JPH0876140A - Spacial optical modulating element and its production - Google Patents
Spacial optical modulating element and its productionInfo
- Publication number
- JPH0876140A JPH0876140A JP3688695A JP3688695A JPH0876140A JP H0876140 A JPH0876140 A JP H0876140A JP 3688695 A JP3688695 A JP 3688695A JP 3688695 A JP3688695 A JP 3688695A JP H0876140 A JPH0876140 A JP H0876140A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- light
- light modulator
- dielectric mirror
- spatial light
- 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.)
- Granted
Links
Landscapes
- Liquid Crystal (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フラットパネルディス
プレイ、光演算素子、ビデオプロジェクタ等に組み込ま
れる空間光変調素子（ＳＬＭ）とその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spatial light modulator (SLM) incorporated in a flat panel display, an optical operation element, a video projector, etc., and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】ディスプレイやプロジェクタ等に組み込
まれる空間光変調素子は、アモルファスシリコン等から
なる光導電体層に書き込み光を入射せしめ、光導電体層
の導電性を書き込み光の強度に応じて変化せしめ、この
変化によって生じた導電性の分布が電源からの電圧によ
って光変調体（液晶）に印加される。一方、光変調体に
読み出し光を入射すると、光変調体には書き込み光の強
度分布に応じた電界が影響しているので入射光は光変調
され、誘電体ミラー層にて反射されて出力される構造に
なっている。2. Description of the Related Art A spatial light modulator incorporated in a display, a projector, or the like makes writing light incident on a photoconductive layer made of amorphous silicon or the like, and changes the conductivity of the photoconductive layer according to the intensity of the writing light. At the very least, the conductivity distribution generated by this change is applied to the light modulator (liquid crystal) by the voltage from the power source. On the other hand, when the reading light is incident on the light modulator, the incident light is optically modulated, reflected by the dielectric mirror layer, and output because the electric field according to the intensity distribution of the writing light influences the light modulator. It has a structure that
【０００３】ところで、読み出し光は書き込み光に比べ
て大幅に強度が強く、誘電体ミラー層だけでは読み出し
光が光導電体層まで到達するのを完全に防ぐことができ
ず、読み出し光が光導電体層まで到達して電荷の乱れを
生じる不利がある。そこで、公表特許平２−５０１３３
４号公報に開示されるように、誘電体ミラー層の内側
（光導電体層側）にＣdＴe遮光層を設けることが知られ
ている。その他、遮光層材料としてＳiＯ2中に多量のニ
ッケル（Ｎi ）や亜鉛（Ｚn ）を含ませたサーメットが
用いられてきた。By the way, the read light is much stronger than the write light, and the dielectric mirror layer alone cannot completely prevent the read light from reaching the photoconductor layer, and the read light is photoconductive. It has the disadvantage of reaching the body layer and causing charge disturbance. Therefore, published Japanese Patent Application No. 2-50133
It is known to provide a CdTe light-shielding layer inside the dielectric mirror layer (on the side of the photoconductor layer) as disclosed in Japanese Patent Laid-Open No. 4 (1994). In addition, a cermet in which a large amount of nickel (Ni) or zinc (Zn) is contained in SiO 2 has been used as a light shielding layer material.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ＣdＴe
遮光層を設けることで読み出し光の光導電体層への到達
を防止できるが、ＣdＴe遮光層の抵抗率は１０6〜１０8
Ω・ｃｍであり、十分な抵抗率と言えず、製造条件によ
っては１０2 Ω・ｃｍとなる場合もある。このため、Ｃ
dＴe遮光層と接合層との界面に電荷が発生してその電荷
が広がり、即ち光導電体層の導電率変化を損失なく液晶
に伝えることができず、その結果液晶（光変調体）の配
向領域が広がり、画像の解像度が低下する。また、前記
サーメットは抵抗率が低く、遮光特性（読み出し光の光
導電体層への到達を防止する能力）も不十分であった。[Problems to be Solved by the Invention] However, CdTe
By providing the light shielding layer, it is possible to prevent the readout light from reaching the photoconductor layer, but the resistivity of the CdTe light shielding layer is 10 6 to 10 8
Ω · cm, which cannot be said to be sufficient resistivity, and may be 10 2 Ω · cm depending on manufacturing conditions. Therefore, C
A charge is generated at the interface between the dTe light-shielding layer and the bonding layer, and the charge spreads, that is, the change in the conductivity of the photoconductor layer cannot be transmitted to the liquid crystal without loss, and as a result, the alignment of the liquid crystal (light modulator). The area is expanded and the resolution of the image is reduced. Further, the cermet has a low resistivity, and the light-shielding property (the ability to prevent the readout light from reaching the photoconductor layer) was insufficient.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決すべく本
発明の空間光変調素子は、光書き込み手段によって光導
電体層に情報を書き込み、この書き込んだ情報に応じて
光変調体を変調させ、この光変調体に入射した読み出し
光を誘電体ミラー層によって反射せしめるようにした空
間光変調素子において、前記光導電体層と誘電体ミラー
層との間にＣdＴe（テルル化カドミウム）にＩ族元素
（Ｈ，Ｌi，Ｎa，Ｋ，Ｃu，Ｒb，Ａg，Ｃs，Ａu，Ｆr）
を不純物として添加した遮光層を設けた。ここで、Ｉ族
元素の添加量は１〜１，０００ｐｐｍ、好ましくは３０
０〜４００ｐｐｍとする。In order to solve the above problems, a spatial light modulator of the present invention writes information in a photoconductor layer by an optical writing means and modulates the light modulator according to the written information. In a spatial light modulator in which the reading light incident on the light modulator is reflected by a dielectric mirror layer, CdTe (cadmium telluride) group I is added between the photoconductor layer and the dielectric mirror layer. Element (H, Li, Na, K, Cu, Rb, Ag, Cs, Au, Fr)
A light-shielding layer to which was added as an impurity was provided. Here, the addition amount of the group I element is 1 to 1,000 ppm, preferably 30
It is set to 0 to 400 ppm.
【０００６】また、前記光導電体層をアモルファスシリ
コン層とし、この光導電体層と遮光層との間に、順にＳ
iＯ2層、ＣdＴeにＩ族元素が添加されたＯ2 リッチな層
及びＣdＴeにＩ族元素が添加された層を積層してなる接
合層を設け、或いは前記誘電体ミラー層をＴiＯ2とＳi
Ｏ2とを交互に積層して構成し、この誘電体ミラー層と
前記遮光層との間に、ＳiＯ2層、ＣdＴeにＩ族元素が添
加されたＯ2 リッチな層及びＣdＴeにＩ族元素が添加さ
れた層を積層してなる接合層を設けることで、光導電体
層と遮光層との接合強度及び遮光層と誘電体ミラー層と
の接合強度を高めるようにしてもよい。Further, the photoconductor layer is an amorphous silicon layer, and S is sequentially provided between the photoconductor layer and the light shielding layer.
A bonding layer formed by laminating an iO 2 layer, an O 2 -rich layer in which a group I element is added to CdTe, and a layer in which a group I element is added to CdTe is provided, or the dielectric mirror layer is formed of TiO 2 and Si.
O 2 is alternately laminated, and a SiO 2 layer, an O 2 -rich layer in which a group I element is added to CdTe, and a group I element in CdTe are provided between the dielectric mirror layer and the light shielding layer. It is also possible to increase the bonding strength between the photoconductor layer and the light-shielding layer and the bonding strength between the light-shielding layer and the dielectric mirror layer by providing a bonding layer formed by stacking layers to which is added.
【０００７】また、本発明の空間光変調素子は、光書き
込み手段によって光導電体層に情報を書き込み、この書
き込んだ情報に応じて光変調体を変調させ、この光変調
体に入射した読み出し光を誘電体ミラー層によって反射
せしめるようにした空間光変調素子において、前記光導
電体層と誘電体ミラー層との間にＣdＴe（テルル化カド
ミウム）にＶ族元素（Ｎ，Ｐ，Ａs，Ｓb，Ｂi ）を不純
物として添加した遮光層を設けた。Further, in the spatial light modulator of the present invention, information is written in the photoconductor layer by the optical writing means, the light modulator is modulated according to the written information, and the read light incident on the light modulator is read. In the spatial light modulator in which the dielectric mirror layer is used to reflect the light, a group V element (N, P, As, Sb, CdTe (cadmium telluride)) is provided between the photoconductive layer and the dielectric mirror layer. A light-shielding layer doped with Bi) was provided.
【０００８】一方、本発明に係る空間光変調素子の製造
方法は、透明電極及び光導電体層がこの順に形成された
基板上に高周波スパッタ法によって順次、接合層、遮光
層、接合層を形成して、この接合層上に誘電体ミラー層
を形成し、この誘電体ミラー層と他の基板表面に形成し
た透明電極との間に光変調体を注入するようにした空間
光変調素子の製造方法において、前記高周波スパッタ法
は基板温度を１２０℃〜２００℃に維持して行い、且つ
遮光層生成のためのスパッタ時間は２時間以上とした。
また、前記基板に誘電体ミラー層を形成した後、基板温
度を１２０℃〜２００℃に維持した状態で、３０分〜２
時間アニール処理を行うことが安定した品質の空間光変
調素子を得る上で好ましい。On the other hand, in the method for manufacturing a spatial light modulator according to the present invention, a bonding layer, a light shielding layer, and a bonding layer are sequentially formed by a high frequency sputtering method on a substrate on which a transparent electrode and a photoconductor layer are formed. Then, a dielectric mirror layer is formed on the bonding layer, and a light modulator is injected between the dielectric mirror layer and a transparent electrode formed on the surface of another substrate to manufacture a spatial light modulator. In the method, the high frequency sputtering method was performed while maintaining the substrate temperature at 120 to 200 ° C., and the sputtering time for forming the light shielding layer was set to 2 hours or more.
Further, after forming the dielectric mirror layer on the substrate, the substrate temperature is maintained at 120 ° C to 200 ° C for 30 minutes to 2 minutes.
It is preferable to perform the time annealing treatment in order to obtain a spatial light modulator having stable quality.
【０００９】また、本発明の空間光変調素子の製造方法
は、透明電極及び光導電体層がこの順に形成された基板
上に高周波スパッタ法によって遮光層を形成して、この
遮光層上に誘電体ミラー層を形成し、この誘電体ミラー
層と他の基板表面に形成した透明電極との間に光変調体
を注入するようにした空間光変調素子の製造方法におい
て、前記遮光層は、基板温度を０〜１００℃とし、放電
ガス圧を１０〜１００mTorr として形成した。Further, in the method for manufacturing a spatial light modulator of the present invention, a light shielding layer is formed by a high frequency sputtering method on a substrate on which a transparent electrode and a photoconductor layer are formed in this order, and a dielectric layer is formed on the light shielding layer. In the method for manufacturing a spatial light modulator in which a body mirror layer is formed and a light modulator is injected between the dielectric mirror layer and a transparent electrode formed on the surface of another substrate, the light shielding layer is a substrate. The temperature was set to 0 to 100 ° C., and the discharge gas pressure was set to 10 to 100 mTorr.
【００１０】[0010]
【作用】スパッタリングによって形成されるＣdＴe膜
（遮光層）の元素の比は、各元素の蒸気圧の違い及び下
地膜（接合層）に対する付着確率の違いにより、化学量
論的組成（１：１）にはならず格子欠陥を有する。この
ため、ドナーやアクセプタの比率が変動し、どちらか多
い方の伝導型になり、自由なキャリヤ濃度も変動するの
で抵抗率にバラツキが生じる。そこで、ＣdＴe（II−VI
族）半導体に対してアクセプタとなるＩ族元素またはＶ
族元素を注入してキャリヤをバンドギャップ内の深い位
置に捕獲し、キャリヤを伝導帯に励起させないようにす
ることで、抵抗率を高いレベルで安定させることが可能
になった。The ratio of elements in the CdTe film (light-shielding layer) formed by sputtering is stoichiometric (1: 1) due to the difference in vapor pressure of each element and the difference in sticking probability to the underlying film (bonding layer). ) And has a lattice defect. As a result, the ratio of donors and acceptors changes, whichever is the larger conductivity type, and the free carrier concentration also changes, resulting in variations in resistivity. Therefore, CdTe (II-VI
Group I element or V that serves as an acceptor for semiconductors
By implanting a group element and trapping the carriers at a deep position in the band gap so as not to excite the carriers into the conduction band, it becomes possible to stabilize the resistivity at a high level.
【００１１】[0011]
【実施例】以下に本発明の実施例を添付図面に基づいて
説明する。ここで、図１は本発明に係る空間光変調素子
を組み込んだプロジェクタの全体構成図であり、ＬＥＤ
を直線状に配列した発光素子アレイ１から放射された書
き込み光Ｆ１はレンズ２で平行光とされ、反射角調整可
能な偏向ミラー３及びレンズ４を介して本発明に係る空
間光変調素子１０の光導電層に結像し、空間光変調素子
１０内の光変調体である液晶を書き込み情報に応じて配
向させる。Embodiments of the present invention will be described below with reference to the accompanying drawings. Here, FIG. 1 is an overall configuration diagram of a projector in which the spatial light modulator according to the present invention is incorporated.
The writing light F1 emitted from the light emitting element array 1 in which is linearly arranged is collimated by the lens 2 and is transmitted through the deflecting mirror 3 and the lens 4 whose reflection angle can be adjusted to the spatial light modulating element 10 of the present invention. An image is formed on the photoconductive layer, and the liquid crystal that is the light modulator in the spatial light modulator 10 is oriented according to the write information.
【００１２】また、読み出し光Ｆ２は球面反射鏡５、偏
光ビームスプリッタ６を介して空間光変調素子１０に入
射して変調され、空間光変調素子１０の誘電体ミラー層
で反射し、反射光Ｆ３がレンズ８を介してスクリーン９
に投影される。The reading light F2 is incident on the spatial light modulator 10 through the spherical reflecting mirror 5 and the polarization beam splitter 6 and is modulated, reflected by the dielectric mirror layer of the spatial light modulator 10, and reflected light F3. Through the lens 8 to the screen 9
Projected on.
【００１３】空間光変調素子１０は全体斜視図である図
２に示すように、ガラス基板１１の一面にＩＴＯ（イン
ジウム・スズ・オキサイド）からなる透明電極１２を形
成し、この透明電極１２上にアモルファスシリコンから
なる光導電体層１３を形成し、この光導電体層１３の上
に接合層１４を介してＣdＴe（テルル化カドミウム）に
Ｉ族元素（Ｈ，Ｌi，Ｎa，Ｋ，Ｃu，Ｒb，Ａg，Ｃs，Ａ
u，Ｆr）を不純物として添加した遮光層１５を形成し、
この遮光層１５の上に接合層１６を介して誘電体ミラー
層１７を形成している。As shown in FIG. 2 which is an overall perspective view of the spatial light modulation element 10, a transparent electrode 12 made of ITO (indium tin oxide) is formed on one surface of a glass substrate 11, and the transparent electrode 12 is formed on the transparent electrode 12. A photoconductor layer 13 made of amorphous silicon is formed, and a group I element (H, Li, Na, K, Cu, Rb) is added to CdTe (cadmium telluride) via a bonding layer 14 on the photoconductor layer 13. , Ag, Cs, A
u, Fr) is added as an impurity to form a light-shielding layer 15,
A dielectric mirror layer 17 is formed on the light shielding layer 15 with a bonding layer 16 interposed therebetween.
【００１４】そして、誘電体ミラー層１７と他のガラス
基板２１の一面に形成した透明電極２２との間に液晶
（光変調体）２３を介設し、更に透明電極１２，２２間
に電源２４を接続することで空間光変調素子１０が完成
する。A liquid crystal (light modulator) 23 is provided between the dielectric mirror layer 17 and the transparent electrode 22 formed on one surface of another glass substrate 21, and a power source 24 is provided between the transparent electrodes 12 and 22. The spatial light modulator 10 is completed by connecting the above.
【００１５】前記接合層１４は要部の拡大断面図である
図３に示すように、光導電体層１３から遮光層１５に向
かって順にＳiＯ2層１４ａ、ＣdＴeにＣu が添加された
Ｏ2リッチなＣdＴe+Ｃu層１４ｂ及びＣdＴeにＣu が添
加されたＣdＴe+Ｃu層１４ｃを積層して構成される。こ
こで、ＣdＴe+Ｃu層１４ｂ及びＣdＴe+Ｃu層１４ｃにお
けるＣu の添加量は遮光層１５と同様に１〜１，０００
ｐｐｍ、好ましくは３００〜４００ｐｐｍとする。As shown in FIG. 3, which is an enlarged cross-sectional view of the main portion of the bonding layer 14, an SiO 2 layer 14a and an O 2 layer in which Cu is added to CdTe are sequentially provided from the photoconductor layer 13 toward the light shielding layer 15. It is configured by laminating a rich CdTe + Cu layer 14b and a CdTe + Cu layer 14c in which Cu is added to CdTe. Here, the addition amount of Cu in the CdTe + Cu layer 14b and the CdTe + Cu layer 14c is 1 to 1,000 as in the light shielding layer 15.
ppm, preferably 300 to 400 ppm.
【００１６】また、接合層１６は前記接合層１４とは順
序を逆にし、遮光層１５から誘電体ミラー層１７に向か
って順にＣdＴeにＣu が添加されたＣdＴe+Ｃu層１６
ａ、ＣdＴeにＣu が添加されたＯ2 リッチなＣdＴe+Ｃu
層１６ｂ及びＳiＯ2層１６ｃを積層して構成される。
尚、誘電体ミラー層１７と液晶２３との間には配向層２
５ａを形成している。Further, the order of the bonding layer 16 is reversed from that of the bonding layer 14, and the CdTe + Cu layer 16 in which Cu is added to CdTe in order from the light shielding layer 15 to the dielectric mirror layer 17 is formed.
a, O 2 -rich CdTe + Cu in which Cu is added to CdTe
The layer 16b and the SiO 2 layer 16c are laminated.
The alignment layer 2 is provided between the dielectric mirror layer 17 and the liquid crystal 23.
5a is formed.
【００１７】次に、サンプル１〜５について具体的な製
造方法を述べる。 （サンプル１）一面側にアモルファスシリコン層をすで
に形成したガラス基板（コーニング社７０５９）を高周
波マグネトロンスパッタ装置内に設置する。この高周波
マグネトロンスパッタ装置内の適当な箇所には、６Ｎ
（６ナイン）以上の純度のＣdＴeターゲットと３Ｎ以上
の純度のＣu ターゲットがセットされ、更に１３．５６
ＭＨz の高周波が印加される。先ず、基板温度を１５０
℃に保持したまま真空度を２×１０-6Torr以下とし、バ
リアブルコンダクタンスバルブを全開状態でＡr ガスを
３mTorr （ミリトール）導入し、ＳiＯ2を３００Ｗ（ワッ
ト）で７分間成長せしめる。次いで、Ａr ガスを維持し
たまま、６Ｎ以上の純度のＯ2 ガスを３mTorr 加え、バ
リアブルコンダクタンスバルブを絞って全ガス圧力が、
例えば９mTorr となるようにしてＯ2 リッチなＣdＴe+
Ｃu層を５分間成長せしめる。更に、バリアブルコンダ
クタンスバルブを開けながら、全ガス圧力を９mTorrに
維持してＯ2 の導入量を少しずつ減らして止め、ＣdＴe
+Ｃu層を５分間成長せしめる。この後、バリアブルコン
ダクタンスバルブを全開しＡr ガスを３mTorr として、
２時間以上かけてＣdＴe+Ｃu遮光層を１．５μｍ成長せ
しめた。このようにして得られたものをサンプル１とす
る。Next, a concrete manufacturing method for Samples 1 to 5 will be described. (Sample 1) A glass substrate (Corning 7059) having an amorphous silicon layer already formed on one surface side is placed in a high frequency magnetron sputtering apparatus. At a suitable place in this high frequency magnetron sputtering device, 6N
A CdTe target having a purity of (6 nines) or higher and a Cu target having a purity of 3N or higher are set, and 13.56
A high frequency of MHz is applied. First, the substrate temperature is set to 150
While maintaining the temperature at 0 ° C., the degree of vacuum is set to 2 × 10 −6 Torr or less, Ar gas is introduced at 3 mTorr (millitorr) with the variable conductance valve fully opened, and SiO 2 is grown at 300 W (watt) for 7 minutes. Next, while maintaining the Ar gas, O 2 gas having a purity of 6N or more was added at 3 mTorr, and the variable conductance valve was throttled to adjust the total gas pressure to
For example, CdTe + rich in O 2 at 9 mTorr
Allow the Cu layer to grow for 5 minutes. Furthermore, while opening the variable conductance valve, the total gas pressure was maintained at 9 mTorr and the amount of O 2 introduced was gradually reduced to CdTe.
Allow + Cu layer to grow for 5 minutes. After that, the variable conductance valve was fully opened and Ar gas was set to 3 mTorr.
The CdTe + Cu light-shielding layer was grown to a thickness of 1.5 μm over 2 hours. The sample thus obtained is referred to as Sample 1.
【００１８】（サンプル２）上記のサンプル１を作るま
での工程は同じであるが、更に引続いて、バリアブルコ
ンダクタンスバルブを絞り、Ａr ガス圧力を９mTorr と
してＣdＴe+Ｃu層を成長せしめる。次いで、Ｏ2 の導入
量を少しづつ増加するとともに全ガス圧力を９mTorr に
維持するためバリアブルコンダクタンスバルブを同時に
少しづつ開く。そして、Ｏ2 の流量がサンプル１で形成
したＯ2 リッチなＣdＴe+Ｃu層を形成した時と同じにな
ったらこの操作を止め、ＣdＴe+Ｃu層を５分間成長せし
める。このようにして得られたものをサンプル２とす
る。(Sample 2) The steps up to the preparation of Sample 1 are the same, but the variable conductance valve is further narrowed down and the CdTe + Cu layer is grown with the Ar gas pressure set to 9 mTorr. Then, the variable conductance valve is simultaneously opened little by little in order to gradually increase the amount of O 2 introduced and maintain the total gas pressure at 9 mTorr. Then, the flow rate of O 2 is stop this operation If the same in a case of forming the O 2 rich CdTe + Cu layer formed in Sample 1, allowed to grow CdTe + Cu layer 5 minutes. The sample thus obtained is referred to as Sample 2.
【００１９】（サンプル３）サンプル２を作製した後、
真空を破らずに、基板温度を１５０℃に維持したまま全
てのスパッタリングを止め、そのままチャンバー内に
１．５時間放置（アニール）してから取り出す。このよ
うにして得られたものをサンプル３とする。(Sample 3) After producing Sample 2,
Without breaking the vacuum, all the sputtering was stopped while maintaining the substrate temperature at 150 ° C., and the substrate was left as it was in the chamber for 1.5 hours (annealing) before taking it out. The sample thus obtained is referred to as Sample 3.
【００２０】（サンプル４）接合層としてのＳiＯ2層、
Ｏ2 リッチなＣdＴe+Ｃu層及びＣdＴe+Ｃu層を形成しな
いで、アモルファスシリコン層上に直接遮光層（ＣdＴe
+Ｃu）を形成し、これをサンプル４とする。(Sample 4) SiO 2 layer as a bonding layer,
Without forming the O 2 -rich CdTe + Cu layer and the CdTe + Cu layer, the light-shielding layer (CdTe) is directly formed on the amorphous silicon layer.
+ Cu) is formed, and this is referred to as Sample 4.
【００２１】（サンプル５）公表特許平２−５０１３３
４号公報に開示されたもの、つまり接合層（Ｃu の添加
なし）はあるが、遮光層をＣdＴe（Ｃu の添加なし）と
したものをサンプル５とする。(Sample 5) Published Japanese Patent Application No. 2-50133
Sample 5 is the one disclosed in Japanese Patent Laid-Open No. 4, that is, the bonding layer (without addition of Cu) is present, but the light-shielding layer is CdTe (without addition of Cu).
【００２２】以上のサンプル１〜５の明暗抵抗率を以下
の（表１）に示す。尚、各サンプルの抵抗率を計るため
に必要な電極についてはＡl 電極を形成した。またサン
プル１〜３についての光学濃度（Optical Density:Ｏ．
Ｄ．）の値は７００ｎｍの波長で２であり、従来と変り
はなかった。なお、光学濃度とは透過率の逆数の自然対
数値である。The bright and dark resistivities of the above samples 1 to 5 are shown in the following (Table 1). An Al electrode was formed as an electrode necessary for measuring the resistivity of each sample. Further, the optical densities (O.D.
D. The value of () is 2 at a wavelength of 700 nm, which is no different from the conventional value. The optical density is the natural logarithm of the reciprocal of the transmittance.
【００２３】[0023]
【表１】 [Table 1]
【００２４】上記の（表１）から以下のことが言える。 サンプル２からＣu が添加されてもアニール処理がな
されないものは、抵抗率が低い。サンプル１にあっては
遮光層を形成する際に、基板温度を１５０℃としつつ２
時間以上としたことによってアニール処理したと同様の
効果が得られ、抵抗率が向上したものと考えられる。 サンプル４と５の比較から、Ｃu を添加することによ
って抵抗率は向上する。 Ｃu が添加され且つ接合層を設け更にアニールが施さ
れたサンプル１，３は従来の素子に比べて、大幅に抵抗
率が向上し、更に明・暗抵抗率の差がなくなる。From the above (Table 1), the following can be said. Sample 2 which is not annealed even if Cu is added has a low resistivity. In Sample 1, when forming the light shielding layer, the substrate temperature was set to 150 ° C.
It is considered that the same effect as the annealing treatment was obtained by setting the time longer than the time, and the resistivity was improved. From the comparison of Samples 4 and 5, the resistivity is improved by adding Cu. Samples 1 and 3 to which Cu was added and which was provided with a bonding layer and further annealed had a significantly improved resistivity as compared with the conventional device, and there was no difference between the bright and dark resistivity.
【００２５】Ｃu 以外の他のＩ族金属であるＡg，Ａuに
ついてもサンプルを作製したが、同様の結果が得られ
た。Samples were also prepared for Ag and Au which are other Group I metals other than Cu, but similar results were obtained.
【００２６】Ｈ2 については、Ａr 中に１０〜５０％と
なるようにＨ2 を混入し、Ｃu 等の金属ターゲットをセ
ットせず、全ガス圧が６．０×１０-3Torrとなるように
導入し、上記と同一の条件でスパッタリングを行い、１
０8 Ω・ｃｍ台の抵抗値が得られた。Regarding H 2 , H 2 is mixed in Ar so as to be 10 to 50%, a metal target such as Cu is not set, and the total gas pressure is 6.0 × 10 -3 Torr. And sputter under the same conditions as above.
0 8 Ω · cm base resistance value is obtained.
【００２７】次に、本発明の別実施例を図４に基づいて
説明する。図４は本発明に係る別の空間光変調素子の斜
視図であり、空間光変調素子３０は、透明基板３１の一
面にＩＴＯからなる透明電極３２を形成し、この透明電
極３２上にアモルファス水素化シリコンからなる光導電
体層３３を形成し、この光導電体層３３の上にＣdＴe
（テルル化カドミウム）にＶ族元素（Ｎ，Ｐ，Ａs，Ｓ
b，Ｂi ）を不純物として添加した遮光層３４を形成
し、この遮光層３４の上に誘電体ミラー層３５を形成し
ている。Next, another embodiment of the present invention will be described with reference to FIG. FIG. 4 is a perspective view of another spatial light modulator according to the present invention. In the spatial light modulator 30, a transparent electrode 32 made of ITO is formed on one surface of a transparent substrate 31, and amorphous hydrogen is formed on the transparent electrode 32. A photoconductor layer 33 made of silicon oxide is formed, and CdTe is formed on the photoconductor layer 33.
(Cadmium telluride) with group V elements (N, P, As, S)
b, Bi) is added as an impurity to form a light shielding layer 34, and a dielectric mirror layer 35 is formed on the light shielding layer 34.
【００２８】そして、誘電体ミラー層３５と他の透明基
板３６の一面に形成した透明電極３７との間に液晶（光
変調体）３８を介設し、更に透明電極３２，３７間に電
源４１を接続することで空間光変調素子３０が完成す
る。A liquid crystal (light modulator) 38 is provided between the dielectric mirror layer 35 and a transparent electrode 37 formed on one surface of another transparent substrate 36, and a power source 41 is provided between the transparent electrodes 32 and 37. The spatial light modulator 30 is completed by connecting the above.
【００２９】以下に具体的な製造方法を述べる。一方の
透明基板３１上にＩＴＯからなる透明電極３２をスパッ
タリング法により形成する。この透明電極３２上に、ａ
-Ｓi：Ｈ（アモルファス水素化シリコン）からなる膜厚
が２０μｍの光導電体層３３をＣＶＤ法により積層す
る。A specific manufacturing method will be described below. A transparent electrode 32 made of ITO is formed on one transparent substrate 31 by a sputtering method. On this transparent electrode 32, a
A photoconductor layer 33 made of Si: H (amorphous silicon hydride) and having a thickness of 20 μm is laminated by the CVD method.
【００３０】そして、光導電体層３３上に、遮光層３４
を積層する。この遮光層３４は窒素（Ｎ）を添加された
ＣdＴeを、高周波マグネトロンスパッタリング法（高周
波スパッタ法の一種である。）により２．３μｍ積層し
たものである。スパッタリングガスにはアルゴン（Ａr
）を用い、このアルゴンに対して窒素ガス（Ｎ2 ）濃
度を２．２％として、成膜圧力（放電ガス圧）１０mTor
r 、高周波電力０．６Ｗ／cm2 、基板温度を室温として
スパッタリングを行う。このようにして得られた遮光層
３４の抵抗率は４×１０8Ω・cmであり、剥がれやひび割
れは認められなかった。Then, a light shielding layer 34 is formed on the photoconductor layer 33.
Are laminated. The light-shielding layer 34 is formed by laminating CdTe added with nitrogen (N) by 2.3 μm by a high frequency magnetron sputtering method (which is a kind of high frequency sputtering method). Argon (Ar
) Is used and the nitrogen gas (N 2 ) concentration is 2.2% with respect to this argon, and the film formation pressure (discharge gas pressure) is 10 mTor.
Sputtering is performed at r, high frequency power of 0.6 W / cm 2 , and substrate temperature of room temperature. The light-shielding layer 34 thus obtained had a resistivity of 4 × 10 8 Ω · cm, and no peeling or cracking was observed.
【００３１】このように、前記遮光層は基板温度を１０
０℃より低い室温とし、放電ガス圧を１０mTorr とし
て、高周波スパッタ法により形成したので、遮光層３４
の抵抗率が１０8Ω・cm以上となり、光導電体層３３の導
電率変化を損失なく液晶３８に伝えることができる。As described above, the light-shielding layer has a substrate temperature of 10
The light shielding layer 34 was formed by the high frequency sputtering method at a room temperature lower than 0 ° C. and a discharge gas pressure of 10 mTorr.
Has a resistivity of 10 8 Ω · cm or more, and the change in conductivity of the photoconductor layer 33 can be transmitted to the liquid crystal 38 without loss.
【００３２】また、得られた遮光層３４の光学濃度を図
５に示す。図５によれば、波長４００〜８００ｎｍで光
学濃度の値は２．５〜７．５であり、十分な遮光性を有
することが確認できる。このように、遮光層３４が抵抗
率が高く、遮光性も十分であるので、空間光変調素子の
画像品質を良好にすることができる。The optical density of the obtained light shielding layer 34 is shown in FIG. According to FIG. 5, the value of the optical density is 2.5 to 7.5 at a wavelength of 400 to 800 nm, and it can be confirmed that the optical density is sufficient. In this way, since the light-shielding layer 34 has a high resistivity and a sufficient light-shielding property, it is possible to improve the image quality of the spatial light modulator.
【００３３】さらに、遮光層３４上に誘電体ミラー層３
５を積層する。この誘電体ミラー層３５はＳiＯ2とＴi
Ｏ2とをＳi 及びＴi をターゲットとして直流スパッタ
法を用いて交互に積層することにより形成する。誘電体
ミラー層３５にも遮光層３４と同様に剥がれやひび割れ
は認められなかった。Further, the dielectric mirror layer 3 is formed on the light shielding layer 34.
5 is laminated. This dielectric mirror layer 35 is made of SiO 2 and Ti.
O 2 and O 2 are formed by alternately stacking Si and Ti as targets using a DC sputtering method. As with the light shielding layer 34, neither peeling nor cracking was observed in the dielectric mirror layer 35.
【００３４】さて、もう一方の透明基板３６上にＩＴＯ
からなる透明電極３７をスパッタリング法により形成す
る。誘電体ミラー層３５及び透明電極３７の上にＳiＯ2
からなる配向層３９ａ及び３９ｂをスパッタリング法に
よりそれぞれ形成する。この配向層３９ａ及び３９ｂは
液晶分子を配向させるためにある。Now, ITO is formed on the other transparent substrate 36.
The transparent electrode 37 made of is formed by the sputtering method. SiO 2 is formed on the dielectric mirror layer 35 and the transparent electrode 37.
Alignment layers 39a and 39b are formed by sputtering. The alignment layers 39a and 39b are for aligning liquid crystal molecules.
【００３５】配向層３９ａ及び３９ｂが形成された透明
基板３１及び３６を、図示していないスペーサー及びシ
ール材を介して貼り合わせ、両基板３１，３６の間に液
晶３８（光変調体）を挟持する。The transparent substrates 31 and 36 on which the alignment layers 39a and 39b are formed are pasted together via a spacer and a sealing material (not shown), and a liquid crystal 38 (light modulator) is sandwiched between the substrates 31 and 36. To do.
【００３６】このように、本空間光変調素子は強い読み
出し光に対応して遮光特性の十分な遮光層を有してお
り、この遮光層により画像品質が極めて良好である。As described above, the present spatial light modulator has the light-shielding layer having a sufficient light-shielding property in response to the strong read light, and the light-shielding layer provides extremely good image quality.
【００３７】Ｎ以外の他のＶ族元素であるＰ，Ａs，Ｓ
b，Ｂi についてもサンプルを作製したが、同様の結果
が得られた。P, As, S which are other V group elements other than N
Samples were also prepared for b and Bi, but similar results were obtained.
【００３８】[0038]
【発明の効果】本発明は上記構成により、次の効果を発
揮する。請求項１の空間光変調素子は、空間光変調素子
の光導電体層と誘電体ミラー層との間に設ける遮光層と
して、ＣdＴe（テルル化カドミウム）にＣu 等のＩ族元
素を不純物として添加したので、高抵抗で且つ抵抗値に
バラツキがなく、更に明・暗抵抗率の差が小さい遮光層
が得られる。The present invention has the following effects due to the above configuration. The spatial light modulation element according to claim 1 is used as a light-shielding layer provided between the photoconductor layer and the dielectric mirror layer of the spatial light modulation element, wherein CdTe (cadmium telluride) is doped with a Group I element such as Cu as an impurity. Therefore, it is possible to obtain a light-shielding layer having high resistance, no variation in resistance value, and a small difference in light / dark resistivity.
【００３９】請求項２の空間光変調素子は、アモルファ
スシリコン層からなる光導電体層と遮光層との間に、Ｓ
iＯ2層、ＣdＴeにＩ族元素が添加されたＯ2 リッチな層
及びＣdＴeにＩ族元素が添加された層を積層してなる接
合層を設けることで、光導電体層と遮光層との剥離を防
止することができる。In the spatial light modulator according to the second aspect of the present invention, an S element is provided between the photoconductor layer made of an amorphous silicon layer and the light shielding layer.
By providing a joining layer formed by laminating an iO 2 layer, an O 2 -rich layer in which a group I element is added to CdTe, and a layer in which a group I element is added to CdTe, a photoconductor layer and a light-shielding layer are formed. Peeling can be prevented.
【００４０】請求項３の空間光変調素子は、ＴiＯ2とＳ
iＯ2とを交互に積層した誘電体ミラー層と遮光層との間
に、ＳiＯ2層、ＣdＴeにＩ族元素が添加されたＯ2 リッ
チな層及びＣdＴeにＩ族元素が添加された層を積層して
なる接合層を設けることで、光導電体層と遮光層との剥
離を防止することができる。A spatial light modulator according to a third aspect is TiO 2 and S.
An SiO 2 layer, an O 2 -rich layer in which a group I element is added to CdTe, and a layer in which a group I element is added to CdTe are provided between a dielectric mirror layer and an opaque layer in which io 2 is alternately laminated. By providing the bonding layer formed by stacking layers, peeling between the photoconductor layer and the light shielding layer can be prevented.
【００４１】請求項４の空間光変調素子は、空間光変調
素子の光導電体層と誘電体ミラー層との間に設ける遮光
層として、ＣdＴe（テルル化カドミウム）にＮ等のＶ族
元素を不純物として添加したので、十分な遮光特性を有
し、しかも抵抗率が高い遮光層が得られる。したがっ
て、画像品質が良好な空間光変調素子を提供することが
できる。According to a fourth aspect of the present invention, in the spatial light modulating element, a V group element such as N is added to CdTe (cadmium telluride) as a light shielding layer provided between the photoconductor layer and the dielectric mirror layer of the spatial light modulating element. Since it is added as an impurity, a light-shielding layer having sufficient light-shielding properties and high resistivity can be obtained. Therefore, it is possible to provide a spatial light modulator having good image quality.
【００４２】また、前記遮光層として、ＣdＴeにＮ等の
Ｖ族元素を不純物として添加した場合には、前述のよう
に抵抗率を高くすることができるとともに、他の材料と
の密着性が良好になるので、光導電体層と遮光層との間
に及び遮光層と誘電体ミラー層との間にそれぞれ接合層
を設けなくてもよい。When CdTe is doped with a group V element such as N as an impurity as the light-shielding layer, the resistivity can be increased as described above and the adhesion with other materials is good. Therefore, it is not necessary to provide a bonding layer between the photoconductive layer and the light shielding layer and between the light shielding layer and the dielectric mirror layer.
【００４３】請求項５の空間光変調素子の製造方法は、
遮光層を高周波スパッタ法によって形成する際の基板温
度を１２０℃〜２００℃に維持し、且つスパッタ時間を
２時間以上とすることで、特別なアニール処理を行うこ
となく高抵抗の遮光層を得ることができる。A method of manufacturing a spatial light modulator according to claim 5 is
By maintaining the substrate temperature at 120 ° C. to 200 ° C. when forming the light shielding layer by the high frequency sputtering method and setting the sputtering time to 2 hours or more, a high resistance light shielding layer is obtained without performing a special annealing treatment. be able to.
【００４４】請求項６の空間光変調素子の製造方法は、
基板上に誘電体ミラー層を形成した後に基板温度を１２
０℃〜２００℃に維持した状態で、３０分〜２時間アニ
ール処理を行うことで、安定した品質の空間光変調素子
を得ることができる。更に、Ｃu を添加し且つ接合層を
設け更にアニールを施すことで、明・暗抵抗率の差が全
くない空間光変調素子を得ることができる。A method of manufacturing a spatial light modulator according to claim 6 is
After forming the dielectric mirror layer on the substrate, the substrate temperature is set to 12
By performing the annealing treatment for 30 minutes to 2 hours while maintaining the temperature at 0 ° C. to 200 ° C., it is possible to obtain the spatial light modulator having stable quality. Further, by adding Cu and providing a bonding layer and further annealing, it is possible to obtain a spatial light modulator having no difference in bright and dark resistivities.
【００４５】請求項７の空間光変調素子の製造方法は、
遮光層を高周波スパッタ法により形成する時の基板温度
を０〜１００℃とし、放電ガス圧を１０〜１００mTorr
とすることで、遮光層の抵抗率を１０8Ω・cm以上とする
ことができ、光導電体層の導電率変化を損失なく液晶に
伝えることができる。A method of manufacturing a spatial light modulator according to claim 7 is
The substrate temperature is 0 to 100 ° C. when the light shielding layer is formed by the high frequency sputtering method, and the discharge gas pressure is 10 to 100 mTorr.
By setting the above, the resistivity of the light shielding layer can be set to 10 8 Ω · cm or more, and the change in the conductivity of the photoconductor layer can be transmitted to the liquid crystal without loss.
【図１】本発明に係る空間光変調素子を組み込んだプロ
ジェクタの全体構成図FIG. 1 is an overall configuration diagram of a projector incorporating a spatial light modulator according to the present invention.
【図２】本発明に係る空間光変調素子の斜視図FIG. 2 is a perspective view of a spatial light modulator according to the present invention.
【図３】本発明に係る空間光変調素子の要部の拡大断面
図FIG. 3 is an enlarged cross-sectional view of a main part of a spatial light modulator according to the present invention.
【図４】本発明に係る別の空間光変調素子の斜視図FIG. 4 is a perspective view of another spatial light modulator according to the present invention.
【図５】別の空間光変調素子の遮光層の光学濃度を示す
図FIG. 5 is a diagram showing an optical density of a light shielding layer of another spatial light modulator.
１０，３０…空間光変調素子、１１，２１…ガラス基
板、３１，３６…透明基板、１２，２２，３２，３７…
透明電極、１３，３３…光導電体層、１４，１６…接合
層、１４ａ，１６ｃ…ＳiＯ2層、１４ｂ，１６ｂ…Ｏ2
リッチなＣdＴe+Ｃu層、１４ｃ，１６ａ…ＣdＴe+Ｃu
層、１５，３４…遮光層、１７，３５…誘電体ミラー
層、２３，３８…液晶（光変調体）。10, 30 ... Spatial light modulators 11, 21, ... Glass substrates, 31, 36 ... Transparent substrates, 12, 22, 32, 37 ...
Transparent electrode, 13, 33 ... Photoconductor layer, 14, 16 ... Bonding layer, 14a, 16c ... SiO 2 layer, 14b, 16b ... O 2
Rich CdTe + Cu layer, 14c, 16a ... CdTe + Cu
Layers, 15, 34 ... Shading layer, 17, 35 ... Dielectric mirror layer, 23, 38 ... Liquid crystal (light modulator).
Claims (7)
報を書き込み、この書き込んだ情報に応じて光変調体を
変調させ、この光変調体に入射した読み出し光を誘電体
ミラー層によって反射せしめるようにした空間光変調素
子において、前記光導電体層と誘電体ミラー層との間に
ＣdＴe（テルル化カドミウム）にＩ族元素（Ｈ，Ｌi，
Ｎa，Ｋ，Ｃu，Ｒb，Ａg，Ｃs，Ａu，Ｆr）を不純物と
して添加した遮光層を設けたことを特徴とする空間光変
調素子。1. An optical writing means writes information in a photoconductor layer, modulates a light modulator in accordance with the written information, and causes a read light incident on the light modulator to be reflected by a dielectric mirror layer. In the spatial light modulation element described above, a group I element (H, Li, CdTe (cadmium telluride)) is added between the photoconductor layer and the dielectric mirror layer.
A spatial light modulator comprising a light shielding layer doped with Na, K, Cu, Rb, Ag, Cs, Au, Fr) as an impurity.
て、前記光導電体層はアモルファスシリコン層からな
り、この光導電体層と遮光層との間には接合層が設けら
れ、この接合層は光導電体層から遮光層に向かって順に
ＳiＯ2層、ＣdＴeにＩ族元素が添加されたＯ2 リッチな
層及びＣdＴeにＩ族元素が添加された層を積層して構成
されることを特徴とする空間光変調素子。2. The spatial light modulator according to claim 1, wherein the photoconductor layer is made of an amorphous silicon layer, and a bonding layer is provided between the photoconductor layer and the light shielding layer. Is composed of a SiO 2 layer, an O 2 -rich layer in which CdTe is added with a Group I element, and a layer in which CdTe is added with a Group I element in this order from the photoconductor layer to the light-shielding layer. Characteristic spatial light modulator.
調素子において、前記誘電体ミラー層はＴiＯ2とＳiＯ2
とを交互に積層してなり、前記遮光層と誘電体ミラー層
との間には接合層が設けられ、この接合層は遮光層から
誘電体ミラー層に向かって順にＣdＴeにＩ族元素が添加
された層、ＣdＴeにＩ族元素が添加されたＯ2 リッチな
層及びＳiＯ2層を積層して構成されることを特徴とする
空間光変調素子。3. The spatial light modulator according to claim 1, wherein the dielectric mirror layer is made of TiO 2 and SiO 2.
Are alternately laminated, and a bonding layer is provided between the light shielding layer and the dielectric mirror layer. The bonding layer is formed by sequentially adding a group I element to CdTe from the light shielding layer toward the dielectric mirror layer. A spatial light modulation element comprising a laminated layer, an O 2 -rich layer in which a Group I element is added to CdTe, and a SiO 2 layer.
報を書き込み、この書き込んだ情報に応じて光変調体を
変調させ、この光変調体に入射した読み出し光を誘電体
ミラー層によって反射せしめるようにした空間光変調素
子において、前記光導電体層と誘電体ミラー層との間に
ＣdＴe（テルル化カドミウム）にＶ族元素（Ｎ，Ｐ，Ａ
s，Ｓb，Ｂi ）を不純物として添加した遮光層を設けた
ことを特徴とする空間光変調素子。4. An optical writing means writes information in the photoconductor layer, modulates the light modulator in accordance with the written information, and causes the read light incident on the light modulator to be reflected by the dielectric mirror layer. In the spatial light modulating device described above, a C-group element (N, P, A) is added between CdTe (cadmium telluride) between the photoconductor layer and the dielectric mirror layer.
A spatial light modulator comprising a light-shielding layer doped with s, Sb, Bi) as an impurity.
された基板上に高周波スパッタ法によって順次、接合
層、遮光層、接合層を形成して、この接合層上に誘電体
ミラー層を形成し、この誘電体ミラー層と他の基板表面
に形成した透明電極との間に光変調体を注入するように
した空間光変調素子の製造方法において、前記高周波ス
パッタ法は基板温度を１２０℃〜２００℃に維持して行
い、且つ遮光層生成のためのスパッタ時間は２時間以上
としたことを特徴とする空間光変調素子の製造方法。5. A bonding layer, a light shielding layer, and a bonding layer are sequentially formed by a high frequency sputtering method on a substrate on which a transparent electrode and a photoconductor layer are formed in this order, and a dielectric mirror layer is formed on the bonding layer. In the method of manufacturing a spatial light modulator in which a light modulator is formed between the dielectric mirror layer and a transparent electrode formed on the surface of another substrate, the high-frequency sputtering method uses a substrate temperature of 120 ° C. A method for manufacturing a spatial light modulator, which is performed at a temperature of up to 200 ° C. and a sputtering time for forming a light shielding layer is 2 hours or more.
法において、前記基板に誘電体ミラー層を形成した後、
基板温度を１２０℃〜２００℃に維持した状態で、３０
分〜２時間アニール処理を行うことを特徴とする空間光
変調素子の製造方法。6. The method for manufacturing a spatial light modulator according to claim 5, wherein after forming a dielectric mirror layer on the substrate,
With the substrate temperature maintained at 120 ° C to 200 ° C, 30
A method for manufacturing a spatial light modulation element, characterized by performing an annealing treatment for a period of from 2 minutes to 2 hours.
された基板上に高周波スパッタ法によって遮光層を形成
して、この遮光層上に誘電体ミラー層を形成し、この誘
電体ミラー層と他の基板表面に形成した透明電極との間
に光変調体を注入するようにした空間光変調素子の製造
方法において、前記遮光層は、基板温度を０〜１００℃
とし、放電ガス圧を１０〜１００mTorr として形成した
ことを特徴とする空間光変調素子の製造方法。7. A light-shielding layer is formed by a high-frequency sputtering method on a substrate on which a transparent electrode and a photoconductor layer are formed in this order, and a dielectric mirror layer is formed on this light-shielding layer. In the method for manufacturing a spatial light modulator in which a light modulator is injected between a transparent electrode formed on the surface of another substrate and the transparent electrode, the light shielding layer has a substrate temperature of 0 to 100 ° C.
And a discharge gas pressure of 10 to 100 mTorr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7036886A JP3006749B2 (en) | 1994-07-04 | 1995-02-24 | Spatial light modulator |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15236194 | 1994-07-04 | ||
| JP6-152361 | 1994-07-04 | ||
| JP7036886A JP3006749B2 (en) | 1994-07-04 | 1995-02-24 | Spatial light modulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0876140A true JPH0876140A (en) | 1996-03-22 |
| JP3006749B2 JP3006749B2 (en) | 2000-02-07 |
Family
ID=26375975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7036886A Expired - Fee Related JP3006749B2 (en) | 1994-07-04 | 1995-02-24 | Spatial light modulator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3006749B2 (en) |
-
1995
- 1995-02-24 JP JP7036886A patent/JP3006749B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3006749B2 (en) | 2000-02-07 |
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