JPH11282033A - Organic and inorganic composite material - Google Patents
Organic and inorganic composite materialInfo
- Publication number
- JPH11282033A JPH11282033A JP8388498A JP8388498A JPH11282033A JP H11282033 A JPH11282033 A JP H11282033A JP 8388498 A JP8388498 A JP 8388498A JP 8388498 A JP8388498 A JP 8388498A JP H11282033 A JPH11282033 A JP H11282033A
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- Japan
- Prior art keywords
- organic
- superlattice
- semiconductor
- inorganic
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体レーザ、非
線形光学素子を初めとする光電子素子用超格子材料とし
ての有機無機複合材料に関する。The present invention relates to an organic-inorganic composite material as a superlattice material for optoelectronic devices such as semiconductor lasers and nonlinear optical devices.
【０００２】[0002]
【従来の技術】従来より、半導体超格子が光電子材料と
して広く用いられており、半導体レーザ、非線形光学素
子を作製する上で不可欠な材料となっている。半導体超
格子は、バンドギャップが異なる２種の半導体Ａ、Ｂを
交互に積層することにより形成され、超格子構造に対応
して価電子帯上端および伝導帯下端のエネルギー順位が
変化する特徴を有する。2. Description of the Related Art Conventionally, semiconductor superlattices have been widely used as optoelectronic materials and have become indispensable materials for producing semiconductor lasers and nonlinear optical elements. The semiconductor superlattice is formed by alternately laminating two kinds of semiconductors A and B having different band gaps, and has a feature that the energy order of the upper end of the valence band and the lower end of the conduction band change according to the superlattice structure. .
【０００３】半導体超格子は、安藤恒也著「半導体ヘテ
ロ構造超格子」〔大槻義彦編「物理学最前線」第１３
巻、共立出版、東京（１９８６年）〕に記載されている
ように、交互積層する半導体のバンドギャップのエネル
ギー的な位置関係により分類され、電子と正孔を同一の
半導体層に閉じ込める超格子をタイプＩ、電子と正孔が
それぞれ異なる半導体層に閉じ込める超格子をタイプII
と呼んで区別される。Semiconductor superlattices are described in Tsuneya Ando, “Semiconductor heterostructure superlattice” [edited by Yoshihiko Otsuki, “Forefront of Physics,” 13
Vol., Kyoritsu Shuppan, Tokyo (1986)], a superlattice that is classified by the energy positional relationship of the band gap of semiconductors stacked alternately and confines electrons and holes in the same semiconductor layer. Type I, a type II superlattice that confines electrons and holes in different semiconductor layers
Are distinguished.
【０００４】図１は、光電子材料として最もよく用いら
れているタイプＩの超格子およびそのバンドギャップの
模式図である。半導体Ａ層１と半導体Ｂ層２を交互積層
することにより、伝導体下端４および価電子帯上端５の
エネルギー順位が周期的に変化する。FIG. 1 is a schematic diagram of a type I superlattice most frequently used as an optoelectronic material and its band gap. By alternately laminating the semiconductor A layer 1 and the semiconductor B layer 2, the energy order of the conductor lower end 4 and the valence band upper end 5 changes periodically.
【０００５】図１の場合、伝導体の電子および価電子帯
の正孔は、共にＡ層からなる量子井戸層６に閉じ込めら
れ量子順位７、８が形成される。量子順位７、８は、超
格子ヘテロ界面でのΔＥv、ΔＥc、ｄAおよびｄBにより
決まり、それらは超格子材料の電気的、光学的性質を決
定するので、半導体超格子ではＥv、Ｅc、ｄAおよびｄB
をパラメータとして適宜調節することにより、材料の光
学的性質および電気的性質を変えることができる。In the case of FIG. 1, the electrons of the conductor and the holes of the valence band are both confined in the quantum well layer 6 composed of the A layer, and quantum ranks 7 and 8 are formed. Quantum rank 7 and 8, Delta] E v at the superlattice hetero interface, Delta] E c, determined by d A and d B, because they determine the electrical, optical properties of the superlattice material, E v in semiconductor superlattices , E c , d A and d B
By appropriately adjusting as a parameter, the optical and electrical properties of the material can be changed.
【０００６】例えば、最も研究がなされているＧａＡｓ
／ＧａＡｌＡｓ超格子では、ｄAおよびｄBを変えること
により、電子および正孔の移動度、吸収・発光スペクト
ルを変化させることが可能である。For example, the most studied GaAs
In the / GaAlAs superlattice, it is possible to change the mobility of electrons and holes and the absorption / emission spectrum by changing d A and d B.
【０００７】また、近年、有機材料と半導体材料をヘテ
ロ接合させた構造を有する有機無機複合超格子材料が提
案されている。例えば、特開平６−３７１２号公報で
は、エネルギーギャップが１.８〜２.８ｅＶの有機半導
体層と、エネルギーギャップが３.０ｅＶ以上の無機半
導体材料を交互に積層した有機無機複合超格子が開示さ
れており、可視光照射により有機層内部のキャリア密度
を増大させる材料構成法が提案されている。In recent years, an organic-inorganic composite superlattice material having a structure in which an organic material and a semiconductor material are heterojunction has been proposed. For example, JP-A-6-3712 discloses an organic-inorganic composite superlattice in which an organic semiconductor layer having an energy gap of 1.8 to 2.8 eV and an inorganic semiconductor material having an energy gap of 3.0 eV or more are alternately laminated. Thus, a material composition method for increasing the carrier density inside the organic layer by irradiating visible light has been proposed.
【０００８】また、特開平２−２０１３２０号公報で
は、有機非線形光学材料を無機半導体と交互に積層する
ことにより、前記非線形光学材料を２次元化し、その非
線形性を増大させる方法が開示されている。Japanese Patent Application Laid-Open No. Hei 2-201320 discloses a method in which an organic nonlinear optical material is alternately laminated with an inorganic semiconductor to make the nonlinear optical material two-dimensional and increase its nonlinearity. .
【０００９】これらは、無機半導体材料をスペーサとす
ることにより有機半導体、有機非線形光学材料を２次元
化し、それらの機能向上を狙った材料であり、電子およ
び正孔の量子順位を、人為的にコントロールして物性を
制御する半導体超格子材料とは構想が異なる。These are two-dimensional organic semiconductors and organic non-linear optical materials by using inorganic semiconductor materials as spacers to improve their functions. The quantum order of electrons and holes is artificially changed. The concept is different from that of a semiconductor superlattice material in which physical properties are controlled by controlling.
【００１０】[0010]
【発明が解決しようとする課題】半導体超格子は、光電
子材料として極めて優れた材料であるが、半導体特有の
欠点も存在する。即ち、半導体材料は共有結合性結晶で
あるので、格子定数が大きく異なる半導体同士を交互に
積層させた場合、良好なヘテロ界面が形成できず超格子
化できないと云う制約がある。Although the semiconductor superlattice is a very excellent material as an optoelectronic material, it also has disadvantages peculiar to semiconductors. In other words, since the semiconductor material is a covalent bond crystal, there is a restriction that when semiconductors having greatly different lattice constants are alternately stacked, a favorable heterointerface cannot be formed and a superlattice cannot be formed.
【００１１】このため半導体超格子は、格子定数が類似
した半導体を交互に積層して形成されるのが通常である
が、格子定数は半導体のバンドギャップのエネルギー位
置に影響するので、半導体超格子ではヘテロ界面でのバ
ンドギャップの変化、即ち、図１におけるΔＥv、ΔＥc
を大きくすることができないと云う問題がある。For this reason, the semiconductor superlattice is usually formed by alternately laminating semiconductors having similar lattice constants. However, since the lattice constant affects the energy position of the band gap of the semiconductor, the semiconductor superlattice is formed. Then, the band gap changes at the hetero interface, that is, ΔE v , ΔE c in FIG.
There is a problem that cannot be increased.
【００１２】例えば、最も典型的なＧａＡｓ／ＧａＡｌ
Ａｓ超格子の場合、ヘテロ界面でのΔＥvは約３０ｍｅ
Ｖ、ΔＥcは２５０ｍｅＶ程度にすぎない。For example, the most typical GaAs / GaAl
In the case of an As superlattice, ΔE v at the heterointerface is about 30 me.
V and ΔE c are only about 250 meV.
【００１３】ヘテロ界面におけるΔＥvおよびΔＥcは、
それぞれ正孔および電子が量子井戸６に閉じ込めるポテ
ンシャル障壁であるので、半導体超格子は電子・正孔を
強く量子井戸に閉じ込めることができない。このため、
半導体超格子の物性制御はある範囲内に限られ、半導体
超格子は電子・正孔の強い量子閉じ込めにより非線形光
学効果を発現する量子光デバイス用材料としては不適切
である。[0013] ΔE v and ΔE c at the hetero interface are
Since the holes and electrons are potential barriers for confining the quantum well 6 respectively, the semiconductor superlattice cannot strongly confine electrons and holes in the quantum well. For this reason,
The control of the physical properties of a semiconductor superlattice is limited to a certain range, and the semiconductor superlattice is unsuitable as a material for a quantum optical device that exhibits a nonlinear optical effect due to strong quantum confinement of electrons and holes.
【００１４】本発明の目的は、電子および正孔を強く閉
じ込める量子井戸を有する超格子材料で構成された光電
子素子用超格子材料としての有機無機複合材料を提供す
ることにある。An object of the present invention is to provide an organic-inorganic composite material as a superlattice material for an optoelectronic device, comprising a superlattice material having a quantum well for strongly confining electrons and holes.
【００１５】[0015]
【課題を解決するための手段】半導体超格子の前記課題
は、バンドギャップが大きな有機絶縁材料と無機半導体
材料を交互積層して作製される本発明の有機無機複合材
料により解決される。The above object of the semiconductor superlattice is solved by the organic-inorganic composite material of the present invention, which is produced by alternately laminating an organic insulating material and an inorganic semiconductor material having a large band gap.
【００１６】有機絶縁材料と無機半導体材料をヘテロ接
合させた場合、両者は主としてファンデルワールス相互
作用により結合し、共有結合が生じない。このため、有
機絶縁材料と無機半導体材料のヘテロ界面には、半導体
超格子の場合のような格子定数に関する制限（格子整合
条件）が存在せず、構造およびバンドギャップが大きく
異なる材料を組み合わせてヘテロ界面を作製する。When an organic insulating material and an inorganic semiconductor material are heterojuncted, they are bonded mainly by van der Waals interaction, and no covalent bond occurs. For this reason, the heterointerface between the organic insulating material and the inorganic semiconductor material does not have a limitation (lattice matching condition) regarding the lattice constant as in the case of the semiconductor superlattice, and heterostructures and materials having greatly different band gaps are combined. Create an interface.
【００１７】上記を達成する本発明の要旨は、有機絶縁
層と無機半導体層が積層接合された超格子構造を有する
有機無機複合材料において、前記有機絶縁層を構成する
材料が、The gist of the present invention to achieve the above is that in an organic-inorganic composite material having a superlattice structure in which an organic insulating layer and an inorganic semiconductor layer are laminated and joined, the material constituting the organic insulating layer is:
【００１８】[0018]
【化２】 Embedded image
【００１９】で示される無水マレイン酸〔化１〕、ビフ
ェニル〔化２〕、１,２,４,５−ベンゾテトラカルボン
酸二無水物〔化３〕、ナフタリン−１,４,５,８−テト
ラカルボン酸二無水物〔化４〕から選ばれることを特徴
とする有機無機複合材料にある。Maleic anhydride [formula 1], biphenyl [formula 2], 1,2,4,5-benzotetracarboxylic dianhydride [formula 3], naphthalene-1,4,5,8- An organic-inorganic composite material characterized by being selected from tetracarboxylic dianhydride [Formula 4].
【００２０】また、本発明の無機半導体層を構成する材
料としては、ＧａＡｓまたはＺｎＳｅが挙げられる。As a material constituting the inorganic semiconductor layer of the present invention, GaAs or ZnSe can be used.
【００２１】本発明では、上記の有機絶縁材料と無機半
導体材料のヘテロ界面の性質を利用することにより、従
来の半導体超格子では不可能であった電子・正孔の強い
量子閉じ込めを実現することができる。In the present invention, by utilizing the property of the heterointerface between the organic insulating material and the inorganic semiconductor material, it is possible to realize strong quantum confinement of electrons and holes, which was impossible with a conventional semiconductor superlattice. Can be.
【００２２】また、前記有機絶縁層と無機半導体層が３
層以上交互に積層され、かつ、有機絶縁層により電子お
よび正孔が無機半導体層内部に２次元的に閉じこめられ
るよう構成されている前記の有機無機複合材料にある。Further, the organic insulating layer and the inorganic semiconductor layer are each composed of 3
The organic-inorganic composite material has a structure in which a plurality of layers are alternately stacked, and wherein the organic insulating layer is configured to two-dimensionally confine electrons and holes inside the inorganic semiconductor layer.
【００２３】また、前記有機絶縁層と無機半導体層のヘ
テロ界面がファンデルワールス作用により接合されてい
る前記の有機無機複合材料にある。Further, there is provided the organic-inorganic composite material, wherein the hetero interface between the organic insulating layer and the inorganic semiconductor layer is joined by van der Waals action.
【００２４】さらにまた、有機絶縁層と無機半導体層の
ヘテロ界面接合の、伝導帯下端のエネルギー変化が１.
３３〜４.０７ｅＶ、価電子帯上端のエネルギー変化が
２.５２〜５.９４ｅＶである前記の有機無機複合材料に
ある。Further, the energy change at the lower end of the conduction band at the hetero interface junction between the organic insulating layer and the inorganic semiconductor layer is 1.
The organic-inorganic composite material has an energy change of 33 to 4.07 eV and an upper end of the valence band of 2.52 to 5.94 eV.
【００２５】[0025]
【発明の実施の形態】図２は、各種半導体および有機化
合物の価電子帯上端のエネルギー順位（Ｅv）、伝導帯
下端エネルギー順位（Ｅc）および両者の差であるバン
ドギャップ（Ｅg）を示したものである。半導体のＥv，
ＥcおよびＥgは、前記の「半導体ヘテロ構造超格子」に
記載されている数値を用いた。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 2 shows the energy order (E v ) at the upper end of the valence band, the energy order (E c ) at the lower end of the conduction band, and the band gap (E g ) which is the difference between the two. It is shown. Semiconductor E v ,
For E c and E g , the numerical values described in the above “semiconductor heterostructure superlattice” were used.
【００２６】有機化合物のＥv，ＥcおよびＥgは、分子
のＥvおよびＥcがそれぞれ分子のイオン化ポテンシャル
および電子親和力で近似できることを利用し、日本化学
会編「化学便覧基礎編」、丸善、東京（１９９３年）記
載の有機分子のイオン化ポテンシャルと電子親和力を用
いて求めた。E v , E c, and E g of the organic compound are obtained by using the fact that E v and E c of the molecule can be approximated by the ionization potential and electron affinity of the molecule, respectively. It was determined using the ionization potential and electron affinity of organic molecules described in Maruzen, Tokyo (1993).
【００２７】記述のように、従来型の半導体超格子を作
製するためには、格子定数が近い半導体材料同士を交互
に積層する必要がある。格子定数が近い半導体のΔＥv
は最大１ｅＶ弱、ΔＥcは最大数百ｅＶ程度であり、従
来の超格子では電子および正孔を量子井戸内部に強く閉
じ込めることができない。As described above, in order to manufacture a conventional semiconductor superlattice, it is necessary to alternately laminate semiconductor materials having similar lattice constants. ΔE v for semiconductors with similar lattice constants
Is less than 1 eV at the maximum and ΔE c is about several hundreds of eV at the maximum. In the conventional superlattice, electrons and holes cannot be strongly confined inside the quantum well.
【００２８】これに対し、有機化合物のＥvは、−８.５
〜−１２ｅＶ程度、Ｅcは−０.２〜−２.５ｅＶ程度で
あり、半導体と比較してより大きなＥg（７〜９ｅＶ）
を有する。従って、無機半導体と有機化合物が交互に積
層された構造を有する本発明の有機無機複合材料によれ
ば、ヘテロ界面でのΔＥvおよびΔＥcを大きくすること
ができ、電子・正孔を量子井戸に強く閉じ込めることが
できる。On the other hand, E v of the organic compound is -8.5.
About −12 eV and E c is about −0.2 to −2.5 eV, which is larger E g (7 to 9 eV) than the semiconductor.
Having. Therefore, according to the organic-inorganic composite material of the present invention having a structure in which an inorganic semiconductor and an organic compound are alternately stacked, ΔE v and ΔE c at the heterointerface can be increased, and electrons and holes can be formed in the quantum well. Can be strongly confined.
【００２９】本発明の有機無機複合材料は、無機層と有
機層を交互に積層して超格子構造とすることにより構成
することもできる。この場合は、図１において半導体Ｂ
層２を有機絶縁材料とした構造となる。The organic-inorganic composite material of the present invention can also be constituted by alternately laminating inorganic layers and organic layers to form a superlattice structure. In this case, the semiconductor B in FIG.
The layer 2 has a structure using an organic insulating material.
【００３０】半導体超格子の場合、ΔＥvおよびΔＥcが
比較的小さいので、電子および正孔が量子井戸の外側に
滲みだし、量子井戸が近接している場合、量子井戸の間
に相互作用が生じる場合がある。しかし、本発明は大き
なΔＥvおよびΔＥcを有するので、量子井戸間の相互作
用が生じない。従って、超格子構造化した場合でも、本
発明の量子井戸は互いに独立してある。In the case of a semiconductor superlattice, since ΔE v and ΔE c are relatively small, electrons and holes seep out of the quantum well, and when the quantum well is in close proximity, interaction between the quantum wells occurs. May occur. However, the present invention has large ΔE v and ΔE c so that no interaction between quantum wells occurs. Therefore, even when a superlattice structure is formed, the quantum wells of the present invention are independent of each other.
【００３１】本発明は、図３に示す様に半導体材料およ
び有機材料を用いて構成できる。有機材料としてはバン
ドギャップが大きく絶縁性の高い化合物であれば特に限
定されない。The present invention can be constituted by using a semiconductor material and an organic material as shown in FIG. The organic material is not particularly limited as long as it is a compound having a large band gap and high insulating properties.
【００３２】例えば、有機材料として、図２に示す様な
有機低分子材料の他に、有機高分子材料、ＬＢ（ラング
ミュア ブロジェット）膜等を用いることも可能である
が、分子線蒸着装置を用いて本発明を実施する場合に
は、化合物の蒸気圧が分子線蒸着に適していることが望
ましい。但し、本発明において、有機層は半導体層を相
互に隔離する絶縁スペーサ層であるので、特開平６−３
７１２号公報、特開平２−２０１３２０号公報の場合の
ように、有機半導体材料、有機機能性材料を用いること
はできない。For example, as the organic material, an organic polymer material, an LB (Langmuir Blodget) film or the like can be used in addition to the organic low molecular material shown in FIG. When the present invention is carried out using the compound, it is desirable that the compound has a vapor pressure suitable for molecular beam deposition. However, in the present invention, the organic layer is an insulating spacer layer for isolating the semiconductor layers from each other.
Organic semiconductor materials and organic functional materials cannot be used as in the case of Japanese Patent Application Laid-Open No. 712 and Japanese Patent Application Laid-Open No. Hei 2-201320.
【００３３】これは、有機半導体材料、有機機能性材料
のバンドギャップが有機絶縁材料と比較して小さいた
め、ヘテロ界面でのΔＥvおよびΔＥcが小さくなり、半
導体層の電子および正孔を強く半導体層に閉じ込めるこ
とができないからである。This is because, since the band gap of the organic semiconductor material and the organic functional material is smaller than that of the organic insulating material, ΔE v and ΔE c at the hetero interface are reduced, and the electrons and holes of the semiconductor layer are strengthened. This is because they cannot be confined in the semiconductor layer.
【００３４】本発明の有機無機複合材料および有機無機
複合超格子は、ヘテロ界面におけるバンドギャップの変
化、即ち、ΔＥvおよびΔＥcを半導体超格子と比較して
大きくでき、電子・正孔の強い量子閉じ込めを実現する
ことができる。In the organic-inorganic composite material and the organic-inorganic composite superlattice of the present invention, the change in the band gap at the heterointerface, that is, ΔE v and ΔE c can be made larger than that of the semiconductor superlattice, and the electron / hole strength is high. Quantum confinement can be realized.
【００３５】[0035]
【実施例】本発明を実施例に基づき説明する。なお、実
施例１は本発明の有機無機複合材料の基本構成例、実施
例２は超格子化した本発明の構成例を示し、実施例３、
４は実施例１の材料構成例、実施例５、６は実施例２の
材料構成例を示したものである。EXAMPLES The present invention will be described based on examples. Example 1 shows a basic configuration example of the organic-inorganic composite material of the present invention, and Example 2 shows a configuration example of the present invention in which a superlattice was formed.
Reference numeral 4 denotes a material configuration example of Example 1, and Examples 5 and 6 show a material configuration example of Example 2.
【００３６】〔実施例１〕図３は、本発明の有機無機複
合材料およびそのバンドギャップの模式図である。本実
施例では、有機絶縁層９に無水マレイン酸〔化１〕、無
機半導体層１０にＧａＡｓを用いて、本発明の有機無機
複合材料を構成した。Example 1 FIG. 3 is a schematic view of the organic-inorganic composite material of the present invention and its band gap. In the present example, the organic-inorganic composite material of the present invention was constituted by using maleic anhydride [formula 1] for the organic insulating layer 9 and GaAs for the inorganic semiconductor layer 10.
【００３７】ＧａＡｓおよび無水マレイン酸のバンドギ
ャップおよびその位置は、図２から分かるように、本実
施例によりタイプＩ型超格子の量子井戸を形成できる。
本実施例では、図中の無水マレイン酸からなる有機絶縁
層９の膜厚ｄoおよびＧａＡｓからなる無機半導体層１
０の膜厚ｄsは約１０ｎｍであり、ＧａＡｓ層中に電子
および正孔が量子力学的に閉じ込められる構造とした。As can be seen from FIG. 2, the band gap of GaAs and maleic anhydride can form a type I superlattice quantum well according to this embodiment.
In this embodiment, the thickness d o of the organic insulating layer 9 made of maleic anhydride and the inorganic semiconductor layer 1 made of GaAs
The film thickness d s of 0 is about 10 nm, and the structure is such that electrons and holes are confined quantum mechanically in the GaAs layer.
【００３８】ＧａＡｓのＥc、Ｅvはそれぞれ約−４.０
７、−５.４３ｅＶであり、無水マレイン酸のＥc、Ｅv
は、それぞれ約−１.４４、−１０.８ｅＶであるので、
本実施例ではヘテロ界面でのΔＥcが約２.６３ｅＶ、Δ
Ｅvが約５.３７ｅＶとなる（図３）。E c and E v of GaAs are each about -4.0.
7 is -5.43eV, E c, E v maleic anhydride
Are about -1.44 and -10.8 eV, respectively.
In this embodiment, ΔE c at the hetero interface is about 2.63 eV, Δ
E v is about 5.37EV (Figure 3).
【００３９】一方、ＧａＡｓ／ＧａＡｌＡｓ超格子のΔ
Ｅc、ΔＥvは、前記のように、それぞれ約３０ｍｅＶ、
２５０ｍｅＶである。On the other hand, Δ of the GaAs / GaAlAs superlattice
E c and ΔE v are approximately 30 meV,
It is 250 meV.
【００４０】このように、本実施例の有機無機複合材料
は、ＧａＡｓ／ＧａＡｌＡｓ超格子よりも大きなΔＥc
およびΔＥvを有し、相当するＧａＡｓ／ＧａＡｌＡｓ
超格子よりも強く電子・正孔を量子井戸１３に閉じ込め
ることが可能である。As described above, the organic-inorganic composite material of this embodiment has a larger ΔE c than the GaAs / GaAlAs superlattice.
And ΔE v and the corresponding GaAs / GaAlAs
It is possible to confine electrons and holes in the quantum well 13 more strongly than in the superlattice.
【００４１】〔実施例２〕図４は、本発明の有機無機複
合材料およびそのバンドギャップの模式図である。本実
施例の有機無機複合超格子は、図１に示した半導体超格
子と基本的に同じ構造を有し、有機絶縁層１４と無機半
導体層１５が交互に積層されている点が実施例１の半導
体超格子と異なる。Example 2 FIG. 4 is a schematic view of the organic-inorganic composite material of the present invention and its band gap. The organic-inorganic hybrid superlattice of the present embodiment has basically the same structure as the semiconductor superlattice shown in FIG. 1, and is different from the first embodiment in that the organic insulating layers 14 and the inorganic semiconductor layers 15 are alternately laminated. Semiconductor superlattice.
【００４２】本実施例の有機無機複合超格子は、有機無
機複合材料を複数個接合した構造を有し、半導体超格子
の多重量子井戸構造に対応する。本実施例では実施例１
同様、有機絶縁層１４に無水マレイン酸、無機半導体層
１５にＧａＡｓを用いて本発明の有機無機複合超格子を
構成した。本実施例では、有機絶縁層１４の膜厚ｄoお
よび無機半導体層１０の膜厚ｄsは約１０ｎｍであり、
ＧａＡｓ層中に電子および正孔が量子力学的に閉じ込め
られる構造とした。The organic-inorganic composite superlattice of this embodiment has a structure in which a plurality of organic-inorganic composite materials are joined, and corresponds to the multiple quantum well structure of a semiconductor superlattice. In this embodiment, the first embodiment
Similarly, the organic-inorganic composite superlattice of the present invention was formed using maleic anhydride for the organic insulating layer 14 and GaAs for the inorganic semiconductor layer 15. In this embodiment, the thickness d o of the organic insulating layer 14 and the thickness d s of the inorganic semiconductor layer 10 are about 10 nm,
The structure is such that electrons and holes are confined quantum mechanically in the GaAs layer.
【００４３】前記のように、半導体超格子の多重量子井
戸構造では、隣接する量子井戸同士が干渉し、相互作用
によりサブバンドと呼ばれる電子状態が出現する場合が
ある。これは、前記半導体超格子のΔＥc、ΔＥvが小さ
いため、量子井戸内に閉じ込められた電子・正孔の波動
関数が井戸の外側に滲みだし、隣接する量子井戸に束縛
される電子・正孔が相互作用することに起因する。As described above, in a multiple quantum well structure of a semiconductor superlattice, adjacent quantum wells may interfere with each other, and an electronic state called a subband may appear due to interaction. This is because, since ΔE c and ΔE v of the semiconductor superlattice are small, the wave function of the electrons and holes confined in the quantum well oozes out of the well and the electrons and positive electrons bound to the adjacent quantum wells. Due to the interaction of the holes.
【００４４】一方、本発明の有機無機複合超格子はΔＥ
c、ΔＥvが大きく井戸からの電子・正孔の波動関数の滲
みだしは極めて少ない。従って本発明の有機無機複合超
格子では、有機絶縁層の膜厚が極端に薄くならない限
り、量子井戸はほぼ独立している。従って実施例１と同
様に、無水マレイン酸とＧａＡｓを用いて構成される本
実施例のΔＥc、ΔＥvは、実施例１の場合と同じであ
り、それぞれ、２.６３ｅＶ、約５.３７ｅＶである。On the other hand, the organic-inorganic hybrid superlattice of the present invention has a ΔE
c , ΔE v is large, and the bleeding of the wave function of electrons and holes from the well is extremely small. Therefore, in the organic-inorganic hybrid superlattice of the present invention, the quantum wells are almost independent unless the thickness of the organic insulating layer becomes extremely thin. Therefore, similarly to the first embodiment, ΔE c and ΔE v of the present embodiment constituted by using maleic anhydride and GaAs are the same as those of the first embodiment, and are 2.63 eV and about 5.37 eV, respectively. It is.
【００４５】このように、本実施例の有機無機複合超格
子は、ＧａＡｓ／ＧａＡｌＡｓ超格子よりも大きなΔＥ
c、ΔＥvを有し、量子井戸１８は相当するＧａＡｓ／Ｇ
ａＡｌＡｓ超格子よりも強く電子・正孔を量子井戸１８
に閉じ込めることが可能である。As described above, the organic-inorganic hybrid superlattice of this embodiment has a ΔE larger than that of the GaAs / GaAlAs superlattice.
c , ΔE v , and the quantum well 18 has a corresponding GaAs / G
Electrons and holes are made stronger in the quantum well 18 than in the aAlAs superlattice.
It is possible to confine it to.
【００４６】〔実施例３〕実施例１と同様に、図３の有
機絶縁層９にビフェニル〔化２〕、無機半導体層１０に
ＧａＡｓを用い、本発明の有機無機複合材料を構成し
た。Example 3 In the same manner as in Example 1, an organic-inorganic composite material of the present invention was constituted by using biphenyl [formula 2] for the organic insulating layer 9 and GaAs for the inorganic semiconductor layer 10 in FIG.
【００４７】図２を見て分かるように、本実施例により
タイプＩ型超格子の量子井戸を形成できる。ＧａＡｓの
Ｅc、Ｅvはそれぞれ約−４.０７ｅＶ、−５.４３ｅＶで
あり、ビフェニルのＥc、Ｅvは、それぞれ約−０.３ｅ
Ｖ、−７.９５ｅＶであるので、本実施例ではヘテロ界
面でのΔＥcが約３.７７ｅＶ、ΔＥvが約２.５２ｅＶと
なる（図３）。As can be seen from FIG. 2, a quantum well of a type I superlattice can be formed by this embodiment. E c and E v of GaAs are about −4.07 eV and −5.43 eV, respectively, and E c and E v of biphenyl are about −0.3 eV, respectively.
V and −7.95 eV, ΔE c and ΔE v at the hetero interface are about 3.77 eV and about 2.52 eV, respectively, in the present embodiment (FIG. 3).
【００４８】このように、本実施例の有機無機複合材料
は、ＧａＡｓ／ＧａＡｌＡｓ半導体超格子よりも大きな
ΔＥcおよびΔＥvを有し、相当するＧａＡｓ／ＧａＡｌ
Ａｓ半導体超格子よりも強く電子・正孔を量子井戸１３
に閉じ込めることが可能である。As described above, the organic-inorganic composite material of this embodiment has ΔE c and ΔE v larger than those of the GaAs / GaAlAs semiconductor superlattice, and the corresponding GaAs / GaAl
Electrons and holes are made stronger in the quantum well 13 than in the As semiconductor superlattice.
It is possible to confine it to.
【００４９】〔実施例４〕実施例１と同様に、有機絶縁
層９に無水マレイン酸〔化１〕、無機半導体層１０にＺ
ｎＳｅを用い、本発明の有機無機複合材料を構成した。Example 4 As in Example 1, maleic anhydride [formula 1] was formed on the organic insulating layer 9 and Z was formed on the inorganic semiconductor layer 10.
The organic-inorganic composite material of the present invention was formed using nSe.
【００５０】図２を見て分かるように、本実施例により
タイプＩ型超格子の量子井戸を形成できる。ＺｎＳｅの
Ｅc、Ｅvはそれぞれ約−４.１４ｅＶ、−６.６４ｅＶで
あり、無水マレイン酸のＥc、Ｅvは、それぞれ約−１.
４４ｅＶ、−１０.８ｅＶであるので、本実施例ではヘ
テロ界面でのΔＥcが約２.７ｅＶ、ΔＥvが約４.１６ｅ
Ｖとなる（図３）。As can be seen from FIG. 2, a quantum well of a type I superlattice can be formed by this embodiment. E c of ZnSe, E v about each -4.14EV, a -6.64eV, E c, E v of maleic anhydride were approximately -1.
Since it is 44 eV and -10.8 eV, in this embodiment, ΔE c at the hetero interface is about 2.7 eV and ΔE v is about 4.16 e.
V (FIG. 3).
【００５１】このように、本実施例の有機無機複合材料
は、大きなＧａＡｓ／ＧａＡｌＡｓ半導体超格子と比較
して、大きなΔＥcおよびΔＥvを有し、相当するＧａＡ
ｓ／ＧａＡｌＡｓ半導体超格子よりも強く電子・正孔を
量子井戸１３に閉じ込めることが可能である。As described above, the organic-inorganic composite material of this embodiment has larger ΔE c and ΔE v than the large GaAs / GaAlAs semiconductor superlattice, and
It is possible to confine electrons and holes in the quantum well 13 more strongly than in the s / GaAlAs semiconductor superlattice.
【００５２】〔実施例５〕実施例２と同様に、図４の有
機絶縁層１４に〔化３〕の１,２,４,５−ベンゾテトラ
カルボン酸二無水物（ピロメリト酸無水物）、無機半導
体層１５にＧａＡｓを用い、本発明の有機無機複合超格
子を構成した。Example 5 In the same manner as in Example 2, 1,2,4,5-benzotetracarboxylic dianhydride (pyromellitic anhydride) of [Chemical Formula 3] was added to the organic insulating layer 14 of FIG. The organic-inorganic hybrid superlattice of the present invention was formed by using GaAs for the inorganic semiconductor layer 15.
【００５３】１,２,４,５−ベンゾテトラカルボン酸二
無水物分子のＥc、Ｅvを算出するため、同分子の分子構
造を分子力場計算により求め、その電子状態を半経験的
分子軌道法により算出した。In order to calculate E c and E v of the 1,2,4,5-benzotetracarboxylic dianhydride molecule, the molecular structure of the molecule was determined by molecular force field calculation, and the electronic state was determined semi-empirically. It was calculated by the molecular orbital method.
【００５４】分子軌道計算の結果、得られる最高被占軌
道（ＨＯＭＯ）および最低空軌道（ＬＵＭＯ）は、それ
ぞれ近似的に分子のＥc、Ｅvを与えることが知られてい
る。本実施例では、Ｂiosym Ｔechnologies Ｉnc.製分
子設計ソフトウエアであるＩnsight／Ｄiscover ２.９
によりＣＶＦＦ分子力場を用いて分子力学計算を行い、
半経験的分子軌道計算プログラムＭＯＰＡＣ Ｖer ６.
０のＭＩＮＤＯ３法を用いて上記無水物分子のＥc、Ｅv
を算出した。It is known that the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) obtained as a result of the molecular orbital calculation approximately give the molecules E c and E v , respectively. In this embodiment, the molecular design software “Insight / Discover 2.9” manufactured by Biosym Technologies Inc. is used.
Performs molecular mechanics calculations using the CVFF molecular force field,
Semi-empirical molecular orbital calculation program MOPAC Ver 6.
E c of the anhydride molecules using MINDO3 method 0, E v
Was calculated.
【００５５】計算の結果、上記無水物分子〔化３〕のＥ
cは約−２.７４ｅＶ、Ｅvは約−１１.２２ｅＶであっ
た。As a result of the calculation, the E of the above anhydride molecule [formula 3]
c is about -2.74eV, E v was about -11.22eV.
【００５６】ＧａＡｓのＥc、Ｅvはそれぞれ約−４.０
７ｅＶ、−５.４３ｅＶであるので、本実施例の有機無
機複合超格子のヘテロ界面でのΔＥcは約１.３３ｅＶ、
ΔＥvは約５.９４ｅＶである（図４）。E c and E v of GaAs are respectively about -4.0.
7 eV and −5.43 eV, ΔE c at the hetero interface of the organic-inorganic hybrid superlattice of this example is about 1.33 eV,
ΔE v is about 5.94 eV (FIG. 4).
【００５７】このように、本実施例の有機無機複合超格
子は、ＧａＡｓ／ＧａＡｌＡｓ半導体超格子と比較して
大きなΔＥcおよびΔＥvを有し、相当するＧａＡｓ／Ｇ
ａＡｌＡｓ半導体超格子よりも強く電子・正孔を量子井
戸１８に閉じ込めることが可能である。As described above, the organic-inorganic hybrid superlattice of this embodiment has a large ΔE c and ΔE v as compared with the GaAs / GaAlAs semiconductor superlattice, and the corresponding GaAs / G
Electrons and holes can be more strongly confined in the quantum well 18 than in the aAlAs semiconductor superlattice.
【００５８】〔実施例６〕実施例２と同様に、図４の有
機絶縁層１４に〔化４〕のナフタリン−１,４,５,８−
テトラカルボン酸二無水物、無機半導体層１５にＺｎＳ
ｅを用い、本発明の有機無機複合超格子を構成した。[Embodiment 6] As in Embodiment 2, the organic insulating layer 14 of FIG. 4 was coated with naphthalene-1,4,5,8-
Tetracarboxylic dianhydride, ZnS for inorganic semiconductor layer 15
The organic-inorganic hybrid superlattice of the present invention was constructed using e.
【００５９】実施例５と同様に、分子力学法および分子
動力学法を用いて上記無水物分子のＥcおよびＥvを算出
した。その結果、同無水物分子のＥcは約−２.７７ｅ
Ｖ、Ｅvは−１０.２３ｅＶであった。[0059] Similarly to Example 5, were calculated E c and E v of the anhydride molecules using molecular mechanics and molecular dynamics method. As a result, E c of the anhydride molecule about -2.77e
V, E v was -10.23eV.
【００６０】ＺｎＳｅのＥc、Ｅvはそれぞれ約−４.１
４ｅＶ、−６.６４ｅＶであるので、本実施例の有機無
機複合超格子のΔＥcおよびΔＥv（図４）は、それぞれ
約１.３７ｅＶ、３.５９ｅＶである。E c and E v of ZnSe are each about -4.1.
Since they are 4 eV and −6.64 eV, ΔE c and ΔE v (FIG. 4) of the organic-inorganic hybrid superlattice of this example are about 1.37 eV and 3.59 eV, respectively.
【００６１】このように、本実施例の有機無機複合超格
子は、ＧａＡｓ／ＧａＡｌＡｓ半導体超格子と比較して
大きなΔＥcおよびΔＥvを有し、相当するＧａＡｓ／Ｇ
ａＡｌＡｓ半導体超格子よりも強く電子・正孔を量子井
戸１８に閉じ込めることが可能である。As described above, the organic-inorganic hybrid superlattice of this embodiment has a large ΔE c and ΔE v as compared with the GaAs / GaAlAs semiconductor superlattice, and the corresponding GaAs / G
Electrons and holes can be more strongly confined in the quantum well 18 than in the aAlAs semiconductor superlattice.
【００６２】[0062]
【発明の効果】本発明の有機無機複合材料および有機無
機複合超格子は、ヘテロ接合界面でのΔＥcおよびΔＥv
を半導体超格子の場合と比較して大きくすることがで
き、相当する構造の半導体超格子と比較して、電子およ
び正孔をより強く量子井戸に閉じ込めることができる。The organic-inorganic composite material and the organic-inorganic composite superlattice of the present invention have ΔE c and ΔE v at the heterojunction interface.
Can be made larger than in the case of a semiconductor superlattice, and electrons and holes can be more strongly confined in the quantum well than in a semiconductor superlattice of a corresponding structure.
【図１】半導体超格子の構造とバンド構造の模式図。FIG. 1 is a schematic view of a structure of a semiconductor superlattice and a band structure.
【図２】半導体材料および有機絶縁材料のバンドギャッ
プのエネルギーレベル図。FIG. 2 is an energy level diagram of a band gap of a semiconductor material and an organic insulating material.
【図３】本発明の有機無機複合材料の構造とバンド構造
の模式図。FIG. 3 is a schematic view of the structure and band structure of the organic-inorganic composite material of the present invention.
【図４】超格子構造を有する本発明の有機無機複合材料
の構造とバンド構造の模式図。FIG. 4 is a schematic view of the structure and band structure of the organic-inorganic composite material of the present invention having a superlattice structure.
１…半導体Ａ層、２…半導体Ｂ層、３…ヘテロ界面、
４，１１，１６…伝導帯下端、５，１２，１７…価電子
帯上端、６，１３，１８…量子井戸、７…電子のエネル
ギー順位、８…正孔のエネルギー順位、９，１４…有機
絶縁層、１０，１５…無機半導体層。1 ... Semiconductor A layer, 2 ... Semiconductor B layer, 3 ... Hetero interface,
4, 11, 16: conduction band bottom, 5, 12, 17 ... valence band top, 6, 13, 18 ... quantum well, 7 ... electron energy rank, 8 ... hole energy rank, 9, 14 ... organic Insulating layer, 10, 15 ... Inorganic semiconductor layer.
─────────────────────────────────────────────────────
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【手続補正書】[Procedure amendment]
【提出日】平成１１年４月１６日[Submission date] April 16, 1999
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項５[Correction target item name] Claim 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２４】さらにまた、有機絶縁層と無機半導体層の
ヘテロ界面接合の、伝導帯下端のエネルギー変化が１.
３３〜３.７７ｅＶ、価電子帯上端のエネルギー変化が
２.５２〜５.９４ｅＶである前記の有機無機複合材料に
ある。Further, the energy change at the lower end of the conduction band at the hetero interface junction between the organic insulating layer and the inorganic semiconductor layer is 1.
The organic-inorganic composite material has an energy change of 33 to 3.77 eV and an upper end of the valence band of 2.52 to 5.94 eV.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３２[Correction target item name] 0032
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３２】例えば、有機材料として、図２に示す様な
有機低分子材料の他に、有機高分子材料、ＬＢ（ラング
ミュア ブロジェット）膜等を用いることも可能である
が、分子線蒸着装置〔The 8th International Confe
rence on UnconventionalPhotoactive Systemes（Ｕ
ＰＳ−８），ＡＢＳＴＲＡＣＴＳ ＰＡＲＴＩＣＩＰＡ
ＮＴＳ ＬＩＳＴ．Ｉ−１０（１９９７年８月）：Ｏrg
nic／ＩnorgnicＨeterostructures of Ｐhthalocyani
ne and Ｃadmium Ｓelenide by Ｍolecular Ｂea
m Ｄeposition．〕を用いて本発明を実施する場合に
は、化合物の蒸気圧が分子線蒸着に適していることが望
ましい。但し、本発明において、有機層は半導体層を相
互に隔離する絶縁スペーサ層であるので、特開平６−３
７１２号公報、特開平２−２０１３２０号公報の場合の
ように、有機半導体材料、有機機能性材料を用いること
はできない。[0032] For example, as an organic material, in addition to the organic low-molecular material such as shown in FIG. 2, an organic polymer material, LB although it is also possible to use (Langmuir Blodgett) film or the like, molecular beam deposition apparatus [ The 8th International Confe
rence on Unconventional Photoactive Systemes (U
PS-8), ABSTRACTS PARTICIPA
NTS LIST. I-10 (August 1997): Org
nic / Inorgnic Heterostructures of Phthalocyani
ne and Cadmium Selenide by Molecular Bea
m Deposition. When the present invention is carried out using the above formula, it is desirable that the compound has a vapor pressure suitable for molecular beam deposition. However, in the present invention, the organic layer is an insulating spacer layer for isolating the semiconductor layers from each other.
Organic semiconductor materials and organic functional materials cannot be used as in the case of Japanese Patent Application Laid-Open No. 712 and Japanese Patent Application Laid-Open No. Hei 2-201320.
Claims (5)
れた超格子構造を有する有機無機複合材料において、前
記有機絶縁層を構成する材料が、 【化１】 で示される無水マレイン酸〔化１〕、ビフェニル〔化
２〕、１,２,４,５−ベンゾテトラカルボン酸二無水物
〔化３〕、ナフタリン−１,４,５,８−テトラカルボン
酸二無水物〔化４〕から選ばれることを特徴とする有機
無機複合材料。1. An organic-inorganic composite material having a superlattice structure in which an organic insulating layer and an inorganic semiconductor layer are laminated and joined, wherein the material constituting the organic insulating layer is: Maleic anhydride [chemical formula 1], biphenyl [chemical formula 2], 1,2,4,5-benzotetracarboxylic dianhydride [chemical formula 3], naphthalene-1,4,5,8-tetracarboxylic acid An organic-inorganic composite material selected from dianhydrides [Chemical Formula 4].
ａＡｓまたはＺｎＳｅである請求項１に記載の有機無機
複合材料。2. The material for forming the inorganic semiconductor layer is G
The organic-inorganic composite material according to claim 1, which is aAs or ZnSe.
上交互に積層され、かつ、有機絶縁層により電子および
正孔が無機半導体層内部に２次元的に閉じこめられるよ
う構成されている請求項１または２に記載の有機無機複
合材料。3. The organic insulating layer and the inorganic semiconductor layer are alternately stacked in three or more layers, and electrons and holes are two-dimensionally confined inside the inorganic semiconductor layer by the organic insulating layer. Item 3. The organic-inorganic composite material according to item 1 or 2.
界面がファンデルワールス作用により接合されている請
求項１，２または３に記載の有機無機複合材料。4. The organic-inorganic composite material according to claim 1, wherein the heterointerface between the organic insulating layer and the inorganic semiconductor layer is joined by van der Waals action.
接合の、伝導帯下端のエネルギー変化が１.３３〜４.０
７ｅＶ、価電子帯上端のエネルギー変化が２.５２〜５.
９４ｅＶである請求項４に記載の有機無機複合材料。5. The energy change at the lower end of the conduction band at the hetero interface junction between the organic insulating layer and the inorganic semiconductor layer is 1.33 to 4.0.
7 eV, the energy change at the upper end of the valence band is 2.52 to 5.
The organic-inorganic composite material according to claim 4, which is 94 eV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8388498A JP2957986B1 (en) | 1998-03-30 | 1998-03-30 | Organic-inorganic composite materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8388498A JP2957986B1 (en) | 1998-03-30 | 1998-03-30 | Organic-inorganic composite materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2957986B1 JP2957986B1 (en) | 1999-10-06 |
| JPH11282033A true JPH11282033A (en) | 1999-10-15 |
Family
ID=13815097
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8388498A Expired - Fee Related JP2957986B1 (en) | 1998-03-30 | 1998-03-30 | Organic-inorganic composite materials |
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| Country | Link |
|---|---|
| JP (1) | JP2957986B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013078219A (en) * | 2011-09-30 | 2013-04-25 | Mitsumi Electric Co Ltd | Actuator and optical scanner device |
| JP2017527118A (en) * | 2014-08-28 | 2017-09-14 | コニカ ミノルタ ラボラトリー ユー．エス．エー．，インコーポレイテッド | Two-dimensional layered material quantum well junction device, multiple quantum well device, and method of manufacturing quantum well device |
-
1998
- 1998-03-30 JP JP8388498A patent/JP2957986B1/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013078219A (en) * | 2011-09-30 | 2013-04-25 | Mitsumi Electric Co Ltd | Actuator and optical scanner device |
| JP2017527118A (en) * | 2014-08-28 | 2017-09-14 | コニカ ミノルタ ラボラトリー ユー．エス．エー．，インコーポレイテッド | Two-dimensional layered material quantum well junction device, multiple quantum well device, and method of manufacturing quantum well device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2957986B1 (en) | 1999-10-06 |
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