JP3199091B2 - Stack of oriented thin films - Google Patents
Stack of oriented thin filmsInfo
- Publication number
- JP3199091B2 JP3199091B2 JP29762193A JP29762193A JP3199091B2 JP 3199091 B2 JP3199091 B2 JP 3199091B2 JP 29762193 A JP29762193 A JP 29762193A JP 29762193 A JP29762193 A JP 29762193A JP 3199091 B2 JP3199091 B2 JP 3199091B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- ferroelectric
- buffer layer
- layer
- 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.)
- Expired - Lifetime
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Semiconductor Integrated Circuits (AREA)
- Formation Of Insulating Films (AREA)
- Inorganic Insulating Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、不揮発性メモリーやキ
ャパシター等の電子素子、更には光変調素子などの作製
に適した配向性薄膜の積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated body of oriented thin films suitable for manufacturing electronic devices such as nonvolatile memories and capacitors, and light-modulating devices.
【０００２】[0002]
【従来の技術】従来、酸化物強誘電体薄膜は強誘電体の
持つ強誘電性、圧電性、焦電性、電気光学効果等の多く
の性質により、不揮発性メモリーを始めとして、表面弾
性波素子、赤外線焦電素子、音響光学素子、電気光学素
子等、多くの応用が期待されている。これらの応用のう
ち、薄膜光導波路構造での低光損失化と単結晶並みの分
極特性や電気光学効果を得るために単結晶薄膜の作製が
不可欠である。そのため、ＢａＴｉＯ3 、ＰｂＴｉ
Ｏ3 、Ｐｂ1-x Ｌａx （Ｚｒ1-y Ｔｉy ）Ｏ3 （ＰＬＺ
Ｔ）、ＬｉＮｂＯ3 、ＫＮｂＯ3 、Ｂｉ4 Ｔｉ3 Ｏ12等
のエピタキシャル強誘電体薄膜が、Ｒｆ−マグネトロン
・スパッタリング、イオン・ビーム・スパッタリング、
レーザー・アブレーション、有機金属化学蒸着（ＭＯＣ
ＶＤ）等の方法によって、酸化物単結晶基板上に数多く
形成されている。また、半導体素子との集積化のために
は、半導体基板上への強誘電体薄膜の作製が必要であ
る。しかし、半導体基板上への強誘電体薄膜のエピタキ
シャル成長は、高成長温度、半導体と強誘電体との間の
相互拡散、半導体の酸化等のために難しい。2. Description of the Related Art Conventionally, an oxide ferroelectric thin film has a surface acoustic wave, including non-volatile memory, due to many properties of a ferroelectric such as ferroelectricity, piezoelectricity, pyroelectricity, and electro-optic effect. Many applications are expected, such as devices, infrared pyroelectric devices, acousto-optic devices, and electro-optic devices. Among these applications, it is indispensable to produce a single-crystal thin film in order to reduce the optical loss in the thin-film optical waveguide structure and obtain polarization characteristics and electro-optic effects comparable to those of a single crystal. Therefore, BaTiO 3 , PbTi
O 3 , Pb 1-x La x (Zr 1-y Ti y ) O 3 (PLZ
T), an epitaxial ferroelectric thin film such as LiNbO 3 , KNbO 3 , Bi 4 Ti 3 O 12 is formed by Rf-magnetron sputtering, ion beam sputtering,
Laser ablation, metal organic chemical vapor deposition (MOC
VD) and many other methods are formed on an oxide single crystal substrate. Further, for integration with a semiconductor element, it is necessary to form a ferroelectric thin film on a semiconductor substrate. However, epitaxial growth of a ferroelectric thin film on a semiconductor substrate is difficult due to a high growth temperature, interdiffusion between the semiconductor and the ferroelectric, oxidation of the semiconductor, and the like.
【０００３】これらの理由のため、半導体基板上へエピ
タキシャルが低温で成長し、強誘電体薄膜のエピタキシ
ャル成長を助け、かつ拡散バリアとしても働くキャッピ
ング層をバッファ層として半導体基板上に形成すること
が必要である。また、強誘電体の屈折率は一般にＧａＡ
ｓよりも小さいが、強誘電体よりも小さい屈折率を持つ
バッファ層が得られれば、半導体レーザー光を強誘電体
薄膜光導波路中に閉じ込めることが可能になり、光変調
素子の半導体レーザー上への作製や光集積回路をＳｉ半
導体集積回路上に作製することが可能になる。これに対
し、本発明者は、ＭｇＯを半導体（１００）基板上へ
（１００）エピタキシャル成長させることを既に提案し
た（米国特許出願Ｄ／９１６２６，出願日１９９１．１
１．２６．、特願平４−３１９２２８号）。この際の結
晶学的関係は、例えばＧａＡｓ上のＢａＴｉＯ3 につい
てはＢａＴｉＯ3 （００１）//ＭｇＯ（１００）//Ｇａ
Ａｓ（１００）、面内方位ＢａＴｉＯ3 ［０１０］//Ｍ
ｇＯ［００１］//ＧａＡｓ［００１］となる構造を作製
することができる。[0003] For these reasons, it is necessary to form a capping layer on a semiconductor substrate as a buffer layer, which grows on a semiconductor substrate at a low temperature, assists the epitaxial growth of a ferroelectric thin film, and also functions as a diffusion barrier. It is. The refractive index of a ferroelectric is generally GaAs.
If a buffer layer having a refractive index smaller than s but smaller than a ferroelectric can be obtained, the semiconductor laser light can be confined in the ferroelectric thin-film optical waveguide, and the light can be condensed on the semiconductor laser of the light modulation element. And an optical integrated circuit can be manufactured on a Si semiconductor integrated circuit. In contrast, the present inventor has already proposed that MgO be (100) epitaxially grown on a semiconductor (100) substrate (US Patent Application D / 91626, filing date 1991.1).
1.26. And Japanese Patent Application No. 4-319228). The crystallographic relationship at this time is, for example, for BaTiO 3 on GaAs, BaTiO 3 (001) // MgO (100) // Ga
As (100), in-plane orientation BaTiO 3 [010] // M
A structure of gO [001] // GaAs [001] can be manufactured.
【０００４】[0004]
【発明が解決しようとする課題】一方、各種の電子部品
に用いられる薄膜電極および薄膜発熱抵抗体としては、
一般に金属が用いられるが、Ａｌ，Ｃｒ等の金属薄膜は
酸化に弱く、Ｐｄ，Ａｇ，Ｐｔ等の貴金属薄膜は酸化に
強い反面、コストが高い。また、強誘電体薄膜を用いた
不揮発性メモリーにおいては、Ｐｔ等の金属電極を用い
るとスイッチングに伴い強誘電体の疲労がみられる。近
年、酸化物電極が強誘電体薄膜のスイッチング疲労を抑
制することが知られ、例えばＪ．Ｌｅｅ等，Ａｐｐｌ．
Ｐｈｙｓ．Ｌｅｔｔ．，６３，２７（１９９３）では、
ＹＢａ2 Ｃｕ3 Ｏx のＰｂ（Ｚｒ0.52Ｔｉ0.48）Ｏ3 の
スイッチング疲労への効果が報告されている。しかし、
超伝導体であるＹＢａ2 Ｃｕ3 Ｏx 薄膜の作製は酸素濃
度のコントロール等の面において容易でない。特開平４
−１８２３９３においては、ＲｕＯ2 等への強誘電体薄
膜の成長が述べられているが、ＲｕＯ2 はＡＢＯ3 型強
誘電体との格子整合性が悪く、ＲｕＯ2 上の強誘電体薄
膜のエピタキシャル成長は難しい。また、特開昭６１−
２２５７１１においては、ＢａＰｂＯ3 等の導電性酸化
物の作製が述べられているが、ペースト法による厚膜で
あり、薄膜を必要とする電子素子には不適である。そこ
で、本発明は、上述の問題点に鑑みてなされたものであ
って、不揮発性メモリーやキャパシター等の電子素子、
更には光変調素子などを作製するに適した配向性薄膜の
積層体を提供することを目的とする。On the other hand, as a thin film electrode and a thin film heating resistor used for various electronic components,
Generally, a metal is used, but a metal thin film such as Al and Cr is weak to oxidation, and a noble metal thin film such as Pd, Ag, and Pt is strong to oxidation, but is expensive. Further, in a nonvolatile memory using a ferroelectric thin film, when a metal electrode such as Pt is used, fatigue of the ferroelectric is observed with switching. In recent years, it has been known that an oxide electrode suppresses switching fatigue of a ferroelectric thin film. Lee et al., Appl.
Phys. Lett. , 63 , 27 (1993)
The effect of YBa 2 Cu 3 O x on switching fatigue of Pb (Zr 0.52 Ti 0.48 ) O 3 has been reported. But,
It is not easy to prepare a YBa 2 Cu 3 O x thin film which is a superconductor in terms of controlling the oxygen concentration. JP 4
182393 describes growth of a ferroelectric thin film on RuO 2 or the like, but RuO 2 has poor lattice matching with an ABO 3 type ferroelectric, and epitaxial growth of a ferroelectric thin film on RuO 2 Is difficult. In addition, Japanese Unexamined Patent Publication No.
Although the production of a conductive oxide such as BaPbO 3 is described in 225711, it is a thick film formed by a paste method and is not suitable for an electronic element requiring a thin film. Therefore, the present invention has been made in view of the above-described problems, and electronic devices such as nonvolatile memories and capacitors,
Furthermore, an oriented thin film suitable for manufacturing light modulation elements, etc.
It is intended to provide a laminate .
【０００５】[0005]
【課題を解決するための手段】本発明者は、不揮発性メ
モリーや光変調素子等の作製に適した配向性強誘電体薄
膜について、鋭意研究を重ねてきたところ、エピタキシ
ャルの強誘電体薄膜をエピタキシャル成長した導電性薄
膜を利用して形成することによって、強誘電体の大きな
残留分極値や大きな電気光学定数等を得ることができる
という知見に基づいて、本発明を完成したものである。
すなわち、本発明の配向性薄膜の積層体は、単結晶基板
上にエピタキシャルのバッファ層と、前記バッファ層の
結晶方位に応じてエピタキシャル成長したペロブスカイ
トＡＢＯ3 型導電性薄膜が形成され、更にその上にエピ
タキシャル成長したＡＢＯ3 型強誘電体薄膜が形成され
ていることを特徴とする。Means for Solving the Problems The present inventors have, for the oriented ferroelectric thin film suitable for producing such as a nonvolatile memory or an optical modulator device was out extensive studies, epitaxy <br/> catcher Le The present invention has been completed based on the knowledge that a large remanent polarization value and a large electro-optical constant of a ferroelectric can be obtained by forming a ferroelectric thin film using a conductive thin film epitaxially grown. It was done.
That is, the laminate of the oriented thin film of the present invention is a single crystal substrate
An epitaxial buffer layer on top of the buffer layer
Made perovskite <br/> preparative ABO 3 type conductive thin film forms epitaxially grown in accordance with the crystal orientation, it is further made epi <br/> Takisharu grown ABO 3 type ferroelectric thin film form thereon It is characterized by the following.
【０００６】以下、本発明について詳細に説明する。本
発明の配向性薄膜の積層体は、酸化物であるＭｇＯ，Ｍ
ｇＡｌ2 Ｏ4 ，ＳｒＴｉＯ3 ，ＢａＺｒＯ3 ，ＬａＡｌ
Ｏ3 ，ＺｎＯ，Ａｌ2 Ｏ3 、単体半導体であるＳｉ，Ｇ
ｅ，ダイアモンド、III −Ｖ系の化合物半導体であるＡ
ｌＡｓ，ＡｌＳｂ，ＡｌＰ，ＧａＡｓ，ＧａＳｂ，Ｉｎ
Ｐ，ＩｎＡｓ，ＩｎＳｂ，ＡｌＧａＰ，ＡｌＩｎＰ，Ａ
ｌＧａＡｓ，ＡｌＩｎＡｓ，ＡｌＡｓＳｂ，ＧａＩｎＡ
ｓ，ＧａＩｎＳｂ，ＧａＡｓＳｂ，ＩｎＡｓＳｂ、II−
VI系の化合物半導体であるＺｎＳ，ＺｎＳｅ，ＺｎＴ
ｅ，ＣｄＳ，ＣｄＳｅ，ＣｄＴｅ，ＨｇＳｅ，ＨｇＴｅ
等より選ばれる単結晶基板であって、エピタキシャルの
バッファ層を表面に持つこれらの単結晶基板上に、前記
バッファ層の結晶方位に応じてエピタキシャル成長した
ペロブスカイトＡＢＯ3 型導電性薄膜が形成され、更に
その上にエピタキシャル成長したＡＢＯ3 型強誘電体薄
膜が形成される。Hereinafter, the present invention will be described in detail. The laminate of the oriented thin film of the present invention is composed of oxides of MgO, M
gAl 2 O 4 , SrTiO 3 , BaZrO 3 , LaAl
O 3, ZnO, Al 2 O 3, Si is a single body semiconductor, G
e, diamond, III-V based compound semiconductor A
lAs, AlSb, AlP, GaAs, GaSb, In
P, InAs, InSb, AlGaP, AlInP, A
lGaAs, AlInAs, AlAsSb, GaInA
s, GaInSb, GaAsSb, InAsSb, II-
VI-based compound semiconductors ZnS, ZnSe, ZnT
e, CdS, CdSe, CdTe, HgSe, HgTe
A single crystal substrate selected from equal, the epitaxial
On these single crystal substrates having a buffer layer on the surface,
<br/> perovskite ABO 3 type conductive thin film epitaxially grown in accordance with the crystal orientation of the buffer layer is made forms and further made epitaxially grown ABO 3 type ferroelectric thin film form thereon.
【０００７】上記バッファ層としては、ＭｇＯ，ＭｇＡ
ｌ2 Ｏ4 等の単層バッファ層、またはＰｂ（Ｚｒ0.53Ｔ
ｉ0.47）Ｏ3 （ＰＺＴ）／ＭｇＯ等の二層以上のバッフ
ァ層を用いることができる。上記ペロブスカイトＡＢＯ
3 型導電性薄膜としては、ＢａＰｂＯ3 または（Ｂａ
1-2x/mＣ2x/m）（Ｐｂ1-4y/nＤ4y/n）Ｏ3 で表される酸
化物導電性薄膜が挙げられる。ここで、Ｃは周期律表Ｉ
ａ族，IIａ族およびIII ａ族より選ばれる少なくとも一
種の原子を表し、Ｄは周期律表IIｂ族，IVａ族，IVｂ
族，Ｖａ族，Ｖｂ族およびVIII族より選ばれる少なくと
も一種の原子を表す。これらの原子のうち、ＣはＬｉ，
Ｎａ，Ｋ，Ｓｒ，Ｙ，Ｌａ，Ｃｅ，Ｇｄの少なくとも一
つが望ましく、ＤはＳｉ，Ｔｉ，Ｖ，Ｆｅ，Ｃｏ，Ｚ
ｎ，Ｚｒ，Ｎｂ，Ｓｎ，Ｓｂ，Ｔａ，Ｂｉの少なくとも
一つが望ましい。ｘおよびｙは、０＜ｘ，ｙ≦１であ
り、ｍはＣの原子価を意味し、ｎはＤの原子価を意味す
る。上記ＡＢＯ3 型強誘電体薄膜のＡは、Ｌｉ，Ｋ，Ｓ
ｒ，Ｂａ，Ｌａ，Ｐｂの少なくとも一つを含み、ＢはＭ
ｇ，Ｔｉ，Ｚｒ，Ｎｂ，Ｔａの少なくとも一つを含む。As the buffer layer, MgO, MgA
buffer layer such as l 2 O 4 or Pb (Zr 0.53 T
i 0.47 ) Two or more buffer layers such as O 3 (PZT) / MgO can be used. The above perovskite ABO
As the type 3 conductive thin film, BaPbO 3 or (Ba
1-2x / m C 2x / m) (Pb 1-4y / n D 4y / n) conductive oxide thin film represented by O 3 and the like. Where C is the periodic table I
a represents at least one atom selected from group a, group IIa and group IIIa, and D represents group IIb, group IVa or group IVb of the periodic table
And represents at least one atom selected from the group consisting of Group V, Group Va, Group Vb and Group VIII. Of these atoms, C is Li,
At least one of Na, K, Sr, Y, La, Ce, and Gd is desirable, and D is Si, Ti, V, Fe, Co, Z
At least one of n, Zr, Nb, Sn, Sb, Ta, and Bi is desirable. x and y are 0 <x, y ≦ 1, m means the valence of C, and n means the valence of D. A of the ABO 3 type ferroelectric thin film is Li, K, S
r, at least one of Ba, La, and Pb, and B is M
g, at least one of Ti, Zr, Nb, and Ta.
【０００８】上記導電性薄膜および強誘電体薄膜は、電
子ビーム蒸着、フラッシュ蒸着、イオン・プレーティン
グ、Ｒｆ−マグネトロン・スパッタリング、イオン・ビ
ーム・スパッタリング、レーザー・アブレーション、モ
レキュラー・ビーム・エピタキシー（ＭＢＥ）、化学蒸
着（ＣＶＤ）、プラズマＣＶＤ、有機金属化学蒸着 （Ｍ
ＯＣＶＤ）等より選ばれる気相成長法およびゾルゲル法
等のウェット・プロセスのいずれかまたはそれらの複数
の方法により形成される。エピタキシャル薄膜成長に影
響する要因としては、材料間の格子定数の差、結晶構造
の差、結晶対称性の差、熱膨張係数の差、表面の静電気
的状態の差等が挙げられるが、格子整合が最も重要な要
因の一つである。[0008] The conductive thin film and the ferroelectric thin film, electrostatic
Electron beam evaporation, flash evaporation, ion plating
, Rf-magnetron sputtering, ion beam
Beam sputtering, laser ablation,
Recursive beam epitaxy (MBE), chemical steam
Deposition (CVD), plasma CVD, metal organic chemical vapor deposition (M
Vapor phase growth method and sol-gel method selected from OCVD)
Any one or more of the wet processes such as
It is formed by the method described above. Factors affecting the epitaxial thin film growth, the difference in lattice constant between the materials, the difference in the crystal structure, the difference in crystal symmetry, the difference in thermal expansion coefficient, including but differentially electrostatically state of the surface, Lattice matching is one of the most important factors.
【０００９】次に、強誘電体層、導電体層および単結晶
基板、更にバッファ層を組合せた本発明の代表的な配向
性薄膜の積層体の例を幾つか下記の表に掲げる。 [0009] Then, the ferroelectric layer, the conductive layer and the single crystal substrate, further Ru listed in typical table of several following examples of the laminate of oriented films of the present invention in combination with the buffer layer.
【００１０】[0010]
【００１１】１）基板上にバッファ層を形成した強誘電
体層、導電体層および酸化物単結晶基板の結晶構造およ
び格子定数の関係を表１に示す。 1) Table 1 shows the relationship between the crystal structure and the lattice constant of the ferroelectric layer, the conductor layer, and the oxide single crystal substrate each having the buffer layer formed on the substrate.
【表１】 [Table 1]
【００１２】２）基板が半導体からなる強誘電体層、導
電体層、バッファ層および半導体単結晶基板の結晶構造
および格子定数の関係を表２に示す。 2) Table 2 shows the relationship between the crystal structure and the lattice constant of the ferroelectric layer, the conductor layer, the buffer layer, and the semiconductor single crystal substrate whose substrate is made of a semiconductor.
【表２】 [Table 2]
【００１３】３）バッファ層を二層形成した強誘電体
層、導電体層、第二バッファ層、第一バッファ層および
半導体単結晶基板の結晶構造および格子定数の関係を表
３に示す。[0013] 3) a ferroelectric layer was formed bilayer buffer layer, conductor layer, the second buffer layer, display the relationship between the crystal structure and lattice constant of the first buffer layer and the semiconductor single crystal substrate
3 is shown.
【表３】 [Table 3]
【００１４】[0014]
【実施例】以下に、実施例によって本発明をより具体的
に説明するが、本発明はこれらの実施例に限定されるも
のではない。参考例１ 金属アルコキシドであるＢａ（ＯＣ2 Ｈ5 ）2 およびＰ
ｂ（ＯＣ3 Ｈ7 ）2 の等モル量を無水の２−メトキシエ
タノールに溶解し、０．５Ｍ溶液を得た。この溶液を攪
拌しつつ２時間蒸留し、更に２２時間還流してダブル・
アルコキシドＢａＰｂ（ＯＣ2 Ｈ4 ＯＣＨ3 ）4 を得
た。この前駆体溶液を０．２μｍのフィルターに通し
て、ＭｇＯ（１００）単結晶基板へ２０００ｒｐｍでス
ピンコーティングを行った。以上の操作はすべて窒素雰
囲気中で行った。スピンコーティングの前に、基板は溶
剤洗浄、塩酸によるエッチング、脱イオン水によるリン
スを行い、最後に窒素気流中でエタノールのスピンコー
ティングによって乾燥した。スピンコーティングされた
基板は、室温にて脱イオン水中でバブリングした酸素雰
囲気中で１０℃／ｓｅｃの速度で急速昇温して３００℃
に２分間保持した後、６５０℃に３０分間保持し、最後
に電気炉の電源を切り冷却した。この結果、ＭｇＯ上に
膜厚０．１μｍのＢａＰｂＯ3 薄膜が、（１１０）に配
向して結晶化したＸ線回折パターンを示した。得られた
ＢａＰｂＯ3 薄膜の抵抗を四端子法によって測定したと
ころ、薄膜は２×１０-4Ω・ｃｍの低い抵抗値を示し
た。ＢａＰｂＯ3 はバンド・ギャップが小さいため金属
的電気伝導を示すが、可視光に対してはこのため透明で
はない。しかし、本参考例におけるＢａＰｂＯ3 薄膜
は、アニール温度、膜厚または組成によっては、可視光
に対してある程度の透明性が観察された。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Reference Example 1 Ba (OC 2 H 5 ) 2 and P which are metal alkoxides
An equimolar amount of b (OC 3 H 7 ) 2 was dissolved in anhydrous 2-methoxyethanol to obtain a 0.5 M solution. The solution was distilled for 2 hours with stirring, refluxed for another 22 hours, and
The alkoxide BaPb (OC 2 H 4 OCH 3 ) 4 was obtained. This precursor solution was passed through a 0.2 μm filter, and spin-coated on a MgO (100) single crystal substrate at 2000 rpm. All of the above operations were performed in a nitrogen atmosphere. Prior to spin coating, the substrate was rinsed with solvent, etched with hydrochloric acid, rinsed with deionized water, and finally dried by spin coating with ethanol in a stream of nitrogen. The spin-coated substrate is rapidly heated to 300 ° C. at a rate of 10 ° C./sec in an oxygen atmosphere bubbled in deionized water at room temperature.
, And then kept at 650 ° C. for 30 minutes. Finally, the electric furnace was turned off and cooled. As a result, an X-ray diffraction pattern in which the BaPbO 3 thin film having a thickness of 0.1 μm was oriented and crystallized (110) on MgO was shown. When the resistance of the obtained BaPbO 3 thin film was measured by a four-terminal method, the thin film showed a low resistance value of 2 × 10 −4 Ω · cm. BaPbO 3 exhibits metallic electrical conductivity due to its small band gap, but is not transparent to visible light. However, the BaPbO 3 thin film in this reference example was observed to have a certain degree of transparency to visible light depending on the annealing temperature, film thickness or composition.
【００１５】次に、上記のＢａＰｂＯ3 （１１０）／Ｍ
ｇＯ（１００）基板上に、Ｐｂ濃度で０．５ＭのＰｂ
（Ｚｒ0.53Ｔｉ0.47）Ｏ3 （ＰＺＴ）の前駆体溶液を２
０００ｒｐｍでスピンコーティングを行った。この前駆
体溶液は、モル比でＰｂ：Ｚｒ：Ｔｉ＝１．００：０．
５３：０．４７のＰｂ（ＣＨ3 ＣＯＯ）2 、Ｚｒ（Ｏ -
i-Ｃ3 Ｈ7 ）4 およびＴｉ（Ｏ -i-Ｃ3 Ｈ7 ）4 を２−
メトキシエタノールに溶解し、６時間蒸留した後、１８
時間還流することにより得た。以上の操作はすべて窒素
雰囲気中で行った。スピンコーティングされた基板は、
１０℃／ｓｅｃで昇温し、酸素雰囲気中３５０℃で１分
間熱分解を行った後、基板を６５０℃で３０分間加熱す
ることによりＰＺＴ薄膜が結晶化した。得られた配向性
薄膜の積層体は、酸化物基板１ａおよびＢａＰｂＯ
3 （１１０）からなる導電体層上に、ＰＺＴ薄膜が（１
１０）に配向した強誘電体層が形成されている。更に、
このＰＺＴ薄膜上にＢａＰｂＯ3 薄膜を上記と同じ方法
によって再度形成した。このようにして作製したＢａＰ
ｂＯ3 ／ＰＺＴ／ＢａＰｂＯ3 ／ＭｇＯ素子を用いて、
ＢａＰｂＯ3 を上下部電極として電圧を印加することに
よりＰＺＴの分極特性を試験したところ、金属電極と比
較して良好なスイッチング特性と疲労特性を示した。Next, the above BaPbO 3 (110) / M
0.5M Pb with a Pb concentration of 0.5M on a gO (100) substrate
(Zr 0.53 Ti 0.47 ) O 3 (PZT)
Spin coating was performed at 000 rpm. This precursor solution has a molar ratio of Pb: Zr: Ti = 1.00: 0.
53: 0.47 Pb (CH 3 COO) 2 , Zr (O −
The i-C 3 H 7) 4 and Ti (O -i-C 3 H 7) 4 2-
After dissolving in methoxyethanol and distilling for 6 hours, 18
Obtained by refluxing for hours. All of the above operations were performed in a nitrogen atmosphere. The spin-coated substrate is
After the temperature was raised at 10 ° C./sec and pyrolysis was performed at 350 ° C. for 1 minute in an oxygen atmosphere, the substrate was heated at 650 ° C. for 30 minutes to crystallize the PZT thin film. Obtained orientation
Stack of thin films, oxides substrate 1a and BaPbO
3 On the conductor layer made of (110), a PZT thin film is
A ferroelectric layer oriented in 10) is formed. Furthermore,
On this PZT thin film, a BaPbO 3 thin film was formed again by the same method as described above. BaP prepared in this manner
Using a bO 3 / PZT / BaPbO 3 / MgO element,
The polarization characteristics of PZT were tested by applying a voltage using BaPbO 3 as the upper and lower electrodes, and showed good switching characteristics and fatigue characteristics as compared with the metal electrodes.
【００１６】[0016]
【００１７】[0017]
【００１８】[0018]
【００１９】実施例１ 参考例１ と同様にして、ＰＺＴの前駆体溶液をＳｒＴｉ
Ｏ3 （１００）単結晶基板上に２０００ｒｐｍでスピン
コーティングし、基板を酸素雰囲気中１０℃／ｓｅｃで
昇温して３５０℃で熱分解した後、６５０℃でアニール
することにより（００１）の方位にエピタキシャルなＰ
ＺＴ薄膜を得た。このＰＺＴ薄膜をエピタキシャル・バ
ッファ層として、ＢａＰｂＯ3 を参考例１と同様にして
形成すると、ＢａＰｂＯ3 は（１００）の方位にエピタ
キシャルに結晶化した。更に、この上に、参考例１と同
様の方法により膜厚０．３５μｍの（Ｐｂ0.72Ｌ
ａ0.28）ＴｉＯ3 （ＰＬＴ）薄膜を形成することによっ
て、ＰＬＴ（００１）／ＢａＰｂＯ3 （１００）／ＰＺ
Ｔ（００１）／ＳｒＴｉＯ3 （１００）の多層エピタキ
シャル構造を得た。図１には、表面にバッファ層１′を
有する酸化物基板１ａ上に導電体層２および強誘電体層
３からなる配向性薄膜の積層体が示されている。このよ
うな強誘電体、導電体、バッファ層および単結晶基板の
組合せの例を前記表１に示してある。[0019] In the same manner as in Example 1 Reference Example 1, SrTi a precursor solution of PZT
The substrate was spin-coated at 2000 rpm on an O 3 (100) single crystal substrate, heated in an oxygen atmosphere at 10 ° C./sec, thermally decomposed at 350 ° C., and annealed at 650 ° C. to obtain the orientation of (001). Epitaxial P
A ZT thin film was obtained. When this PZT thin film was used as an epitaxial buffer layer and BaPbO 3 was formed in the same manner as in Reference Example 1 , BaPbO 3 was crystallized epitaxially in the (100) direction. Further, a 0.35 μm-thick (Pb 0.72 L) film was formed thereon in the same manner as in Reference Example 1.
By forming a 0.28 ) TiO 3 (PLT) thin film, PLT (001) / BaPbO 3 (100) / PZ
A multilayer epitaxial structure of T (001) / SrTiO 3 (100) was obtained. FIG. 1 shows a laminate of an oriented thin film composed of a conductor layer 2 and a ferroelectric layer 3 on an oxide substrate 1a having a buffer layer 1 'on the surface. An example of such a combination of a ferroelectric, a conductor, a buffer layer and a single crystal substrate is shown in Table 1 above.
【００２０】次に、上記ＰＬＴ表面に櫛形の上部Ａｌ電
極を設けることにより、ＰＬＴ薄膜光導波路にプリズム
・カップリングによりレーザー光を導入した。図２に示
すように、ＰＬＴ薄膜の上部電極４であるＡｌと下部電
極であるＢａＰｂＯ3 （導電体層２）との間に電圧を印
加すると、電気力線５の電気光学効果によるブラッグ反
射により導入されたレーザー光のスイッチングが可能と
なった。この際、下部電極を形成することなくＰＬＴの
表面に対向する櫛形電極４′のみを設けた図３に示す一
般的なコプレーナー型素子に比べて、電極間間隔がＰＬ
Ｔの膜厚に等しい０．３５μｍとすることが容易であ
る。その結果、ＰＬＴの膜厚方向に有効に電圧を印加す
ることが可能なために駆動電圧が低く、電極間幅が電極
の微細加工技術による制約を受けないために素子の作製
が極めて容易となった。このように、絶縁性の基板上に
エピタキシャル電極薄膜が作製可能なため、エピタキシ
ャル強誘電体薄膜が電極上に作製できる。したがって、
エピタキシャル電極を設けることなくして、従来絶縁性
基板上または絶縁性薄膜上に作製不可能であったキャパ
シター型電極構造を有する素子の作製が可能となった。Next, a laser beam was introduced into the PLT thin-film optical waveguide by prism coupling by providing a comb-shaped upper Al electrode on the PLT surface. As shown in FIG. 2, when a voltage is applied between Al, which is the upper electrode 4 of the PLT thin film, and BaPbO 3 (the conductor layer 2), which is the lower electrode, the Bragg reflection of the lines of electric force 5 due to the electro-optic effect causes Switching of the introduced laser light is now possible. At this time, as compared with the general coplanar type element shown in FIG. 3 in which only the comb-shaped electrode 4 'facing the surface of the PLT without forming the lower electrode, the distance between the electrodes is PL.
It is easy to set the thickness to 0.35 μm, which is equal to the thickness of T. As a result, it is possible to effectively apply a voltage in the thickness direction of the PLT, so that the driving voltage is low, and the width between electrodes is not restricted by the fine processing technology of the electrodes. Was. Thus, since an epitaxial electrode thin film can be formed on an insulating substrate, an epitaxial ferroelectric thin film can be formed on an electrode. Therefore,
Without providing an epitaxial electrode, an element having a capacitor-type electrode structure, which could not be conventionally formed on an insulating substrate or an insulating thin film, can be manufactured.
【００２１】実施例２ ターゲット表面をＵＶレーザー・パルスにより瞬間的に
加熱して蒸着するエキシマ・レーザー・デポジション法
によって、ＧａＡｓ（１００）単結晶基板上にエピタキ
シャル・バッファ層を形成した。すなわち、レーザー
は、波長３０８ｎｍのＸｅＣｌエキシマ・レーザーを用
い、パルス周期４Ｈｚ、パルス長１７ｎｓ、エネルギー
１３０ｍＪ（ターゲット表面でのエネルギー密度１．３
Ｊ／ｃｍ 2 ）の条件とした。ターゲットは金属Ｍｇを用
い、ＭｇＯを反応成長させた。ＧａＡｓ単結晶基板は溶
剤洗浄後、硫酸系の溶液でエッチングを行った。更に、
この基板を脱イオン水とエタノールでリンスし、最後に
窒素気流下でエタノールによるスピン乾燥を行った。 ス
ピン乾燥後に、基板を直ちにデポジション・チャンバー
に導入し、３５０℃に加熱して４００ オン グ ストローム のエピ
タキシャルＭｇＯ（１００）バッファ層の成膜を行っ
た。続いて、７００℃でＭｇＯバッファ層上へ膜厚１０
００ オン グ ストローム のＢａＰｂＯ 3 （１００）を、更に膜厚
２０００ オン グ ストローム のＢａＴｉＯ 3 （００１）をその場
エピタキシャル成長した。得られた配向性薄膜の積層体
の層構造を図４に示す。この層構造は、表面にバッファ
層１′を有する半導体基板１ｂ上に導電体層２および強
誘電体層３が形成されている。このような強誘電体、導
電体、バッファ層および半導体単結晶基板の組合せの例
を前記表２に示してある。 Embodiment 2 A target surface is instantaneously irradiated with a UV laser pulse.
Excimer laser deposition method to deposit by heating
By means of epitaxy on a GaAs (100) single crystal substrate.
A shallow buffer layer was formed. That is, the laser
Uses a 308nm wavelength XeCl excimer laser
Pulse period 4Hz, pulse length 17ns, energy
130 mJ (energy density 1.3 on the target surface)
J / cm 2 ). The target is metal Mg
Then, MgO was grown by reaction. GaAs single crystal substrate
After the cleaning with the agent, etching was performed with a sulfuric acid-based solution. Furthermore,
Rinse this substrate with deionized water and ethanol, and finally
Spin drying with ethanol was performed under a nitrogen stream. S
Immediately after the pin is dried, the substrate is
It was introduced into 400 on grayed Strom epi heated to 350 ° C.
Deposition of a MgO (100) buffer layer
Was. Subsequently, a film thickness of 10 was formed on the MgO buffer layer at 700 ° C.
00 BaPbO 3 ON grayed Strom (100), further thickness
2000 on grayed BaTiO of Strom 3 (001) situ
It was epitaxially grown. Laminate of obtained oriented thin film
Is shown in FIG. This layer structure has a buffer on the surface.
A conductor layer 2 on a semiconductor substrate 1b having a layer 1 ';
A dielectric layer 3 is formed. Such ferroelectric, conductive
Example of combination of conductor, buffer layer and semiconductor single crystal substrate
Are shown in Table 2 above.
【００２２】実施例３ 実施例２と同様にして、 エキシマ・レーザー・デポジシ
ョン法によってＧａＡｓ（１００）単結晶基板にエピタ
キシャルＭｇＯバッファ層の成膜を行った。次に、先の
実施例と同様にして、前駆体溶液よりＰＺＴ、ＢａＰｂ
Ｏ3 、更にＰＬＴを形成することにより、ＰＬＴ（００
１）／ＢａＰｂＯ3 （１００）／ＰＺＴ（００１）／Ｍ
ｇＯ（１００）／ＧａＡｓ（１００）の多層エピタキシ
ャル構造を得た。図５には、表面に第一バッファ層１′
ａおよび第二バッファ層１′ｂを有する半導体基板１ｂ
上に、導電体層２および強誘電体層３からなる配向性強
誘電体薄膜が示されている。このような強誘電体、導電
体、第二バッファ層、第一バッファ層および半導体単結
晶基板の組合せの例を前記表３に示してある。次に、上
記ＰＬＴ表面に櫛形の上部Ａｌ電極を設けることによ
り、レーザー光を導入した。図６に示すように、ＰＬＴ
薄膜導波路に導入されたレーザー光は、ＰＬＴ薄膜の上
部電極４であるＡｌと下部電極であるＢａＰｂＯ3 （導
電体層２）との間に電圧を印加すると、電気力線５の電
気光学効果によるブラッグ反射によりレーザー光のスイ
ッチングが可能となった。したがって、この素子は実施
例１と同様に光導波路として利用可能である。また、Ｐ
ＬＴの表面に対向する櫛形電極４′のみを設けた図７に
示す素子に比べて、ＰＬＴの膜厚方向に有効に電圧を印
加することが可能なために駆動電圧が低く、更に電極間
幅が電極の微細加工による制約を受けないために素子の
作製が極めて容易となった。Example 3 In the same manner as in Example 2 , an epitaxial MgO buffer layer was formed on a GaAs (100) single crystal substrate by excimer laser deposition. Next, in the same manner as in the previous example, PZT, BaPb
O 3 and PLT to form PLT (00
1) / BaPbO 3 (100) / PZT (001) / M
A multilayer epitaxial structure of gO (100) / GaAs (100) was obtained. In FIG. 5 , the first buffer layer 1 'is provided on the surface.
a and a semiconductor substrate 1b having a second buffer layer 1'b
Above, an oriented ferroelectric thin film composed of the conductor layer 2 and the ferroelectric layer 3 is shown. Table 3 shows examples of combinations of such ferroelectrics, conductors, second buffer layers, first buffer layers, and semiconductor single crystal substrates. Next, a laser beam was introduced by providing a comb-shaped upper Al electrode on the surface of the PLT. As shown in FIG. 6, PLT
When a voltage is applied between the Al, which is the upper electrode 4 of the PLT thin film, and the BaPbO 3 (the conductor layer 2), which is the lower electrode, the laser light introduced into the thin film waveguide causes the electro-optic effect of the electric flux lines 5. Switching of laser light was enabled by the Bragg reflection. Therefore, this element can be used as an optical waveguide as in the first embodiment. Also, P
Compared to the device shown in FIG. 7 in which only the comb-shaped electrode 4 'facing the LT surface is provided, the drive voltage is lower because the voltage can be applied more effectively in the thickness direction of the PLT, and the width between the electrodes is further reduced. However, there is no restriction due to the fine processing of the electrodes, so that the fabrication of the element has become extremely easy.
【００２３】以上の実施例では、ゾルゲル法またはエキ
シマ・レーザー・デポジション法およびそれらの両方法
により成膜したが、成膜プロセスはこれらに限定される
ものではなく、前述したとおり、電子ビーム蒸着、フラ
ッシュ蒸着、Ｒｆ−マグネトロン・スパッタリング、イ
オン・ビーム・スパッタリング、イオン・プレーティン
グ、ＭＢＥ、イオン化クラスター・ビーム・エピタキシ
ー、ＣＶＤ、ＭＯＣＶＤ、プラズマＣＶＤ等の気相成長
法およびゾルゲル法以外のウェット・プロセスが、同様
に本発明の配向性薄膜の積層体の作製に有効である。 In the above embodiments, the sol-gel method or the exhaust
Shima laser deposition method and both methods
The film formation process is limited to these.
However, as described above, electron beam evaporation, flash
Flash deposition, Rf-magnetron sputtering,
On-beam sputtering, ion plating
, MBE, ionized cluster beam epitaxy
-, CVD, MOCVD, vapor phase growth such as plasma CVD
Processes other than wet process and sol-gel process are similar
In addition, the present invention is effective for producing a laminate of the oriented thin film of the present invention.
【００２４】[0024]
【発明の効果】本発明の配向性強誘電体薄膜を含む配向
性薄膜の積層体は、エピタキシャルの強誘電体薄膜が作
製可能であるため、強誘電体の大きな残留分極値や大き
な電気光学定数等を得ることができる。また、強誘電体
と基板との間にエピタキシャルの酸化物電極を設けたた
め、低電圧駆動が可能な光変調素子や高性能な不揮発性
メモリー等のスイッチング素子の作製が可能となる。さ
らに、半導体基板へのエピタキシャルの酸化物電極とそ
れによるエピタキシャルの強誘電体薄膜の作製が可能な
ため、ＧａＡｓ系半導体レーザー上へ光変調素子やＳｉ
半導体集積回路上に光集積回路を作製することなどが可
能になる。The orientation including the oriented ferroelectric thin film of the present invention
Laminate sex films, since the ferroelectric thin film of the epitaxial can be produced, it is possible to obtain a large residual polarization value of the ferroelectric and large electro-optic constant and the like. Moreover, strong due to the provision of the oxide electrode of epitaxial between the dielectric and the substrate, it is possible to produce the switching elements of the optical modulator and high-performance non-volatile memory or the like which can be driven at a low voltage. Moreover, since making a ferroelectric thin film of the oxide electrode and the epitaxial by its epitaxial to the semiconductor substrate it is possible, the light modulation element or Si on GaAs-based semiconductor laser
For example, an optical integrated circuit can be manufactured over a semiconductor integrated circuit.
【図１】 ＳｒＴｉＯ3 （１００）基板上にエピタキシ
ャルＰＬＴ（００１）／ＢａＰｂＯ3 （１００）／ＰＺ
Ｔ（００１）を形成した実施例１の多層構造の配向性薄
膜の積層体を示す。FIG. 1 shows an epitaxial PLT (001) / BaPbO 3 (100) / PZ on a SrTiO 3 (100) substrate.
Orientation thin film of multilayer structure of Example 1 in which T (001) was formed
1 shows a stack of films .
【図２】 実施例１の配向性薄膜の積層体におけるＰＬ
Ｔ表面に上部電極を配設した電気光学効果による光スイ
ッチング素子を示す。FIG. 2 shows a PL in a laminate of an oriented thin film of Example 1 .
4 shows an optical switching element based on the electro-optic effect in which an upper electrode is disposed on a T surface.
【図３】 導電体層を設けることなく基板上のＰＬＴ表
面に電極を配設した電気光学効果による光スイッチング
素子を示す。FIG. 3 shows an optical switching element based on the electro-optic effect in which electrodes are provided on a PLT surface on a substrate without providing a conductor layer.
【図４】 ＧａＡｓ（１００）基板上にＢａＴｉＯ
3 （００１）／ＢａＰｂＯ3 （１００）／ＭｇＯ（１０
０）を形成した実施例２の多層構造の配向性薄膜の積層
体を示す。FIG. 4 shows BaTiO on a GaAs (100) substrate.
3 (001) / BaPbO 3 (100) / MgO (10
Lamination of Oriented Thin Film of Multi-layer Structure of Example 2 Forming 0)
Show body .
【図５】 ＧａＡｓ（１００）基板上のエピタキシャル
ＰＬＴ（００１）／ＢａＰｂＯ3 （１００）／ＰＺＴ
（００１）／ＭｇＯ（１００）を形成した実施例３の多
層構造の配向性薄膜の積層体を示す。FIG. 5: Epitaxial PLT (001) / BaPbO 3 (100) / PZT on GaAs (100) substrate
The laminate of the oriented thin film having a multilayer structure of Example 3 in which (001) / MgO (100) is formed is shown.
【図６】 実施例３の配向性薄膜の積層体におけるＰＬ
Ｔ表面に上部電極を配設した電気光学効果による光スイ
ッチング素子を示す。FIG. 6 is a graph showing a PL in a laminate of an oriented thin film of Example 3 .
4 shows an optical switching element based on the electro-optic effect in which an upper electrode is disposed on a T surface.
【図７】 導電体層を設けることなく基板およびバッフ
ァ層上のＰＬＴ表面に電極を配設した電気光学効果によ
る光スイッチング素子を示す。FIG. 7 shows an optical switching element based on the electro-optic effect in which electrodes are provided on the surface of a PLT on a substrate and a buffer layer without providing a conductor layer.
１ａ…酸化物基板、１ｂ…半導体基板、１′…バッファ
層、１′ａ…第一バッファ層、１′ｂ…第二バッファ
層、２…導電体層、３…強誘電体層、４…上部電極、
４′…櫛形電極、５…電気力線。1a ... oxide substrate, 1b ... semiconductor substrate, 1 '... buffer layer, 1'a ... first buffer layer, 1'b ... second buffer layer, 2 ... conductor layer, 3 ... ferroelectric layer, 4 ... Upper electrode,
4 ': Comb-shaped electrode, 5: Electric force lines.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−234809（ＪＰ，Ａ) 特開 平４−182393（ＪＰ，Ａ) Ｔ．Ａｚｕｍａ ｅｔ ａｌ．，”Ｐ ｒｅｐａｒａｔｉｏｎ ａｎｄ ｂａｓ ｉｃ ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｂ ａＴｉＯ３−ＢａＰｂＯ３ ｍｕｌｔｉ ｌａｙｅｒ ｔｈｉｎ ｆｉｌｍｓ ｂ ｙ ｍｅｔａｌ−ａｌｋｏｘｉｄｅｓ ｍｅｔｈｏｄ”，Ｊｐｎ．Ｊ．Ａｐｐ ｌ．Ｐｈｙｓ．Ｐａｒｔ １，Ｖｏｌ. 32，Ｎｏ．９Ｂ，Ｓｅｐ．1993，ｐｐ. 4089−4091 (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 H01B 3/00 H01L 21/314 H01L 21/822 H01L 27/04 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-234809 (JP, A) JP-A-4-182393 (JP, A) Azuma et al. , "Preparation and basic properties of BaTiO3-BaPbO3 multi layer thin films by metal-alkoxides method", Jpn. J. Appl. Phys. Part 1, Vol. 32, No. 9B, Sep. 1993, pp. 4089-4091 (58) Fields investigated (Int. Cl. 7 , DB name) C30B 1/00-35/00 H01B 3/00 H01L 21/314 H01L 21/822 H01L 27/04 CA (STN ) REGISTRY (STN)
Claims (2)
ァ層と、前記バッファ層の結晶方位に応じてエピタキシ
ャル成長したペロブスカイトＡＢＯ3 型導電性薄膜が形
成され、更にその上にエピタキシャル成長したＡＢＯ3
型強誘電体薄膜が形成されていることを特徴とする配向
性薄膜の積層体。1. An epitaxial buffer on a single crystal substrate.
And § layer, wherein according to the crystal orientation of the buffer layer epitaxy <br/> turbocharger Le grown perovskite ABO 3 type conductive thin film made form <br/>, ABO 3 was further epitaxially grown thereon
Laminate of oriented films type ferroelectric thin film is characterized by being made form.
求項１記載の配向性薄膜の積層体。2. A laminate of oriented films of the conductive thin film according to claim 1 wherein the BaPbO 3.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29762193A JP3199091B2 (en) | 1993-11-04 | 1993-11-04 | Stack of oriented thin films |
| US08/439,371 US5650362A (en) | 1993-11-04 | 1995-05-11 | Oriented conductive film and process for preparing the same |
| US08/620,752 US5656382A (en) | 1993-11-04 | 1996-03-18 | Oriented conductive film and process for preparing the same |
| JP2000287904A JP3513532B2 (en) | 1993-11-04 | 2000-09-22 | Optical switching element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29762193A JP3199091B2 (en) | 1993-11-04 | 1993-11-04 | Stack of oriented thin films |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000287904A Division JP3513532B2 (en) | 1993-11-04 | 2000-09-22 | Optical switching element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07133199A JPH07133199A (en) | 1995-05-23 |
| JP3199091B2 true JP3199091B2 (en) | 2001-08-13 |
Family
ID=17848935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29762193A Expired - Lifetime JP3199091B2 (en) | 1993-11-04 | 1993-11-04 | Stack of oriented thin films |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3199091B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003146767A (en) * | 2001-11-09 | 2003-05-21 | National Institute Of Advanced Industrial & Technology | Method of producing ceramic sintered compact and inorganic film, ceramic sintered compact, and inorganic film |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000019301A (en) * | 1998-06-29 | 2000-01-21 | Kyocera Corp | Optical lens and optical recording device using that |
| JP5024310B2 (en) * | 2002-03-25 | 2012-09-12 | セイコーエプソン株式会社 | Inkjet recording head and inkjet printer |
| JP4401300B2 (en) * | 2003-03-04 | 2010-01-20 | 富士通株式会社 | Method for forming (001) oriented perovskite film and apparatus having such perovskite film |
| CN109371462A (en) * | 2018-12-05 | 2019-02-22 | 石家庄铁道大学 | Epitaxial growth organic metal halide perovskite monocrystal thin films preparation method |
-
1993
- 1993-11-04 JP JP29762193A patent/JP3199091B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| Ｔ．Ａｚｕｍａ ｅｔ ａｌ．，"Ｐｒｅｐａｒａｔｉｏｎ ａｎｄ ｂａｓｉｃ ｐｒｏｐｅｒｔｉｅｓ ｏｆ ＢａＴｉＯ３−ＢａＰｂＯ３ ｍｕｌｔｉｌａｙｅｒ ｔｈｉｎ ｆｉｌｍｓ ｂｙ ｍｅｔａｌ−ａｌｋｏｘｉｄｅｓ ｍｅｔｈｏｄ"，Ｊｐｎ．Ｊ．Ａｐｐｌ．Ｐｈｙｓ．Ｐａｒｔ １，Ｖｏｌ．３２，Ｎｏ．９Ｂ，Ｓｅｐ．１９９３，ｐｐ．４０８９−４０９１ |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003146767A (en) * | 2001-11-09 | 2003-05-21 | National Institute Of Advanced Industrial & Technology | Method of producing ceramic sintered compact and inorganic film, ceramic sintered compact, and inorganic film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07133199A (en) | 1995-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5650362A (en) | Oriented conductive film and process for preparing the same | |
| TWI284974B (en) | Electronic and optical devices and methods of forming these devices | |
| JP2819067B2 (en) | Cubic metal oxide thin films grown epitaxially on silicon | |
| US5348775A (en) | Production of PT/PZT/PLZT laser `direct write` patterns | |
| KR100417743B1 (en) | Ferroelectric memory with ferroelectric thin film having thickness of 90 nanometers or less, and method of making same | |
| KR100671375B1 (en) | Thin film multilayer body, electronic device using such thin film multilayer body, actuator, and method for manufacturing actuator | |
| JP2924574B2 (en) | Oriented ferroelectric thin film device | |
| JPH06196648A (en) | Oriented ferroelectric thin film device | |
| JPH11502673A (en) | Laminated superlattice material and low-temperature manufacturing method of electronic device including the same | |
| JP4483849B2 (en) | Ferroelectric thin film | |
| GB2250751A (en) | Process for the production of dielectric thin films; pyroelectric sensor | |
| KR100442543B1 (en) | Method for manufacturing thin layer of layered superlattice material and electronic device having two thin layer | |
| JPH1174502A (en) | Silicon functional motherboard and photointegrating oxide device | |
| US20060228064A1 (en) | Electronic and optical devices and methods of forming these devices | |
| US20040048455A1 (en) | Method of making layered superlattice material with improved microstructure | |
| JP3047316B2 (en) | Epitaxial ferroelectric thin film device and method for producing the same | |
| JPH10223476A (en) | Ferroelectric thin film and its manufacture | |
| JP3199091B2 (en) | Stack of oriented thin films | |
| JP2864912B2 (en) | Oriented ferroelectric thin film | |
| JP3513532B2 (en) | Optical switching element | |
| JPWO2004068235A1 (en) | Optical deflection element and manufacturing method thereof | |
| JP4399059B2 (en) | Thin film structure | |
| US6890768B2 (en) | Method of making layered superlattice material with ultra-thin top layer | |
| EP0544399A2 (en) | Epitaxial magnesium oxide as a buffer layer for formation of subsequent layers on tetrahedral semiconductors | |
| KR101213606B1 (en) | Method for manufacturing oxide thin film device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080615 Year of fee payment: 7 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090615 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100615 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110615 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120615 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130615 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term |