environmental temperature dependence of the emission wavelength.
前記の課題を解決する為の研究を鋭意押し進めて行った結果、トリス−エチルシクロペンタジエニル−エルビウムを用いて構成された電子移動可能体が極めて高性能なものであることを見出すに至った。 As a result of eagerly pursuing research for solving the above-mentioned problems, it has been found that an electron-movable body composed of tris-ethylcyclopentadienyl-erbium has extremely high performance. .
上記知見に基づいて本願発明が達成されたものである。 The present invention has been achieved based on the above findings.
すなわち、前記の課題は、
基体上に電子デバイス用導電性ヘテロ構造化合物の膜を形成する方法であって、
トリス−エチルシクロペンタジエニル−エルビウムを分解させる工程を有する
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成方法によって解決される。
That is, the above problem is
A method of forming a conductive heterostructure compound film for an electronic device on a substrate, comprising :
Tris - is solved by an electronic device for conducting heterostructure compound film forming method comprising Rukoto to have a step of Ru to decompose erbium - ethylcyclopentadienyl.
又、Ｅｒ，ＥｒＮ，ＥｒＰ，ＥｒＡｓ，ＥｒＳｂ、酸素と結合したＥｒを含むＧａＡｓ又はＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の群の中から選ばれる電子デバイス用導電性ヘテロ構造化合物の膜を形成する方法であって、
トリス−エチルシクロペンタジエニル−エルビウムを分解させる工程を有する
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成方法によって解決される。
In addition, the conductivity for an electronic device selected from the group of Er, ErN, ErP, ErAs, ErSb, GaAs containing Er bonded to oxygen, or Ga (1-x) In x P (x is a number of 0 to 1). A method for forming a film of a functional heterostructure compound comprising:
Tris - is solved by an electronic device for conducting heterostructure compound film forming method comprising Rukoto to have a step of Ru to decompose erbium - ethylcyclopentadienyl.
特に、発光デバイスにおける導電性ヘテロ構造化合物膜を形成する上記電子デバイス用導電性ヘテロ構造化合物膜形成方法によって解決される。
上記トリス−エチルシクロペンタジエニル−エルビウムの分解は、熱、プラズマ、光、レーザの群の中から選ばれる手法により行われる。
In particular, the problem is solved by the above-described method for forming a conductive heterostructure compound film for an electronic device that forms a conductive heterostructure compound film in a light-emitting device.
The above tris-ethylcyclopentadienyl-erbium is decomposed by a method selected from the group consisting of heat, plasma, light, and laser.
又、電子デバイス用導電性ヘテロ構造化合物の膜を形成する為の材料であって、
トリス−エチルシクロペンタジエニル−エルビウムからなる
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成材料によって解決される。
Also, a material for forming a film of a conductive heterostructure compound for electronic devices ,
This is solved by a conductive heterostructure compound film- forming material for electronic devices , characterized by comprising tris-ethylcyclopentadienyl-erbium.
又、Ｅｒ，ＥｒＮ，ＥｒＰ，ＥｒＡｓ，ＥｒＳｂ、酸素と結合したＥｒを含むＧａＡｓ又はＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の群の中から選ばれる電子デバイス用導電性ヘテロ構造化合物膜を形成する為の材料であって、
トリス−エチルシクロペンタジエニル−エルビウムからなる
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成材料によって解決される。
In addition, the conductivity for an electronic device selected from the group of Er, ErN, ErP, ErAs, ErSb, GaAs containing Er bonded to oxygen, or Ga (1-x) In x P (x is a number of 0 to 1). A material for forming a functional heterostructure compound film ,
This is solved by a conductive heterostructure compound film- forming material for electronic devices , characterized by comprising tris-ethylcyclopentadienyl-erbium.
特に、発光デバイスにおける電子デバイス用導電性ヘテロ構造化合物膜を形成する上記電子デバイス用導電性ヘテロ構造化合物膜形成材料によって解決される。 In particular, the problem is solved by the conductive heterostructure compound film forming material for an electronic device that forms the conductive heterostructure compound film for an electronic device in a light emitting device.
トリス−エチルシクロペンタジエニル−エルビウム［（ＥｔＣｐ）３Ｅｒ］は、融点が７０℃以下で、気化させる温度において液体であり、気化特性が良好である。従って、高性能な電子デバイスが得られる。特に、波長安定性や発光効率が良く、発光波長の環境温度依存性が極めて小さなエルビウムを添加した電子デバイスが得られる。 Tris-ethylcyclopentadienyl-erbium [(EtCp) 3 Er] has a melting point of 70 ° C. or lower, is a liquid at the vaporization temperature, and has good vaporization characteristics. Therefore, a high-performance electronic device can be obtained. In particular, it is possible to obtain an electronic device to which erbium is added, which has good wavelength stability and luminous efficiency and has extremely small dependence of the emission wavelength on the environmental temperature.
尚、本願出願人は、先に、Ｒ１Ｒ２Ｒ３Ｌｎ〔Ｒ１，Ｒ２，Ｒ３はがエチルシクロペンタジエニル基（（Ｃ２Ｈ５）Ｃ５Ｈ４−）、イソプロピルシクロペンタジエニル基（（ｉ−Ｃ３Ｈ７）Ｃ５Ｈ４−）、ノルマルブタンシクロペンタジエニル基（（ｎ−Ｃ４Ｈ９）Ｃ５Ｈ４−）などのアルキル基、シリコン系化合物の基、及びアミノ基の群の中から選ばれる基〕で表される化合物からなるランタニド系膜形成材料、及びこのランタニド系膜形成材料で構成された膜をゲート酸化膜として用いた半導体素子を提案（特願２０００−２８００６２）している。 In addition, the applicant of the present application previously described R 1 R 2 R 3 Ln [R 1 , R 2 , R 3 is an ethylcyclopentadienyl group ((C 2 H 5 ) C 5 H 4 —), isopropyl cyclo pentadienyl ((i-C 3 H 7 ) C 5 H 4 -), normal butane cyclopentadienyl group ((n-C 4 H 9 ) C 5 H 4 -) alkyl radicals, such as, silicon compound A lanthanide-based film-forming material comprising a compound represented by the following formula: a group selected from the group of amino groups], and a semiconductor device using a film composed of the lanthanide-based film-forming material as a gate oxide film Proposed (Japanese Patent Application 2000-280062).
しかしながら、この提案（特願２０００−２８００６２）は、電子移動可能体に関するものではない。すなわち、ゲート酸化膜に関するものに過ぎない。そればかりか、特願２０００−２８００６２の具体的実施例で挙げられている［（ｉ−Ｃ３Ｈ７）Ｃ５Ｈ４］３Ｌｎを用いて電子移動可能体膜を形成した半導体素子は、［（Ｃ２Ｈ５）Ｃ５Ｈ４］３Ｌｎを用いて電子移動可能体膜を形成した半導体素子に比べて劣るものであった。 However, this proposal (Japanese Patent Application No. 2000-280062) does not relate to an electronically movable body. That is, it only relates to the gate oxide film. In addition, a semiconductor element in which an electron transferable body film is formed using [(i-C 3 H 7 ) C 5 H 4 ] 3 Ln, which is mentioned in a specific example of Japanese Patent Application No. 2000-280062, [(C 2 H 5 ) C 5 H 4 ] 3 Ln was inferior to a semiconductor element in which an electron transferable body film was formed.
本発明の電子移動可能体形成方法は、電子移動可能体を形成する方法である。特に、Ｅｒ，ＥｒＮ，ＥｒＰ，ＥｒＡｓ，ＥｒＳｂ、酸素と結合したＥｒを含むＧａＡｓ又はＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の群の中から選ばれる電子移動可能体を形成する方法である。又、発光デバイスにおける電子移動可能体を形成する方法である。そして、トリス−エチルシクロペンタジエニル−エルビウムを分解させ、基体上に電子移動可能体を設けるものである。トリス−エチルシクロペンタジエニル−エルビウムの分解は、熱、プラズマ、光、レーザの群の中から選ばれる手法により行われる。中でも、熱分解、光分解、反応分解、プラズマ分解、マイクロ波分解の群の中から選ばれる手法を用いて行われる。 The electron movable body forming method of the present invention is a method of forming an electron movable body. In particular, an electron transferable body selected from the group consisting of Er, ErN, ErP, ErAs, ErSb, GaAs containing Er bonded to oxygen, or Ga (1-x) In x P (x is a number from 0 to 1). It is a method of forming. Further, it is a method of forming an electron movable body in a light emitting device. Then, tris-ethylcyclopentadienyl-erbium is decomposed to provide an electron-movable body on the substrate. The decomposition of tris-ethylcyclopentadienyl-erbium is performed by a method selected from the group consisting of heat, plasma, light, and laser. Above all, it is carried out using a method selected from the group of thermal decomposition, photolysis, reaction decomposition, plasma decomposition, and microwave decomposition.
本発明の電子移動可能体形成材料は、電子移動可能体を形成する為の材料である。特に、Ｅｒ，ＥｒＮ，ＥｒＰ，ＥｒＡｓ，ＥｒＳｂ、酸素と結合したＥｒを含むＧａＡｓ又はＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の群の中から選ばれる電子移動可能体を形成する材料である。又、発光デバイスにおける電子移動可能体を形成する材料である。そして、トリス−エチルシクロペンタジエニル−エルビウムからなる。 The electron movable body forming material of the present invention is a material for forming an electron movable body. In particular, an electron transferable body selected from the group consisting of Er, ErN, ErP, ErAs, ErSb, GaAs containing Er bonded to oxygen, or Ga (1-x) In x P (x is a number from 0 to 1). Is a material that forms Further, it is a material for forming an electron movable body in a light emitting device. And tris-ethylcyclopentadienyl-erbium.
本発明の電子移動可能体は、上記電子移動可能体形成方法により基体上に形成されてなる電子移動可能体である。電子移動可能体は、例えばＥｒ，ＥｒＮ，ＥｒＰ，ＥｒＡｓ，ＥｒＳｂの群の中から選ばれる少なくとも一つからなる。或いは、Ｅｒ及び／又は酸素と結合したＥｒを含むＧａＡｓ又はＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）である。Ｅｒ及び／又は酸素と結合したＥｒの含有割合は、特に、薄膜１ｃｍ３当たり１０１５〜１０２２個である。本発明の電子移動可能体は、Ｇａ，Ｉｎ，Ｐを含む層とＧａ，Ｉｎ，Ｐを含む層との間に、上記電子移動可能体形成方法により形成されてなる電子移動可能体膜を有するものである。或いは、Ｇａ，Ｉｎ，Ｐを含む層及びＧａ，Ａｓを含む層と、Ｇａ，Ａｓを含む層及びＧａ，Ｉｎ，Ｐを含む層との間に、上記電子移動可能体形成方法により形成されてなる電子移動可能体膜を有するものである。特に、Ｇａ，Ｉｎ，Ｐを含む層及びＧａ，Ａｓを含む層と、Ｇａ，Ａｓを含む層及びＧａ，Ｉｎ，Ｐを含む層との間に、前記Ｇａ，Ａｓを含む層に隣接して上記電子移動可能体形成方法により形成されてなる電子移動可能体膜を有するものである。若しくは、上記電子移動可能体形成方法により形成されてなる電子移動可能体膜と上記電子移動可能体形成方法により形成されてなる電子移動可能体膜との間に、Ｇａ，Ｉｎ，Ｐを含む層及び／又はＧａ，Ａｓを含む層を有するものである。Ｇａ，Ｉｎ，Ｐを含む層は、例えばＧａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）である。 The electron movable body of the present invention is an electron movable body formed on a substrate by the electron movable body forming method. The electron movable body is made of at least one selected from the group of, for example, Er, ErN, ErP, ErAs, and ErSb. Alternatively, it is GaAs containing Er combined with Er and / or oxygen, or Ga (1-x) In x P (x is a number of 0 to 1). The content ratio of Er combined with Er and / or oxygen is particularly 10 15 to 10 22 per 1 cm 3 of the thin film. The electron transferable body of the present invention has an electron transferable body film formed by the above-described electron transferable body forming method between a layer containing Ga, In, and P and a layer containing Ga, In, and P. Is. Alternatively, it is formed between the layer containing Ga, In, P and the layer containing Ga, As and the layer containing Ga, As and the layer containing Ga, In, P by the above-described method of forming an electron movable body. It has an electron-transferable body film. In particular, a layer containing Ga, In, P and a layer containing Ga, As, and a layer containing Ga, As and a layer containing Ga, In, P are adjacent to the layer containing Ga, As, P. It has an electron transferable body film formed by the above-mentioned electron transferable body forming method. Alternatively, a layer containing Ga, In, and P between the electron movable body film formed by the electron movable body forming method and the electron movable body film formed by the electron movable body forming method. And / or a layer containing Ga and As. The layer containing Ga, In, and P is, for example, Ga (1-x) In x P (x is a number from 0 to 1).
以下、更に具体的な実施例を挙げて説明する。 Hereinafter, more specific examples will be described.
［実施例１］
［トリス−エチルシクロペンタジエニル−エルビウムの合成］
トリス−エチルシクロペンタジエニル−エルビウム（ＥｔＣｐ３Ｅｒ）が次のようにして合成された。
先ず、市販のエチルシクロペンタジエンと粉末状の金属ナトリウムとを溶媒中で反応させ、エチルシクロペンタジエニルナトリウムを合成した。この時の溶媒は、テトラヒドロフラン、ヘキサンなどであって、有機金属に不活性なものなら用いられる。又、粉末状の金属ナトリウムの代わりにＮａＨ，ＮａＮＨ２でも可能である。アルキルリチウム等を用いてエチルシクロペンタジエニルリチウムを合成しても良い。
合成されたエチルシクロペンタジエニルナトリウムと無水塩化エルビウムとを溶媒中で反応させ、ＥｔＣｐ３Ｅｒを合成した。この時の溶媒はテトラヒドロフラン、ヘキサンなどであって、有機金属に不活性なものなら用いられる。
溶媒を濃縮後、残渣からＥｔＣｐ３Ｅｒを溶媒抽出または蒸留抽出によって回収し、得られた粗生物を精密蒸留によって精製し、ＥｔＣｐ３Ｅｒを得た。
[Example 1]
[Synthesis of Tris-ethylcyclopentadienyl-erbium]
Tris-ethylcyclopentadienyl-erbium (EtCp 3 Er) was synthesized as follows.
First, commercially available ethylcyclopentadiene and powdered metallic sodium were reacted in a solvent to synthesize ethylcyclopentadienyl sodium. The solvent at this time is tetrahydrofuran, hexane, or the like, and any one that is inert to the organic metal is used. Further, NaH and NaNH 2 can be used instead of powdered metal sodium. Ethylcyclopentadienyl lithium may be synthesized using alkyl lithium or the like.
The synthesized ethylcyclopentadienyl sodium and anhydrous erbium chloride were reacted in a solvent to synthesize EtCp 3 Er. The solvent at this time is tetrahydrofuran, hexane or the like, and any one which is inert to the organic metal is used.
After the solvent was concentrated, EtCp 3 Er was recovered from the residue by solvent extraction or distillation extraction, and the resulting crude product was purified by precision distillation to obtain EtCp 3 Er.
このようにして得られたＥｔＣｐ３Ｅｒは、ＴＧ−ＤＴＡ分析によれば、気化特性が良好であることが判明した。又、融点は７０℃以下であり、気化させる温度において液体であることも判った。
又、化学組成も理論式と一致していた。更に、ＩＣＰ−ＭＡＳＳによれば、金属不純物は検出限界以下の高純度品であることが確認された。
尚、上記の合成が数回試みられた。その際の収率は３５〜７５％であった。
これに対して、トリス−シクロペンタジエニル−エルビウム（Ｃｐ３Ｅｒ）の収率は３５％より低く、ＥｔＣｐ３Ｅｒの製造コストはＣｐ３Ｅｒの製造コストよりも低いことが判った。
又、Ｅｒの代わりに、Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｔｍ，Ｙｂが用いられて同様に行われ、トリス−エチルシクロペンタジエニル−Ｌｎが合成された。
EtCp 3 Er thus obtained was found to have good vaporization characteristics according to TG-DTA analysis. It was also found that the melting point was 70 ° C. or lower, and it was a liquid at the vaporizing temperature.
The chemical composition also agreed with the theoretical formula. Furthermore, according to ICP-MASS, it was confirmed that the metal impurities are high-purity products having a detection limit or less.
The above synthesis was tried several times. The yield at that time was 35 to 75%.
In contrast, the yield of tris-cyclopentadienyl-erbium (Cp 3 Er) was found to be lower than 35%, and the production cost of EtCp 3 Er was lower than the production cost of Cp 3 Er.
Further, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, and Yb are used in place of Er, and the same procedure is performed to synthesize tris-ethylcyclopentadienyl-Ln. It was done.
次に、上記のようにして得られたＥｔＣｐ３Ｅｒを用いて電子デバイス用（導電性）ヘテロ構造化合物の膜を成膜した。
図１は成膜装置（ＭＯＣＶＤ）の概略図である。同図中、１ａ，１ｂ，１ｃ，１ｄ，１ｅは原料容器、３は加熱器、４は分解反応炉、５は基板である。
容器１ａ，１ｂ，１ｃ，１ｄ，１ｅには、各々、トリエチルガリウム（ＴＥＧ）、トリメチルインジウム（ＴＭＩ）、ＥｔＣｐ３Ｅｒ、ターシャリ−ブチルアルシン（ＴＢＡｓ）、ターシャリ−ブチルフォスフィン（ＴＢＰ）が入れられており、室温〜１５０℃の範囲の温度で保持されている。そして、キャリアガスとして水素が１〜２０００ｍｌ／ｍｉｎの割合で吹き込まれた。分解反応炉４内は０．１ａｔｍにされ、基板温度は流す原料種によって４５０℃〜７００℃に変化させた。初めにＴＢＡｓとＴＥＧとが、次にＴＢＰとＴＥＧとＴＭＩとが、その次にＴＢＰとＥｔＣｐ３Ｅｒとが、最後にＴＢＰとＴＥＧとＴＭＩとが流された。このようにして、基板５上に薄膜が形成された。
成膜後に基板を取り出し、膜の断面のＳＥＭ像を観測すると共に、ＳＩＭＳプロファイルの結果とを合わせることによって、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＥｒＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成されていることが確認された。
Next, a film of an electronic device (conductive) heterostructure compound was formed using EtCp 3 Er obtained as described above.
FIG. 1 is a schematic view of a film forming apparatus (MOCVD). In the figure, 1a, 1b, 1c, 1d, and 1e are raw material containers, 3 is a heater, 4 is a decomposition reaction furnace, and 5 is a substrate.
The
The substrate is taken out after film formation, and the SEM image of the cross section of the film is observed, and by combining with the result of the SIMS profile, the substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1). It was confirmed that a film of a (conductive) heterostructure compound for electronic devices having a structure of / ErP / Ga (1-x) In x P (x is a number from 0 to 1) was formed on the substrate.
［実施例２〜６］
実施例１において、ＴＢＰの代わりに水素、希釈酸素、アルキルヒドラジン、ＴＢＡｓ、トリメチルアンチモンをＥｔＣｐ３Ｅｒと共に流した以外は同様に行った。
そして、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／Ｅｒ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用ヘテロ構造化合物（化合物半導体）の膜が基板上に作成された素子（実施例２）、
基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／Ｅｒ２Ｏ３／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子（実施例３）、
基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＥｒＮ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子（実施例４）、
基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＥｒＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子（実施例５）、
基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＥｒＳｂ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子（実施例６）を得た。
尚、上記実施例において、熱分解の代わりに、プラズマ、光、レーザー、マイクロ波による分解手段を用いて同様に行った処、同様な結果が得られた。
[Examples 2 to 6]
In Example 1, hydrogen, diluted oxygen, alkyl hydrazine, TBAs, and trimethylantimony were flowed together with EtCp 3 Er in place of TBP.
An electronic device having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / Er / Ga (1-x) In x P (x is a number from 0 to 1). A device in which a film of a heterostructure compound (compound semiconductor) is prepared on a substrate (Example 2),
Electrons having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1) / Er 2 O 3 / Ga (1-x) In x P (x is a number from 0 to 1) An element (Example 3) in which a film of a (conductive) heterostructure compound for a device is formed on a substrate,
For electronic devices having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / ErN / Ga (1-x) In x P (x is a number from 0 to 1) ( A device in which a film of a conductive) heterostructure compound is formed on a substrate (Example 4);
For electronic devices having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / ErAs / Ga (1-x) In x P (x is a number from 0 to 1) ( A device in which a film of a conductive) heterostructure compound is formed on a substrate (Example 5),
For electronic devices having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / ErSb / Ga (1-x) In x P (x is a number from 0 to 1) ( An element (Example 6) in which a film of a conductive) heterostructure compound was formed on a substrate was obtained.
In the above examples, similar results were obtained when the same procedure was performed using plasma, light, laser, and microwave decomposition means instead of thermal decomposition.
又、ＥｔＣｐ３Ｅｒの代わりに、ＥｔＣｐ３Ｃｅ，ＥｔＣｐ３Ｐｒ，ＥｔＣｐ３Ｎｄ，ＥｔＣｐ３Ｐｍ，ＥｔＣｐ３Ｓｍ，ＥｔＣｐ３Ｅｕ，ＥｔＣｐ３Ｇｄ，ＥｔＣｐ３Ｔｂ，ＥｔＣｐ３Ｄｙ，ＥｔＣｐ３Ｈｏ，ＥｔＣｐ３Ｔｍ，ＥｔＣｐ３Ｙｂが用いられて同様に行われた。そして、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＣｅＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＰｒＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＮｄＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＰｍＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＳｍＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＥｕＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＧｄＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＴｂＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＤｙＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＨｏＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＴｍＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＹｂＰ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成された素子が得られた。 Also, instead of EtCp 3 Er, EtCp 3 Ce, EtCp 3 Pr, EtCp 3 Nd, EtCp 3 Pm, EtCp 3 Sm, EtCp 3 Eu, EtCp 3 Gd, EtCp 3 Tb, EtCp 3 Dy, EtCp 3 Ho, EtCp 3 Tm, EtCp 3 Yb was used in the same way. An electronic device having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / CeP / Ga (1-x) In x P (x is a number from 0 to 1). A device in which a film of a (conductive) heterostructure compound is prepared on a substrate, substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / PrP / Ga (1-x) An element in which a film of a (conductive) heterostructure compound for an electronic device having a structure of In x P (x is a number from 0 to 1) is formed on a substrate, substrate / GaAs / Ga (1-x) In x P ( x is a number of 0 to 1 ) / NdP / Ga (1-x) In x P (x is a number of 0 to 1) structure (conductive) heterostructure compound film for electronic devices is formed on the substrate Device, substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / PmP / Ga (1-x) In x An element in which a film of a (conductive) heterostructure compound for an electronic device having a structure of P (x is 0 to 1) is formed on a substrate, substrate / GaAs / Ga (1-x) In x P (x is 0 to 1 ) / SmP / Ga (1-x) In x P (x is a number from 0 to 1) structure for an electronic device (conductive) heterostructure compound film formed on a substrate , Substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / EuP / Ga (1-x) In x P (x is a number from 0 to 1) Device in which a film of (conductive) heterostructure compound is formed on a substrate, substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / GdP / Ga (1-x) In x P (x is 0-1 number of) elements film electronic devices (conductive) heterostructure compound of structure has been created on the substrate, For electronic devices having a structure of substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / TbP / Ga (1-x) In x P (x is a number from 0 to 1) ( Device in which a film of a (conductive) heterostructure compound is formed on a substrate, substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1 ) / DyP / Ga (1-x) In x An element in which a film of a (conductive) heterostructure compound for an electronic device having a structure of P (x is 0 to 1) is formed on a substrate, substrate / GaAs / Ga (1-x) In x P (x is 0 to 1 ) / HoP / Ga (1-x) In x P (x is a number from 0 to 1) structure for an electronic device (conductive) heterostructure compound film formed on a substrate , substrate / GaAs / Ga (1-x ) in x P (x is the number of 0~1) / TmP / Ga (1 -x) in x P (x Structural electronic devices 0-1 number) (conductive) element film is created on a substrate of the heterostructure compound, substrate / GaAs / Ga (1-x ) In x P (x is 0-1 Number) / YbP / Ga (1-x) In x P (x is a number from 0 to 1), an element in which a film of a (conductive) heterostructure compound for an electronic device was formed on a substrate was obtained. .
［実施例７］
図１の成膜装置を用いた。容器１ａ，１ｂ，１ｃ，１ｄ，１ｅには、各々、ＴＥＧ，ＴＭＩ，ＥｔＣｐ３Ｅｒ，ＴＢＡｓ，ＴＢＰが入れられており、室温〜１５０℃の範囲の温度で保持されている。そして、キャリアガスとして水素が１〜２０００ｍｌ／ｍｉｎの割合で吹き込まれた。分解反応炉４内は０．１ａｔｍにされ、基板温度は流す原料種によって４５０℃〜７００℃に変化させた。初めにＴＢＡｓとＴＥＧとが、次にＴＢＰとＴＥＧとＴＭＩとが、その次にＴＢＡｓとＴＥＧとＥｔＣｐ３Ｅｒとが、最後にＴＢＰとＴＥＧとＴＭＩとが流された。尚、ＥｔＣｐ３Ｅｒを流す際、Ａｒ希釈酸素（酸素濃度３８ｐｐｍ）を１〜５０ｍｌ／ｍｉｎの割合で同時に供給した。
このようにして、基板５上に薄膜が形成された。
[Example 7]
The film forming apparatus of FIG. 1 was used. The
In this way, a thin film was formed on the substrate 5.
成膜後に基板を取り出し、膜の断面のＳＥＭ像を観測すると共に、ＳＩＭＳプロファイルの結果とを合わせることによって、基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＧａＡｓ：Ｅｒ，Ｏ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成されていることが確認された。尚、Ｅｒの濃度は約５×１０１７個／ｃｍ３であった。
この素子（発光デバイス）の発光スペクトルを観察した処、室温で波長１．５μｍ帯に高輝度でシャープな発光が観察された。又、その発光波長は環境温度に対して極めて安定であった。
The substrate is taken out after film formation, and the SEM image of the cross section of the film is observed, and by combining with the result of the SIMS profile, the substrate / GaAs / Ga (1-x) In x P (x is a number from 0 to 1). / GaAs: Er, O / Ga (1-x) In x P (x is a number from 0 to 1) structure for electronic device (conductive) heterostructure compound film is formed on the substrate confirmed. The Er concentration was about 5 × 10 17 pieces / cm 3 .
When the emission spectrum of this element (light-emitting device) was observed, high-intensity and sharp light emission was observed in the wavelength band of 1.5 μm at room temperature. The emission wavelength was extremely stable with respect to the environmental temperature.
［実施例８］
実施例７において、ＧａＩｎＰ膜とＧａＡｓ：Ｅｒ，Ｏ膜との界面にＥｒを添加していないＧａＡｓ膜を持つ、すなわち基板／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）／ＧａＡｓ／ＧａＡｓ：Ｅｒ，Ｏ／ＧａＡｓ／Ｇａ（１−ｘ）ＩｎｘＰ（ｘは０〜１の数）の構造の電子デバイス用ヘテロ構造化合物（化合物半導体）の膜が基板上に作成されている素子を作成した。尚、ＧａＡｓ膜はＴＢＡｓとＴＥＧとを流すことによって成膜された。
この素子（発光デバイス）は、実施例７の素子のものよりも発光効率に優れていた。
[Example 8]
In Example 7, a GaAs film to which Er is not added is provided at the interface between the GaInP film and the GaAs: Er, O film, that is, the substrate / GaAs / Ga (1-x) In x P (x is 0 to 1) . Number) / GaAs / GaAs: Er, O / GaAs / Ga (1-x) In x P (x is a number from 0 to 1) heterostructure compound (compound semiconductor) film for electronic devices is formed on the substrate. The element that has been created was created. The GaAs film was formed by flowing TBAs and TEG.
This element (light-emitting device) was superior in luminous efficiency to that of the element of Example 7.
［実施例９］
図１の成膜装置を用いた。容器１ａ，１ｂ，１ｃ，１ｄ，１ｅには、各々、ＴＥＧ，ＴＭＩ，ＥｔＣｐ３Ｅｒ，ＴＢＡｓ，ＴＢＰが入れられており、室温〜１５０℃の範囲の温度で保持されている。そして、キャリアガスとして水素が１〜２０００ｍｌ／ｍｉｎの割合で吹き込まれた。分解反応炉４内は０．１ａｔｍにされ、基板温度は流す原料種によって４５０℃〜７００℃に変化させた。初めにＴＢＰとＥｔＣｐ３Ｅｒとが、次にＴＢＰとＴＭＩとが、最後にＴＢＰとＥｔＣｐ３Ｅｒとが流された。
このようにして、基板５上に薄膜が形成された。
成膜後に基板を取り出し、膜の断面のＳＥＭ像を観測すると共に、ＳＩＭＳプロファイルの結果とを合わせることによって、基板／ＥｒＰ／ＩｎＰ／ＥｒＰの構造の電子デバイス用（導電性）ヘテロ構造化合物の膜が基板上に作成されていることが確認された。
[Example 9]
The film forming apparatus of FIG. 1 was used. The
In this way, a thin film was formed on the substrate 5.
The substrate is taken out after the film formation, and the SEM image of the cross section of the film is observed, and by combining with the result of the SIMS profile, the film of the substrate / ErP / InP / ErP structure (conductive) heterostructure compound for electronic devices It was confirmed that was produced on the substrate.
１ａ，１ｂ，１ｃ，１ｄ，１ｅ 原料容器
３ 加熱器
４ 分解反応炉
５ 基板
代理人 宇 高 克 己
1a, 1b, 1c, 1d, 1e Raw material container 3 Heater 4 Decomposition reactor 5 Substrate
Agent Katsumi Udaka
Claims (3)
トリス−エチルシクロペンタジエニル−エルビウムを分解させる工程を有する
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成方法。 A method of forming a conductive heterostructure compound film for an electronic device on a substrate, comprising:
A method for forming a conductive heterostructure compound film for an electronic device, comprising the step of decomposing tris-ethylcyclopentadienyl-erbium.
トリス−エチルシクロペンタジエニル−エルビウムを分解させる工程を有する
ことを特徴とする電子デバイス用導電性ヘテロ構造化合物膜形成方法。 Conductive heterogeneity for electronic devices selected from the group consisting of Er, ErN, ErP, ErAs, ErSb, GaAs containing Er bonded to oxygen, or Ga (1-x) In x P (x is a number from 0 to 1). A method of forming a film of a structural compound comprising:
A method for forming a conductive heterostructure compound film for an electronic device, comprising the step of decomposing tris-ethylcyclopentadienyl-erbium.
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| FR2646020B1 (en) * | 1989-04-13 | 1991-07-12 | Lecorre Alain | COMPOSITE MATERIAL COMPRISING A LAYER OF A III-V COMPOUND AND A LAYER OF RARE EARTHS PNICTURE, METHOD OF MANUFACTURE AND APPLICATION |
| JP4183787B2 (en) * | 1997-11-28 | 2008-11-19 | Ｔｄｋ株式会社 | Manufacturing method of substrate for electronic device |
| JP2000022269A (en) * | 1998-07-02 | 2000-01-21 | Nec Corp | Blue semiconductor laser element |
| JP4463403B2 (en) * | 2000-09-14 | 2010-05-19 | 株式会社トリケミカル研究所 | Gate oxide film forming material and gate oxide film forming method |
| JP2002338590A (en) * | 2001-05-15 | 2002-11-27 | Kojundo Chem Lab Co Ltd | Tris(ethylcyclopentadienyl)lanthanoid, method of producing the same and method of producing oxide thin film through vapor-phase |
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