JP2010064942A - Method for producing perovskite oxide thin film, and perovskite oxide thin film - Google Patents
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical group [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002113 barium titanate Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
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- 239000002159 nanocrystal Substances 0.000 abstract description 45
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- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 229910002367 SrTiO Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 238000004070 electrodeposition Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000003980 solgel method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
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- 238000000984 pole figure measurement Methods 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 239000006200 vaporizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910019606 La0.5Sr0.5CoO3 Inorganic materials 0.000 description 1
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
本発明は、例えば圧電体として有用なペロブスカイト酸化物を用いて薄膜を製造する方法、及び該方法により製造されたペロブスカイト酸化物薄膜に関する。 The present invention relates to a method for producing a thin film using a perovskite oxide useful as a piezoelectric material, for example, and a perovskite oxide thin film produced by the method.
Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3（以後、ＰＺＴという。）又は（Ｐｂ，Ｌａ）（Ｚｒ，Ｔｉ）Ｏ3（以後、ＰＬＺＴという。）を用いた強誘電体からなる薄膜は、コンデンサ、サーミスタ、フィルタ及びメモリ等、種々の強誘電体デバイスの製造に用いられているが、鉛を含有しない材料使用の要求からＰＺＴ又はＰＬＺＴの機能に匹敵する機能を有するチタン酸バリウム（ＢａＴｉＯ3）を用いた薄膜の開発がなされている。 A thin film made of a ferroelectric material using Pb (Zr, Ti) O 3 (hereinafter referred to as PZT) or (Pb, La) (Zr, Ti) O 3 (hereinafter referred to as PLZT) includes a capacitor, a thermistor, Barium titanate (BaTiO 3 ) having a function comparable to that of PZT or PLZT is used because of the requirement of using materials that do not contain lead, although it is used for manufacturing various ferroelectric devices such as filters and memories. Thin films are being developed.
そのようなチタン酸バリウムを用いて薄膜を製造する方法として、後記する特許文献１にはＭＯＣＶＤ（Metal Organic Chemical Vapor Deposition）といった気相法を用いる方法が開示されている。 As a method for producing a thin film using such barium titanate, Patent Document 1 described later discloses a method using a vapor phase method such as MOCVD (Metal Organic Chemical Vapor Deposition).
すなわち、β−ジケトン系有機金属錯体であるＢａ（ＤＰＭ）2（ＤＰＭ：ジピバロイルメタン（（ＣＨ3）3・Ｃ・ＣＯ・ＣＨ2・ＣＯ・Ｃ・（ＣＨ3）3））、Ｓｒ（ＤＰＭ）2、Ｔｉ（Ｏ−ｉＰｒ）2（ＤＰＭ）2をそれぞれ適宜の溶媒に溶解させた３つの液体材料を予め用意しておき、各液体材料を所要の流量で混合器に導入して混合した後、得られた混合液を気化器に導入し、そこで所要温度まで昇温させて気化させることによって原料ガスを生成する。 That is, Ba (DPM) 2 (DPM: dipivaloylmethane ((CH 3 ) 3 · C · CO · CH 2 · CO · C · (CH 3 ) 3 )), which is a β-diketone organometallic complex Three liquid materials prepared by dissolving Sr (DPM) 2 and Ti (O-iPr) 2 (DPM) 2 in respective appropriate solvents are prepared in advance, and each liquid material is introduced into the mixer at a required flow rate. After mixing, the obtained mixed liquid is introduced into a vaporizer, where it is heated to a required temperature and vaporized to generate a raw material gas.
気化器には搬送ガスも導入されるようになっており、生成された原料ガスは搬送ガスによって、基板が収納された反応炉内へ給送される。この反応炉には酸素も供給されるようになっており、また、反応炉内の基板は加熱器によって略４５０℃に加熱されるようになっている。 A carrier gas is also introduced into the vaporizer, and the generated raw material gas is fed into the reaction furnace in which the substrate is accommodated by the carrier gas. Oxygen is also supplied to the reaction furnace, and the substrate in the reaction furnace is heated to about 450 ° C. by a heater.
そして、反応炉内に給送された原料ガスは反応炉に供給される酸素と混合され、加熱器によって加熱された基板の表面で酸化・分解反応が進行することにより、基板表面にＢＳＴ（チタン酸バリウム・ストロンチウム）膜が堆積する。このようにして生成されたＢＳＴ膜はアモルファス構造であるので、５００℃から６００℃で３０分間程度アニール化処理することにより単結晶化させる。
しかしながら、このようにペロブスカイト型の結晶構造を有する金属酸化物、すなわちペロブスカイト酸化物の薄膜を気相法で製造する従来の方法にあっては、気相法を実施するための製造装置に要するコストが高いのに加え、当該製造装置によって一度に処理できる基板の枚数が少ないため製造コストが嵩むという問題があった。 However, in the conventional method of manufacturing a metal oxide having a perovskite crystal structure, that is, a thin film of perovskite oxide, by a vapor phase method, the cost required for a manufacturing apparatus for performing the vapor phase method In addition, the manufacturing cost increases because the number of substrates that can be processed at one time by the manufacturing apparatus is small.
一方、例えば有機金属化合物を所要の溶媒に溶解させた溶液を基板の表面又は該基板上に形成された基層の表面に塗布する液相法にあっては、かかる問題を解決することはできるものの、塗布した後に基板を略１０００℃以上の高温で焼成しなければならず、そのような高温で焼成した薄膜は前記基板又は基層と当該薄膜との界面で反応が生起され、焼成した膜の機能が低下又は損失するという問題があった。 On the other hand, for example, in a liquid phase method in which a solution in which an organometallic compound is dissolved in a required solvent is applied to the surface of a substrate or the surface of a base layer formed on the substrate, such a problem can be solved. After the coating, the substrate must be fired at a high temperature of about 1000 ° C. or higher, and the thin film fired at such a high temperature causes a reaction at the interface between the substrate or the base layer and the thin film, and the fired film functions. There has been a problem of decrease or loss.
本発明は、斯かる事情に鑑みてなされたものであって、液相法によって所要の機能を有するペロブスカイト酸化物薄膜を製造する方法、及び当該方法により製造されたペロブスカイト酸化物薄膜を提供する。 This invention is made | formed in view of such a situation, Comprising: The method of manufacturing the perovskite oxide thin film which has a required function by a liquid phase method, and the perovskite oxide thin film manufactured by the said method are provided.
本発明者らは、所定の基板又は適宜の基板の表面に成膜した所定の基層上に、直径がナノメートル（ｎｍ）サイズの結晶粒子（以後、ナノ結晶粒子ともいう）を堆積させることにより、１０００℃未満の温度で焼成して結晶を生長させるとともに生長した各結晶の結晶方位が揃ったエピタキシャルな膜を生成することができ、これによって単結晶膜と同等の機能を示すという知見を得て本発明を完成するに至った。 The present inventors deposit nanometer (nm) diameter crystal particles (hereinafter also referred to as nanocrystal particles) on a predetermined substrate or a predetermined base layer formed on the surface of an appropriate substrate. , It can be baked at a temperature of less than 1000 ° C. to grow crystals and to produce an epitaxial film in which the crystal orientations of the grown crystals are aligned, thereby obtaining the same function as a single crystal film. The present invention has been completed.
すなわち、（１）本発明に係るペロブスカイト酸化物薄膜の製造方法は、一般式ＭＴｉＯ3で表される第１ペロブスカイト酸化物（Ｍは、Ｂａ、Ｓｒ若しくはＣａ、又はそれらの混合物を表す）を主成分としたエピタキシャルな薄膜を製造する方法において、前記第１ペロブスカイト酸化物を主成分とし、適宜直径の結晶粒子群を所定の溶媒に分散させた分散液を調製する工程と、前記結晶粒子群の調製に用いた第１ペロブスカイト酸化物とは異なる適宜の第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上、又は、適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に、前記分散液中の結晶粒子群を堆積させる堆積工程と、堆積させて得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成する焼成工程とを実施することを特徴とする。 That is, (1) the method for producing a perovskite oxide thin film according to the present invention mainly uses a first perovskite oxide represented by the general formula MTiO 3 (M represents Ba, Sr or Ca, or a mixture thereof). In the method for producing an epitaxial thin film as a component, a step of preparing a dispersion in which the first perovskite oxide is a main component and a crystal particle group having an appropriate diameter is dispersed in a predetermined solvent; The second perovskite oxide is formed on a first substrate made of a single crystal mainly composed of an appropriate second perovskite oxide different from the first perovskite oxide used for the preparation, or on an appropriate second substrate. A deposition step of depositing a group of crystal particles in the dispersion on an epitaxial base layer mainly composed of an object, and a first substrate or a second substrate obtained by the deposition as 1 Which comprises carrying out the firing step of firing at a suitable temperature below 00 ° C..
本発明のペロブスカイト酸化物薄膜の製造方法にあっては、例えばＢａＴｉＯ3というような成膜対象の第１ペロブスカイト酸化物を主成分とし、ナノメートルサイズの適宜直径を有する結晶粒子群を所定の溶媒に分散させた分散液を調製する。 In the method for producing a perovskite oxide thin film of the present invention, for example, a first perovskite oxide to be deposited such as BaTiO 3 as a main component and a crystal particle group having an appropriate diameter of nanometer size is used as a predetermined solvent. A dispersion liquid is prepared in the form of a dispersion.
そのような分散液を調製するには、例えばＴｉおよび他の金属のアルコキシドをアルコール系混合溶媒に互いに等モル量溶解させた前駆体溶液を適宜温度で加水分解する工程を含むゾル−ゲル法によって行うことができる。 In order to prepare such a dispersion, for example, by a sol-gel method including a step of hydrolyzing a precursor solution in which equimolar amounts of Ti and other metal alkoxides are dissolved in an alcohol-based mixed solvent at an appropriate temperature. It can be carried out.
次に、例えばＳｒＴｉＯ3というように、第１ペロブスカイト酸化物とは異なる適宜の第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上に、前述した分散液中の結晶粒子群を堆積させる。結晶粒子群を堆積するには後述する電気泳動電着法、又は、分散液中に基板を浸漬させる、所謂ディップ法によって行うことができる。
結晶粒子群の堆積はまた、例えばシリコンといった適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に実施することもできる。
Next, on the first substrate made of a single crystal mainly composed of an appropriate second perovskite oxide different from the first perovskite oxide, for example, SrTiO 3 , the above-described crystal particle group in the dispersion is added. Deposit. The crystal particle group can be deposited by an electrophoretic electrodeposition method to be described later or a so-called dip method in which a substrate is immersed in a dispersion.
The deposition of the crystal grain group can also be performed on an epitaxial base layer that is formed on an appropriate second substrate such as silicon and has the second perovskite oxide as a main component.
このような第１基板又は基層を構成する第２ペロブスカイト酸化物は、結晶の単位格子の構造が第１ペロブスカイト酸化物を構成する結晶の単位格子の構造と略同一の立方晶又は正方晶であり、また、両者の格子定数が十分に近いものが選択される。
ここで格子定数が十分に近いとは、両格子定数の差が１０％以内であることをいう。
これによって、堆積工程において、第１ペロブスカイト酸化物を主成分とする結晶粒子がその方位を第１基板又は基層の結晶方位と略揃った様態で堆積されるのである。
The second perovskite oxide constituting the first substrate or base layer is a cubic or tetragonal crystal whose crystal unit cell structure is substantially the same as the crystal unit cell structure constituting the first perovskite oxide. In addition, those having sufficiently close lattice constants are selected.
Here, that the lattice constant is sufficiently close means that the difference between the two lattice constants is within 10%.
As a result, in the deposition step, crystal grains mainly composed of the first perovskite oxide are deposited in such a manner that the orientation thereof is substantially aligned with the crystal orientation of the first substrate or base layer.
このようにして結晶粒子群を堆積させた後、得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成することによって、第１ペロブスカイト酸化物が所要の機能を発揮するように活性化させる。 After the crystal particle group is deposited in this manner, the first substrate or the second substrate obtained is fired at an appropriate temperature of less than 1000 ° C. so that the first perovskite oxide exhibits a required function. Activate.
このように従来の焼成温度に比べて低い温度で焼成するため、第１基板の表面又は前述した基層の表面と第１ペロブスカイト酸化物薄膜との界面において反応が発生することが防止され、第１ペロブスカイト酸化物薄膜の機能が低下することが回避される。 As described above, since the firing is performed at a temperature lower than the conventional firing temperature, it is possible to prevent a reaction from occurring at the interface between the surface of the first substrate or the surface of the base layer and the first perovskite oxide thin film. It is avoided that the function of the perovskite oxide thin film deteriorates.
一方、かかる焼成工程中、堆積された結晶粒子の内、第１基板又は基層の結晶方位と揃っていない結晶粒子が回動等を行って、その結晶方位が第１基板又は基層の結晶方位と揃うため、エピタキシャルな薄膜が形成される。
また、焼成工程によって結晶粒子が成長するため、第１ペロブスカイト酸化物薄膜が緻密化される。
これによって、第１ペロブスカイト酸化物薄膜上に他のペロブスカイト酸化物薄膜を重層させる積層構造を、両薄膜間の界面での反応を防止しつつ構築することができる。
On the other hand, during the firing step, among the deposited crystal particles, the crystal particles that are not aligned with the crystal orientation of the first substrate or the base layer rotate, and the crystal orientation becomes the crystal orientation of the first substrate or base layer. As a result, an epitaxial thin film is formed.
Further, since the crystal grains grow by the firing process, the first perovskite oxide thin film is densified.
Thus, a laminated structure in which another perovskite oxide thin film is overlaid on the first perovskite oxide thin film can be constructed while preventing a reaction at the interface between the two thin films.
（２）また、本発明に係るペロブスカイト酸化物薄膜の製造方法は必要に応じて、前記分散液として、平均直径が略５ｎｍ以上略１５ｎｍ以下の適宜寸法の結晶粒子群を分散させたものを用いることを特徴とする。 (2) Further, in the method for producing a perovskite oxide thin film according to the present invention, a dispersion of crystal particles having an appropriate size having an average diameter of about 5 nm to about 15 nm is used as the dispersion as necessary. It is characterized by that.
本発明のペロブスカイト酸化物薄膜の製造方法にあっては、前述した分散液として、平均直径が略５ｎｍ以上略１５ｎｍ以下の適宜寸法の結晶粒子群を分散させたものを用いる。 In the method for producing a perovskite oxide thin film of the present invention, as the above-mentioned dispersion liquid, a dispersion of crystal particles having an appropriate size having an average diameter of about 5 nm to about 15 nm is used.
このように微小直径であり、運動の自由度が大きい結晶粒子群を第１基板上又は基層上に堆積させるため、結晶粒子はよりその方位を第１基板又は基層の結晶方位と揃えて堆積され易い。 In order to deposit a group of crystal grains having such a small diameter and a large degree of freedom of movement on the first substrate or the base layer, the crystal grains are deposited with the orientation more aligned with the crystal orientation of the first substrate or base layer. easy.
また、微小直径の結晶粒子にあってはより低い温度で焼成しても所要の機能を発揮させる活性化を行うことができる。従って、第１基板又は基層との界面における反応を更に防止することができる。 Further, in the case of a crystal particle having a small diameter, activation can be performed so that a required function can be exhibited even when firing at a lower temperature. Therefore, the reaction at the interface with the first substrate or the base layer can be further prevented.
（３）また、本発明に係るペロブスカイト酸化物薄膜の製造方法は必要に応じて、前記焼成工程は略４００℃以上略８００℃以下の適宜温度で行うことを特徴とする。 (3) Moreover, the manufacturing method of the perovskite oxide thin film based on this invention is characterized by performing the said baking process at the appropriate temperature of about 400 degreeC or more and about 800 degrees C or less as needed.
本発明のペロブスカイト酸化物薄膜の製造方法にあっては、略４００℃以上略８００℃以下の適宜温度で焼成を行う。
このように、従来の焼成温度より低い温度で焼成するため、第１基板又は基層との界面における反応を防止することができる。
また、焼成工程によって結晶粒子が成長するため、第１ペロブスカイト酸化物薄膜が緻密化される。これによって、第１ペロブスカイト酸化物薄膜上に他のペロブスカイト酸化物薄膜を重層させる積層構造を、両薄膜間の界面での反応を防止しつつ構築することができる。
In the method for producing a perovskite oxide thin film of the present invention, firing is performed at an appropriate temperature of about 400 ° C. or higher and about 800 ° C. or lower.
In this way, since the firing is performed at a temperature lower than the conventional firing temperature, the reaction at the interface with the first substrate or the base layer can be prevented.
Further, since the crystal grains grow by the firing process, the first perovskite oxide thin film is densified. Thus, a laminated structure in which another perovskite oxide thin film is overlaid on the first perovskite oxide thin film can be constructed while preventing a reaction at the interface between the two thin films.
（４）更に、本発明に係るペロブスカイト酸化物薄膜の製造方法は必要に応じて、前記堆積工程は、導電性の第１基板又は導電性の基層が形成された導電性の第２基板を用い、前記分散液中に浸漬された前記第１基板又は第２基板に所定の電圧を印加することによって行うことを特徴とする。 (4) Further, in the method for producing a perovskite oxide thin film according to the present invention, the deposition step uses a conductive first substrate or a conductive second substrate on which a conductive base layer is formed, as necessary. , By applying a predetermined voltage to the first substrate or the second substrate immersed in the dispersion.
本発明のペロブスカイト酸化物薄膜の製造方法にあっては、分散液中に浸漬された導電性の第１基板、又は導電性の基層が形成された導電性の第２基板に所定の電圧を印加して、分散液中の結晶粒子を第１基板上、又は第２基板に形成された基層上に堆積させる、所謂電気泳動電着によって堆積工程を実施する。 In the method for producing a perovskite oxide thin film according to the present invention, a predetermined voltage is applied to the conductive first substrate immersed in the dispersion or the conductive second substrate on which the conductive base layer is formed. Then, the deposition step is performed by so-called electrophoretic electrodeposition in which the crystal particles in the dispersion are deposited on the first substrate or the base layer formed on the second substrate.
電気泳動電着にて結晶粒子を堆積させる場合、所要形状のマスクを用いることによって堆積物をマスクに応じた形状になすことができる。また、印加する電圧、印加時間等を調整することにより、堆積物の厚さを容易に制御することができる。 When crystal particles are deposited by electrophoretic electrodeposition, the deposit can be shaped according to the mask by using a mask having a required shape. In addition, the thickness of the deposit can be easily controlled by adjusting the voltage to be applied, the application time, and the like.
（５）一方、本発明に係るペロブスカイト酸化物薄膜は、一般式ＭＴｉＯ3で表される第１ペロブスカイト酸化物（Ｍは、Ｂａ、Ｓｒ若しくはＣａ、又はそれらの混合物を表す）を主成分としたエピタキシャルな薄膜であって、前記第１ペロブスカイト酸化物を主成分とし、適宜直径の結晶粒子群を所定の溶媒に分散させた分散液中の前記結晶粒子群を、当該結晶粒子群の調製に用いた第１ペロブスカイト酸化物とは異なる第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上、又は、適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に堆積させ、得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成してなることを特徴とする。 (5) On the other hand, the perovskite oxide thin film according to the present invention is mainly composed of the first perovskite oxide represented by the general formula MTiO 3 (M represents Ba, Sr or Ca, or a mixture thereof). An epitaxial thin film comprising the first perovskite oxide as a main component and the crystal particle group in a dispersion in which a crystal particle group having an appropriate diameter is dispersed in a predetermined solvent is used for the preparation of the crystal particle group. Formed on a first substrate made of a single crystal mainly composed of a second perovskite oxide different from the first perovskite oxide, or on an appropriate second substrate, and the second perovskite oxide as a main component The first substrate or the second substrate obtained by being deposited on the epitaxial base layer is fired at an appropriate temperature of less than 1000 ° C.
本発明のペロブスカイト酸化物薄膜にあっては、第１ペロブスカイト酸化物を主成分とし、適宜直径の結晶粒子群を所定の溶媒に分散させた分散液中の前記結晶粒子群を、当該結晶粒子群の調製に用いた第１ペロブスカイト酸化物とは異なる第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上、又は、適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に堆積させ、得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成してなるため、前述した如く堆積工程において、第１ペロブスカイト酸化物を主成分とする結晶粒子がその方位を第１基板又は基層の結晶方位と揃えて堆積され易い。 In the perovskite oxide thin film of the present invention, the crystal particle group in a dispersion containing the first perovskite oxide as a main component and appropriately dispersed crystal particles having a diameter in a predetermined solvent is used as the crystal particle group. The second perovskite oxide is formed on a first substrate made of a single crystal mainly composed of a second perovskite oxide different from the first perovskite oxide used in the preparation of the second perovskite oxide, or on an appropriate second substrate. The first perovskite oxide is deposited on the epitaxial base layer containing as a main component and the obtained first or second substrate is baked at an appropriate temperature of less than 1000 ° C. Crystal grains having the main component are easily deposited with the orientation aligned with the crystal orientation of the first substrate or the base layer.
また、従来の焼成温度に比べて低い温度で焼成されているため、第１基板の表面又は基層の表面と第１ペロブスカイト酸化物薄膜との界面において反応が発生することが防止され、第１ペロブスカイト酸化物薄膜の機能が低下することが回避される。 Further, since the firing is performed at a temperature lower than the conventional firing temperature, it is possible to prevent a reaction from occurring at the interface between the surface of the first substrate or the surface of the base layer and the first perovskite oxide thin film, and the first perovskite. It is avoided that the function of the oxide thin film deteriorates.
一方、かかる焼成中、堆積された結晶粒子の内、第１基板又は基層の結晶方位と揃っていない結晶粒子が回動等を行って、その結晶方位が第１基板又は基層の結晶方位と揃うため、エピタキシャルな薄膜が得られる。
また、焼成工程によって結晶粒子が成長するため、第１ペロブスカイト酸化物薄膜が緻密化される。
On the other hand, during the firing, among the deposited crystal particles, the crystal particles that are not aligned with the crystal orientation of the first substrate or the base layer rotate and the crystal orientation is aligned with the crystal orientation of the first substrate or base layer. Therefore, an epitaxial thin film can be obtained.
Further, since the crystal grains grow by the firing process, the first perovskite oxide thin film is densified.
（６）また、本発明に係るペロブスカイト酸化物薄膜は必要に応じて、前記結晶粒子群の平均直径は略５ｎｍ以上略１５ｎｍ以下の適宜寸法であることを特徴とする。 (6) In addition, the perovskite oxide thin film according to the present invention is characterized in that the average diameter of the crystal particle group has an appropriate dimension of about 5 nm to about 15 nm as necessary.
本発明のペロブスカイト酸化物薄膜にあっては、結晶粒子群の平均直径は略５ｎｍ以上略１５ｎｍ以下の適宜寸法であるため、結晶粒子群の運動の自由度が大きく、当該結晶粒子はよりその方位を第１基板又は基層の結晶方位と略揃えた状態で堆積され、より均一にエピタキシャルな薄膜を形成することができる。
また、微小直径の結晶粒子にあってはより低い温度で焼成しても所要の機能を発揮させる活性化を行うことができる。従って、第１基板又は基層との界面における反応を更に防止することができる。
In the perovskite oxide thin film of the present invention, since the average diameter of the crystal particle group is an appropriate dimension of about 5 nm to about 15 nm, the degree of freedom of movement of the crystal particle group is large, and the crystal particle has more orientation. Can be deposited in a state substantially aligned with the crystal orientation of the first substrate or base layer, and a more uniform epitaxial thin film can be formed.
Further, in the case of a crystal particle having a small diameter, activation can be performed so that a required function can be exhibited even when firing at a lower temperature. Therefore, the reaction at the interface with the first substrate or the base layer can be further prevented.
（７）また、本発明に係るペロブスカイト酸化物薄膜は必要に応じて、堆積させて得られた第１基板又は第２基板を略４００℃以上略８００℃以下の適宜温度で焼成してなることを特徴とする。 (7) The perovskite oxide thin film according to the present invention is formed by firing the first substrate or the second substrate obtained by deposition at an appropriate temperature of about 400 ° C. to about 800 ° C., if necessary. It is characterized by.
本発明のペロブスカイト酸化物薄膜にあっては、堆積させて得られた第１基板又は第２基板を略４００℃以上略８００℃以下の適宜温度で焼成してなるため、第１基板又は基層との界面における反応を防止することができる。 In the perovskite oxide thin film of the present invention, the first substrate or the second substrate obtained by deposition is baked at an appropriate temperature of about 400 ° C. or higher and about 800 ° C. or lower. Reaction at the interface can be prevented.
また、焼成によって結晶粒子が成長するため、第１ペロブスカイト酸化物薄膜が緻密化される。これによって、第１ペロブスカイト酸化物薄膜上に他のペロブスカイト酸化物薄膜を重層させる積層構造を、両薄膜間の界面での反応を防止しつつ構築することができる。 Moreover, since crystal grains grow by firing, the first perovskite oxide thin film is densified. Thus, a laminated structure in which another perovskite oxide thin film is overlaid on the first perovskite oxide thin film can be constructed while preventing a reaction at the interface between the two thin films.
（８）更に、本発明に係るペロブスカイト酸化物薄膜は必要に応じて、前記第１基板又は前記第２基板及び基層は導電性になしてあり、前記分散液中に浸漬された第１基板又は第２基板に所定の電圧を印加することによって当該第１基板又は第２基板に結晶粒子群を堆積させてなることを特徴とする。 (8) Furthermore, in the perovskite oxide thin film according to the present invention, if necessary, the first substrate or the second substrate and the base layer are conductive, and the first substrate immersed in the dispersion or A crystal grain group is deposited on the first substrate or the second substrate by applying a predetermined voltage to the second substrate.
本発明のペロブスカイト酸化物薄膜にあっては、分散液中に浸漬された第１基板または第２基板に所定の電圧を印加することによって当該第１基板又は基層に結晶粒子群を堆積させてなるため、所要形状のマスクを用いることによって堆積物をマスクに応じた形状になすことができる。また、印加する電圧、印加時間等を調整することにより、堆積物の厚さを容易に制御することができる。 In the perovskite oxide thin film of the present invention, a predetermined voltage is applied to the first substrate or the second substrate immersed in the dispersion to deposit crystal particles on the first substrate or the base layer. Therefore, the deposit can be formed into a shape corresponding to the mask by using a mask having a required shape. In addition, the thickness of the deposit can be easily controlled by adjusting the voltage to be applied, the application time, and the like.
（９）ところで、本発明に係るペロブスカイト酸化物薄膜は、前記第１ペロブスカイト酸化物はチタン酸バリウムであることを特徴とする。
本発明のペロブスカイト酸化物薄膜にあっては、前記第１ペロブスカイト酸化物はチタン酸バリウムであるので、強誘電体の薄膜を得ることができる。
(9) The perovskite oxide thin film according to the present invention is characterized in that the first perovskite oxide is barium titanate.
In the perovskite oxide thin film of the present invention, since the first perovskite oxide is barium titanate, a ferroelectric thin film can be obtained.
本発明に係るペロブスカイト酸化物薄膜の製造方法を図１に基づいて説明する。
図１は、本発明に係るペロブスカイト酸化物薄膜の製造手順を示すフローチャートである。
図１に示したように、成膜対象のペロブスカイト酸化物を主成分とし、平均直径が略５ｎｍ以上略１５ｎｍ以下、好ましくは略５ｎｍ以上略１０ｎｍ以下の適宜直径のナノ結晶粒子を所定溶媒中に分散させた分散液を調製する（ステップＳ１）。
The manufacturing method of the perovskite oxide thin film based on this invention is demonstrated based on FIG.
FIG. 1 is a flowchart showing a procedure for producing a perovskite oxide thin film according to the present invention.
As shown in FIG. 1, nanocrystalline particles having an appropriate diameter mainly composed of a perovskite oxide to be deposited and having an average diameter of about 5 nm to about 15 nm, preferably about 5 nm to about 10 nm, in a predetermined solvent. A dispersed dispersion is prepared (step S1).
かかるナノ結晶粒子には、後述する基層とすべく所要量のＮｂを導入させてもよい。Ｎｂの導入はナノ結晶粒子を調製する際に行ってもよいし、ナノ結晶粒子の分散液に添加しておき、後述する堆積を行う際に行うようにしてもよい。 A necessary amount of Nb may be introduced into the nanocrystal particles to form a base layer described later. Nb may be introduced when preparing the nanocrystal particles, or may be added to the dispersion liquid of the nanocrystal particles, and may be performed when the deposition described later is performed.
次に、この分散液中に、例えば、対象電極としての所定材料の基板と対向電極とを浸漬させ、両電極間に所定の電圧を印加することによって前記基板の表面に前記ナノ結晶粒子を、乾燥時の厚さが数十ｎｍ〜数百ｎｍとなるように堆積させる（ステップＳ２）。 Next, in this dispersion, for example, a substrate of a predetermined material as a target electrode and a counter electrode are immersed, and the nanocrystal particles are applied to the surface of the substrate by applying a predetermined voltage between both electrodes. It is deposited so that the thickness at the time of drying is several tens nm to several hundreds nm (step S2).
なお、かかる堆積は、前述した分散液に基板を所定時間浸漬させるディップ法によっても行うことができる。
このようにして堆積させた基板を分散液から取り出して乾燥させた後、酸化雰囲気中又は中性雰囲気中、略４００℃以上略８００℃以下の適宜温度で焼成して所要の薄膜を得る（ステップＳ３）。
Such deposition can also be performed by a dipping method in which the substrate is immersed in the dispersion liquid described above for a predetermined time.
The substrate thus deposited is taken out from the dispersion and dried, and then fired at an appropriate temperature of about 400 ° C. to about 800 ° C. in an oxidizing atmosphere or a neutral atmosphere to obtain a required thin film (step) S3).
これによって、基板上に各ナノ結晶粒子の結晶方位が揃ったエピタキシャルな薄膜を生成することができ、該薄膜は、単結晶的物性、結晶異方性物性といった所要の機能を発揮する。
また、焼成温度が略４００℃以上略８００℃以下と低いため、生成した薄膜と基板との界面において反応が発生することが回避される。
以下、前述した各工程について詳述する。
As a result, an epitaxial thin film in which the crystal orientations of the nanocrystal particles are aligned can be formed on the substrate, and the thin film exhibits required functions such as single crystal physical properties and crystal anisotropic physical properties.
In addition, since the firing temperature is as low as about 400 ° C. or more and about 800 ° C. or less, it is avoided that a reaction occurs at the interface between the thin film produced and the substrate.
Hereinafter, each process mentioned above is explained in full detail.
（ナノ結晶粒子分散液の調製）
薄膜に係るペロブスカイト酸化物は、一般式ＭＴｉＯ3で表すことができ、Ｍは、Ｂａ、Ｓｒ又はＣａを表す。従って、ＢａＴｉＯ3、ＳｒＳｉＯ3、ＣａＴｉＯ3は、対象とするペロブスカイト酸化物に含まれる。さらに、Ｍは、Ｂａ、Ｓｒ又はＣａの混合系を表し、したがって、例えば、Ｂａ1-xＣａxＴｉＯ3、Ｂａ1-x-yＣａxＳｒyＴｉＯ3などの構造式で表されるものも本発明の対象とするペロブスカイト酸化物に含まれる。
(Preparation of nanocrystal particle dispersion)
The perovskite oxide according to the thin film can be represented by the general formula MTiO 3 , where M represents Ba, Sr or Ca. Therefore, BaTiO 3 , SrSiO 3 , and CaTiO 3 are included in the perovskite oxide of interest. Furthermore, M book, Ba, represent mixed system of Sr or Ca, therefore, for example, also those represented by the structural formula such as Ba 1-x Ca x TiO 3 , Ba 1-xy Ca x Sr y TiO 3 It is contained in the perovskite oxide which is the subject of the invention.
ペロブスカイト酸化物によるエピタキシャルな薄膜の製造において出発原料となるのは、対象とするペロブスカイト酸化物のナノ結晶粒子である。
かかるナノ結晶粒子群の平均直径は、前述した如く略５ｎｍ以上略１５ｎｍ以下が好ましく、より好ましくは、略５ｎｍ以上略１０ｎｍ以下である。
In the production of an epitaxial thin film using perovskite oxide, the starting material is nanocrystal particles of the target perovskite oxide.
As described above, the average diameter of the nanocrystal particle group is preferably about 5 nm to about 15 nm, and more preferably about 5 nm to about 10 nm.
ここで、平均直径が略５ｎｍ未満のナノ結晶粒子にあっては高濃度分散液の作製が困難であり、単位体積の分散液中に含まれる結晶粒子質量が小さいという不都合がある一方、平均直径が略１５ｎｍを超えるナノ結晶粒子にあっては、低温でのエピタキシャル化が困難であり、１０００℃を越える温度で焼成しなければならないという不都合がある。 Here, in the case of nanocrystal particles having an average diameter of less than about 5 nm, it is difficult to prepare a high-concentration dispersion, and there is a disadvantage that the mass of crystal particles contained in a unit volume of dispersion is small. However, in the case of nanocrystal particles exceeding 15 nm, it is difficult to epitaxialize at a low temperature, and there is an inconvenience that they must be fired at a temperature exceeding 1000 ° C.
一方、平均直径を略１０ｎｍ以下にした場合、適切な濃度を持つ分散液の作製が容易であり、かつ低温でのエピタキシャル化が可能という優れた効果を奏する。
かかる直径のナノ結晶粒子を調製するには、例えばゾル−ゲル法を用いることができる。
On the other hand, when the average diameter is about 10 nm or less, it is easy to produce a dispersion having an appropriate concentration, and an excellent effect is possible in that it can be epitaxialized at a low temperature.
In order to prepare nanocrystal particles having such a diameter, for example, a sol-gel method can be used.
ここで、ゾル−ゲル法とは、チタン酸バリウムの場合、Ｔｉおよび他の金属のアルコキシド（好ましくは、例えば、チタンイソプロポキシド、バリウムエトキシドなど）をアルコール系混合溶媒（好ましくはメタノール／メトキシエタノール混合溶媒）に等モル量（好ましくは、０．５〜１．２ｍｏｌ／Ｌ）溶解した前駆体溶液を適宜温度（好ましくは−３０°〜０℃）で加水分解する工程を含むものである。 Here, in the case of barium titanate, the sol-gel method refers to an alkoxide of Ti and other metals (preferably, for example, titanium isopropoxide, barium ethoxide, etc.) mixed with an alcohol-based mixed solvent (preferably methanol / methoxy). It includes a step of hydrolyzing a precursor solution dissolved in an equimolar amount (preferably 0.5 to 1.2 mol / L) in an ethanol mixed solvent) at an appropriate temperature (preferably −30 ° to 0 ° C.).
具体的には次のような操作を行う。
図２は、ゾル−ゲル法にてナノ結晶粒子液を調製する手順を示すフローチャートである。
図２に示したように、例えば、容量比でメタノール：２−メトキシメタノール（以後、ＥＧＭＭＥという）＝３：２となるように混合した混合液に、ジエトキシバリウム（Ｂａ（ＯＣ2Ｈ5）2）を添加して略２４時間撹拌した後、これにテトライソプロポキシチタン（Ｔｉ（Ｏ-ｉ-Ｃ3Ｈ7）4）をモル濃度比で、Ｂａ：Ｔｉ＝１：１になるように添加して略２４時間撹拌することによって前駆体溶液を調製する。このとき前駆体溶液の濃度は１．１ｍｏｌ／Ｌである。なお、前駆体溶液の調製操作は窒素ガス雰囲気中で実施する。
Specifically, the following operation is performed.
FIG. 2 is a flowchart showing a procedure for preparing a nanocrystal particle liquid by a sol-gel method.
As shown in FIG. 2, for example, diethoxybarium (Ba (OC 2 H 5 )) was added to a mixed solution in which methanol: 2-methoxymethanol (hereinafter referred to as EGMME) = 3: 2 by volume ratio. 2 ) was added and stirred for about 24 hours, and then tetraisopropoxytitanium (Ti (Oi-C 3 H 7 ) 4 ) was added to this at a molar concentration ratio of Ba: Ti = 1: 1. The precursor solution is prepared by adding and stirring for approximately 24 hours. At this time, the concentration of the precursor solution is 1.1 mol / L. In addition, preparation operation of a precursor solution is implemented in nitrogen gas atmosphere.
次に、体積比で純水：ＥＧＭＭＥ＝１：１になるように両者を混合させた加水分解用溶液を予め用意しておき、この加水分解用溶液を加水分解用溶液中の水がＢａに対してモル濃度比で例えば１０倍となるように添加しつつ、略−３０℃で１０分間、前記前駆体溶液の加水分解を行うことによって、バリウム−酸化チタン酸が重合してなり、直径が数ｎｍ〜十数ｎｍのコロイド、即ちナノサイズのコロイドを生成させた後、９０℃で１時間程度、エージングを行ってゲル化させる。
そして、得られたゲルから分離した液体を除去し、適宜の溶媒を添加した後、超音波を２４時間程度印加することによってナノ結晶粒子の分散液を得る。
Next, a hydrolysis solution in which both are mixed so that the volume ratio is pure water: EGMME = 1: 1 is prepared in advance, and the water in the hydrolysis solution is changed to Ba in the hydrolysis solution. On the other hand, the precursor solution is hydrolyzed at approximately −30 ° C. for 10 minutes while being added so that the molar concentration ratio is, for example, 10 times. After a colloid of several nm to several tens of nm, that is, a nano-sized colloid is formed, it is gelled by aging at 90 ° C. for about 1 hour.
And after removing the liquid isolate | separated from the obtained gel and adding a suitable solvent, the dispersion liquid of a nanocrystal particle | grain is obtained by applying an ultrasonic wave for about 24 hours.
前述した溶媒としては、エタノール、プロパノール、EGMME等を用いることができる。
このとき、例えば、エージングの温度をより高温にすることによりナノ結晶粒子の直径を小さくすることができ、エージングの温度をより低温にすることによりナノ結晶粒子の直径を大きくすることができる。
As the above-mentioned solvent, ethanol, propanol, EGMME or the like can be used.
At this time, for example, the diameter of the nanocrystal particles can be reduced by increasing the aging temperature, and the diameter of the nanocrystal particles can be increased by decreasing the aging temperature.
また、このようにして調製した分散液には所要の直径より大きな直径のナノ結晶粒子が存在する場合があるが、分散液を適宜時間静置することによって当該ナノ結晶粒子を沈殿させ、上部液層部分を分取することによって当該ナノ結晶粒子を除去することができる。 Further, in the dispersion prepared in this way, nanocrystal particles having a diameter larger than a required diameter may be present, but by allowing the dispersion to stand for an appropriate period of time, the nanocrystal particles are precipitated, The nanocrystal particles can be removed by separating the layer portion.
（堆積）
基板への堆積は電気泳動電着（ＥＰＤ）法にて行うことができる。
図３は、堆積に用いる電気泳動装置の構成を説明する模式的説明図であり、図中、１は貯留槽である。貯留槽１内には、前述した如くナノ結晶粒子を分散させた分散液Ｓが貯留してあり、該分散液Ｓ中に、正極４及び負極３が所定の距離を隔てて対向配置してある。正極４及び負極３には電源装置２から直流電圧が所定時間だけ印加されるようになっており、電源装置２から正極４及び負極３に直流電圧が印加された場合、分散液Ｓ中のナノ結晶粒子Ｐ，Ｐ，…が電気泳動によって負極３（又は正極４）の表面に移動してそこに堆積し、薄膜を形成する。
このとき、堆積対象の電極の表面に所要パターンのマスクを予め形成しておくことにより、所要パターンのナノ結晶粒子膜を生成することができる。
なお、膜厚は印加時間及び／又は印加電圧によって調整することができる。
(Deposition)
Deposition on the substrate can be performed by electrophoretic electrodeposition (EPD).
FIG. 3 is a schematic explanatory view for explaining the configuration of the electrophoresis apparatus used for deposition, in which 1 is a storage tank. In the storage tank 1, the dispersion liquid S in which the nanocrystal particles are dispersed is stored as described above, and the positive electrode 4 and the negative electrode 3 are arranged to face each other with a predetermined distance in the dispersion liquid S. . A direct current voltage is applied to the positive electrode 4 and the negative electrode 3 from the power supply device 2 for a predetermined time, and when a direct current voltage is applied to the positive electrode 4 and the negative electrode 3 from the power supply device 2, The crystal particles P, P,... Migrate to the surface of the negative electrode 3 (or the positive electrode 4) by electrophoresis and deposit there to form a thin film.
At this time, a nanocrystal particle film having a required pattern can be generated by previously forming a mask having a required pattern on the surface of the electrode to be deposited.
The film thickness can be adjusted by the application time and / or the applied voltage.
図３に示したように、チタン酸バリウムを主成分とするナノ結晶粒子Ｐ，Ｐ，…にあっては、有機溶媒に分散させた場合はプラスに帯電しているので、電気泳動によって負極３に堆積する。 As shown in FIG. 3, the nanocrystal particles P, P,... Mainly composed of barium titanate are positively charged when dispersed in an organic solvent. To deposit.
従って、このような電気泳動を実施するに先立って、ナノ結晶粒子Ｐ，Ｐ，…が堆積する側の電極、図３にあっては負極３を、本発明に係るペロブスカイト酸化物薄膜の基板とすべく、例えばＳｒＴｉＯ3といったペロブスカイト型の結晶構造を有する単結晶に微量のＮｂをドープしてなる基板によって構成しておく。 Therefore, prior to performing such electrophoresis, the electrode on the side on which the nanocrystal particles P, P,... Are deposited, the negative electrode 3 in FIG. 3, and the substrate of the perovskite oxide thin film according to the present invention. For example, a single crystal having a perovskite crystal structure, such as SrTiO 3, is made of a substrate doped with a small amount of Nb.
このように、ペロブスカイト型の結晶構造を有する単結晶の基板上に、ＢａＴｉＯ3のナノ結晶粒子を堆積させるため、各ナノ結晶粒子はその結晶方位を基板の結晶方位と揃えて堆積し易い。
また、堆積された際に結晶方位が揃っていない場合であっても、後述するような焼成操作中に、当該ナノ結晶粒子が回動して結晶方位が揃うものと考えられる。
In this way, since BaTiO 3 nanocrystal particles are deposited on a single crystal substrate having a perovskite crystal structure, each nanocrystal particle is easily deposited with its crystal orientation aligned with the crystal orientation of the substrate.
Further, even when the crystal orientations are not aligned when deposited, it is considered that the nanocrystal particles are rotated to align the crystal orientations during the firing operation as described later.
ところで、前述した負極３は、例えばシリコンというように半導電性を有する材料を用いてなる基板の表面に、ＳｒＴｉＯ3に微量のＮｂをドープしてなるペロブスカイト型の結晶構造を有し、エピタキシャルで導電性を具備する基層を形成してなるものであってもよい。 By the way, the negative electrode 3 described above has a perovskite crystal structure in which a small amount of Nb is doped into SrTiO 3 on the surface of a substrate made of a semiconductive material such as silicon, and is epitaxial. It may be formed by forming a base layer having conductivity.
かかる基層は、例えば、Ｓｒ（ＯＣ2Ｈ5）2及びＴｉ（Ｏ-ｉ-Ｃ3Ｈ7）4をEGMMEといった有機溶媒に溶解させた溶液に適量の無水酢酸及び粘性調整剤、例えばポリエチレングリコール（PEG）を加え、例えばスピンコート法によりシリコン基板の表面に塗布した後、この基板を１０００℃程度の温度で焼成することによって形成することができる。 Such a base layer is prepared by, for example, adding an appropriate amount of acetic anhydride and a viscosity modifier such as polyethylene glycol in a solution in which Sr (OC 2 H 5 ) 2 and Ti (Oi-C 3 H 7 ) 4 are dissolved in an organic solvent such as EGMME. (PEG) can be added and applied to the surface of the silicon substrate by, for example, spin coating, and then the substrate can be baked at a temperature of about 1000 ° C.
また、前同様の操作を行って調製したＳｒＴｉＯ3のナノ結晶粒子の分散液を予め用意しておき、電気泳動電着法にて堆積させた後、酸化雰囲気中又は中性雰囲気中、略４００℃以上略８００℃以下の適宜温度で焼成することによってＳｒＴｉＯ3の基層を作製してもよい。 In addition, after preparing a dispersion of SrTiO 3 nanocrystal particles prepared by performing the same operation as described above and depositing it by an electrophoretic electrodeposition method, it is approximately 400 in an oxidizing atmosphere or a neutral atmosphere. The base layer of SrTiO 3 may be produced by firing at an appropriate temperature of not less than 800 ° C. and not more than 800 ° C.
なお、このような基板又は基層に用いる材料としては、ＳｒＴｉＯ3以外にも、例えばＬａ0.5Ｓｒ0.5ＣｏＯ3、Ｌａ0.7Ｓｒ0.3ＭｎＯ3、ＬａＮｉＯ3、ＢａＰｂＯ3というように、その結晶の単位格子の構造が薄膜に係るペロブスカイト酸化物（第１ペロブスカイト酸化物）を構成する結晶の単位格子の構造と略同一の立方晶又は正方晶であり、また、両者の格子定数が十分に近いペロブスカイト酸化物（第２ペロブスカイト酸化物）を用いることができる。
ここで格子定数が十分に近いとは、両格子定数の差が１０％以内であることをいう。
In addition to SrTiO 3 , the material used for such a substrate or base layer is, for example, La 0.5 Sr 0.5 CoO 3 , La 0.7 Sr 0.3 MnO 3 , LaNiO 3 , BaPbO 3 , the unit cell of the crystal. A perovskite oxide having substantially the same cubic or tetragonal structure as the unit cell structure of the crystal constituting the perovskite oxide (first perovskite oxide) relating to the thin film, and having a lattice constant close enough to each other ( Second perovskite oxide) can be used.
Here, that the lattice constant is sufficiently close means that the difference between the two lattice constants is within 10%.
ところで、図３に示した電気泳動装置では、正極４及び負極３を分散液Ｓ中に浸漬させるようになしてあるが、本発明はこれに限らず、貯留槽１の内周壁に正極４を着脱可能に予め固定しておくようにしてもよいし、貯留槽１の内周壁を正極で構成するようになしてもよい。
一方、１００ｎｍ以下の厚さであって、マスクを用いない場合は、前述した分散液に基板を所定時間浸漬させるディップ法によっても行うことができる。
Incidentally, in the electrophoresis apparatus shown in FIG. 3, the positive electrode 4 and the negative electrode 3 are immersed in the dispersion S. However, the present invention is not limited to this, and the positive electrode 4 is provided on the inner peripheral wall of the storage tank 1. You may make it fix beforehand so that attachment or detachment is possible, and you may make it comprise the inner peripheral wall of the storage tank 1 with a positive electrode.
On the other hand, when the thickness is 100 nm or less and a mask is not used, it can also be performed by a dipping method in which the substrate is immersed in the above-described dispersion for a predetermined time.
（焼成）
次に、このような電気泳動電着法によってナノ結晶粒子の薄膜が形成された基板を焼成することによって、所要の機能を発揮し得るようになす、所謂活性化を行ってペロブスカイト酸化物薄膜を得る。
(Baking)
Next, by firing the substrate on which the nanocrystalline particle thin film is formed by such an electrophoretic electrodeposition method, the perovskite oxide thin film is formed by performing so-called activation so that the required function can be exhibited. obtain.
焼成は略４００℃以上略８００℃以下の適宜温度で行う。かかる焼成によって薄膜を構成する各ナノ結晶粒子が生長するため、薄膜が緻密化される。 Firing is performed at an appropriate temperature of about 400 ° C. to about 800 ° C. Since each nanocrystal particle which comprises a thin film grows by this baking, a thin film is densified.
ここで、焼成温度が略４００℃未満の場合は、焼成された薄膜が所要の機能を発揮することができず、焼成温度が略８００℃を超えた場合は、基板の表面又は前述した基層の表面とペロブスカイト酸化物薄膜との界面において反応が発生するため、ペロブスカイト酸化物薄膜の機能が低下又は損失する。 Here, when the firing temperature is less than about 400 ° C., the fired thin film cannot perform the required function, and when the firing temperature exceeds about 800 ° C., the surface of the substrate or the above-described base layer Since a reaction occurs at the interface between the surface and the perovskite oxide thin film, the function of the perovskite oxide thin film is reduced or lost.
このように、略４００℃以上略８００℃以下と従来の焼成温度に比べて低い温度で焼成することができるため、基板の表面又は前述した基層の表面とペロブスカイト酸化物薄膜との界面において反応が発生することが防止され、ペロブスカイト酸化物薄膜の機能が低下することが回避される。 Thus, since it can be fired at a temperature of about 400 ° C. or higher and about 800 ° C. or lower, which is lower than the conventional baking temperature, there is a reaction at the substrate surface or the interface between the surface of the base layer and the perovskite oxide thin film. Generation | occurrence | production is prevented and it is avoided that the function of a perovskite oxide thin film falls.
更に、前述した如くペロブスカイト酸化物薄膜が緻密化されることにより、チタン酸バリウムからなる当該ペロブスカイト酸化物薄膜上に他のペロブスカイト酸化物薄膜を重層させる積層構造を、両薄膜間の界面での反応を防止しつつ構築することができる。
次に、本発明方法によってペロブスカイト酸化物薄膜を製造した結果について説明する。
Furthermore, as described above, the perovskite oxide thin film is densified, so that a layered structure in which another perovskite oxide thin film is formed on the perovskite oxide thin film made of barium titanate is reacted at the interface between the two thin films. It can be constructed while preventing this.
Next, the result of manufacturing a perovskite oxide thin film by the method of the present invention will be described.
ペロブスカイト酸化物薄膜としてチタン酸バリウム（ＢａＴｉＯ3）の成膜に適用させた場合について説明する。
薄膜の形成には、（００１）ＳｒＴｉＯ3にＮｂを導入してなる基板、及びＢａＴｉＯ3からなり平均直径が８ｎｍから１０ｎｍのナノ結晶粒子を用いた。ナノ結晶粒子は、図２に示したゾル−ゲル法に従って調製した。
A case where the perovskite oxide thin film is applied to the film formation of barium titanate (BaTiO 3 ) will be described.
For the formation of the thin film, a substrate formed by introducing Nb into (001) SrTiO 3 and nanocrystalline particles made of BaTiO 3 and having an average diameter of 8 nm to 10 nm were used. Nanocrystalline particles were prepared according to the sol-gel method shown in FIG.
前記ナノ結晶粒子をエタノールに分散させた分散液を予め用意しておき、この分散液に負極たる前記基板及び正極を相互に１．０ｃｍの距離を隔てて対向させた状態で浸漬させ、両極に５Ｖの電圧を５分間印加して、基板の表面にナノ結晶粒子を電気泳動電着させた。なお、正極にはＰｔ／Ｔｉ／ＳｉＯ2／Ｓｉにて構成した基板を用いた。
そして、この基板を空気中、８００℃又は６００℃で３０分間焼成してＢａＴｉＯ3薄膜を得た。なお、昇温速度は２０℃／分とした。
A dispersion liquid in which the nanocrystal particles are dispersed in ethanol is prepared in advance, and the substrate and the positive electrode, which are negative electrodes, are immersed in the dispersion liquid with a distance of 1.0 cm between each other, and are immersed in both electrodes. A voltage of 5 V was applied for 5 minutes to electrophoretically deposit nanocrystal particles on the surface of the substrate. Incidentally, the positive electrode using the substrate constituted by Pt / Ti / SiO 2 / Si .
Then, in the air the board to obtain a BaTiO 3 thin film was baked for 30 minutes at 800 ° C. or 600 ° C.. The temperature rising rate was 20 ° C./min.
図４は、電気泳動電着した後の基板の表面状態を示すＳＥＭ画像図である。
図４から明らかな如く、基板の表面には複数のナノ結晶粒子が均一に堆積されていた。
なお、このときの膜厚は略１００ｎｍであった。
FIG. 4 is an SEM image showing the surface state of the substrate after electrophoretic electrodeposition.
As apparent from FIG. 4, a plurality of nanocrystal particles were uniformly deposited on the surface of the substrate.
In addition, the film thickness at this time was about 100 nm.
一方、図５は、８００℃で焼成して得られたＢａＴｉＯ3薄膜のＳＥＭ画像図である。
図５から明らかな如く、基板上にＢａＴｉＯ3のナノ結晶粒子が略均一に堆積されており、堆積されたナノ結晶粒子は焼成操作によって直径が５０ｎｍ程度に生長していた。
次に、このように形成した薄膜がエピタキシャルなものであるか否かを検討した結果について説明する。
On the other hand, FIG. 5 is an SEM image of a BaTiO 3 thin film obtained by baking at 800 ° C.
As apparent from FIG. 5, BaTiO 3 nanocrystal particles were deposited substantially uniformly on the substrate, and the deposited nanocrystal particles were grown to a diameter of about 50 nm by the firing operation.
Next, the result of studying whether the thin film thus formed is epitaxial will be described.
図６は、８００℃で焼成した薄膜についてＸＲＤ測定を行った結果を示すグラフであり、図７は、６００℃で焼成した薄膜についてＸＲＤ測定を行った結果を示すグラフである。なお、両図中、白丸印はＢａＴｉＯ3を示しており、黒丸印はＳｒＴｉＯ3を示している。 FIG. 6 is a graph showing the results of XRD measurement for a thin film fired at 800 ° C., and FIG. 7 is a graph showing the results of XRD measurement for a thin film fired at 600 ° C. In both figures, white circles indicate BaTiO 3 and black circles indicate SrTiO 3 .
両図６、図７から明らかなように、（００１）面及び（００２）面において基板たるＳｒＴｉＯ3及び薄膜たるＢａＴｉＯ3に係る鋭尖なピークが現れている一方、その他の領域、特に３０°付近の領域に他のピークが現れていない。従って、当該薄膜の基板と平行な面は、エピタキシャルなものであると言える。 As apparent from FIGS. 6 and 7, sharp peaks related to SrTiO 3 as a substrate and BaTiO 3 as a thin film appear on the (001) plane and the (002) plane, while other regions, particularly 30 °. No other peaks appear in the nearby area. Therefore, it can be said that the plane parallel to the substrate of the thin film is epitaxial.
図８は、８００℃で焼成した薄膜についてポールフィギュア測定を行った結果を示すものであり、（ａ）は２次元的に、（ｂ）は３次元的に表している。
ポールフィギュア測定は、あおり角を０°から９０°まで２．５°ずつ変化させ、各あおり角においてφスキャンを行うことによって実施した。
FIG. 8 shows the result of pole figure measurement performed on a thin film fired at 800 ° C., where (a) represents two-dimensionally and (b) represents three-dimensionally.
The pole figure measurement was performed by changing the tilt angle by 2.5 ° from 0 ° to 90 ° and performing φ scan at each tilt angle.
図８（ａ）及び（ｂ）から明らかなように、４回対称の鋭尖な回折ピークが現れており、薄膜構成粒子の面内の結晶方位も揃っており、基板に対しエピタキシャル的であることを示していた。 As is apparent from FIGS. 8A and 8B, a sharp diffraction peak having a 4-fold symmetry appears, the crystal orientation in the plane of the thin film constituting particles is uniform, and it is epitaxial with respect to the substrate. It showed that.
なお、前述した電気泳動電着によってナノ結晶粒子を基板上又は基層上に堆積させる堆積工程と、前述した焼成工程とを所要回数繰り返すことにより、数百ｎｍから１μｍ程度の厚さのエピタキシャルな薄膜を形成することができる。 In addition, an epitaxial thin film having a thickness of about several hundred nm to 1 μm is obtained by repeating the deposition step for depositing nanocrystal particles on the substrate or the base layer by the above-described electrophoretic electrodeposition and the firing step described above as many times as necessary. Can be formed.
更に、前述したゾル−ゲル法に則して、ＳｒＴｉＯ3からなり、平均直径が略５ｎｍ以上略１５ｎｍ以下の適宜寸法のナノ結晶粒子を調製しておき、前述した如くＢａＴｉＯ3のナノ結晶粒子にて構成したエピタキシャルな薄膜上に、ＳｒＴｉＯ3のナノ結晶粒子にて構成したエピタキシャルな薄膜を、前述した堆積工程及び焼成工程を行うことによって形成することもできる。そして、ＢａＴｉＯ3のナノ結晶粒子にて構成したエピタキシャルな薄膜とＳｒＴｉＯ3のナノ結晶粒子にて構成したエピタキシャルな薄膜とを交互に重層させる操作を所要回数繰り返すことによって所要の積層構造を形成することができる。 Furthermore, in accordance with the sol-gel method described above, nanocrystal particles having an appropriate size of SrTiO 3 and having an average diameter of about 5 nm to about 15 nm are prepared, and the BaTiO 3 nanocrystal particles are formed as described above. An epitaxial thin film composed of SrTiO 3 nanocrystal particles can be formed on the epitaxial thin film configured as described above by performing the above-described deposition step and firing step. Then, the required laminated structure is formed by repeating the operation of alternately laminating the epitaxial thin film composed of BaTiO 3 nanocrystal particles and the epitaxial thin film composed of SrTiO 3 nanocrystal particles as many times as necessary. Can do.
なお、ＳｒＴｉＯ3のナノ結晶粒子には所要量のＮｂを導入しておくことによって当該薄膜層を電極層とすることができる。このとき、各層の堆積工程において所要のマスクを用いることによって、所要の積層構造になすことができる。
また、ＢａＴｉＯ3のナノ結晶粒子に代えてＣａＴｉＯ3のナノ結晶粒子を用いることもできる。
The thin film layer can be used as an electrode layer by introducing a necessary amount of Nb into the SrTiO 3 nanocrystal particles. At this time, a required laminated structure can be obtained by using a required mask in the deposition process of each layer.
Further, instead of BaTiO 3 nanocrystal particles, CaTiO 3 nanocrystal particles can also be used.
１ 貯留槽
２ 電源装置
３ 負極
４ 正極
Ｓ 分散液
Ｐ ナノ粒子
DESCRIPTION OF SYMBOLS 1 Storage tank 2 Power supply device 3 Negative electrode 4 Positive electrode S Dispersion liquid P Nanoparticle
Claims (9)
前記第１ペロブスカイト酸化物を主成分とし、適宜直径の結晶粒子群を所定の溶媒に分散させた分散液を調製する工程と、
前記結晶粒子群の調製に用いた第１ペロブスカイト酸化物とは異なる適宜の第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上、又は、適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に、前記分散液中の結晶粒子群を堆積させる堆積工程と、
堆積させて得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成する焼成工程と
を実施することを特徴とするペロブスカイト酸化物薄膜の製造方法。 In the method for producing an epitaxial thin film mainly composed of a first perovskite oxide represented by the general formula MTiO 3 (M represents Ba, Sr or Ca, or a mixture thereof)
Preparing a dispersion in which the first perovskite oxide is a main component and a crystal particle group having an appropriate diameter is dispersed in a predetermined solvent;
Formed on a first substrate made of a single crystal mainly composed of an appropriate second perovskite oxide different from the first perovskite oxide used for the preparation of the crystal particle group, or on an appropriate second substrate; A deposition step of depositing crystal particles in the dispersion on an epitaxial base layer mainly composed of the second perovskite oxide;
A method for producing a perovskite oxide thin film, comprising performing a firing step of firing the first substrate or the second substrate obtained by deposition at an appropriate temperature of less than 1000 ° C.
前記第１ペロブスカイト酸化物を主成分とし、適宜直径の結晶粒子群を所定の溶媒に分散させた分散液中の前記結晶粒子群を、当該結晶粒子群の調製に用いた第１ペロブスカイト酸化物とは異なる第２ペロブスカイト酸化物を主成分とした単結晶からなる第１基板上、又は、適宜の第２基板上に形成され、前記第２ペロブスカイト酸化物を主成分としたエピタキシャルな基層上に堆積させ、得られた第１基板又は第２基板を１０００℃未満の適宜温度で焼成してなることを特徴とするペロブスカイト酸化物薄膜。 An epitaxial thin film mainly composed of a first perovskite oxide represented by the general formula MTiO 3 (M represents Ba, Sr or Ca, or a mixture thereof),
The first perovskite oxide used in the preparation of the crystal particle group, the crystal particle group in a dispersion in which the first perovskite oxide is a main component and the crystal particle group having an appropriate diameter is dispersed in a predetermined solvent; Is formed on a first substrate made of a single crystal mainly composed of different second perovskite oxide or on an appropriate second substrate and deposited on an epitaxial base layer mainly composed of the second perovskite oxide. A perovskite oxide thin film obtained by firing the obtained first substrate or second substrate at an appropriate temperature of less than 1000 ° C.
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