JP6260982B2 - Particle-oriented ceramics - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、粒子配向セラミックスに関する。 The present invention relates to particle-oriented ceramics.
圧電材料やリチウムイオン二次電池等に用いられる無機材料が持つ機能性は、結晶の構造と結晶方位に依存することが多い。これまで、機能性の向上を図る手法として、組成の変化による結晶構造の制御や結晶方位を揃える粒子配向化などの検討がなされている。
特に、セラミックスを圧電材料として用いる場合、外部電圧を加えて分極のベクトル方向を揃える必要があるが、その機能性から結晶方位を一方向に揃えた配向セラミックスの研究が盛んに行われている。
The functionality of inorganic materials used for piezoelectric materials and lithium ion secondary batteries often depends on the crystal structure and crystal orientation. So far, as a method for improving functionality, studies have been made on controlling the crystal structure by changing the composition and orienting the grains to align the crystal orientation.
In particular, when ceramics are used as a piezoelectric material, it is necessary to apply an external voltage to align the vector direction of polarization, but due to its functionality, research on oriented ceramics in which the crystal orientation is aligned in one direction has been actively conducted.
例えば、非特許文献１では、ビスマス層状構造強誘電体の粒子が板状に成長することを利用し、ホット・フォージング法(押しつぶしながら焼結する方法)で緻密なｃ軸方向への粒子配向セラミックスを得ている。
また、非特許文献２では、ビスマス層状構造強誘電体の一つであるＢｉＴの板状の粒子を合成し、ドクターブレードによりテープキャスティングしたグリーンシートを焼結することで緻密なｃ軸方向への粒子配向セラミックスを得ている。ここでＢｉＴとはチタン酸ビスマスのことであり、組成式はＢｉ4Ｔｉ3Ｏ12である。
さらに、非特許文献３では、ＢｉＴはｃ軸方向とａ(ｂ)軸方向でごく僅かに磁化率が異なることを利用、スラリー状にしたＢｉＴを強磁場中(１０Ｔ以上)で堆積することでａ(ｂ)軸方向に粒子が揃ったグリーンシートを作製し、これを焼結することで緻密なａ(ｂ)軸方向への粒子配向セラミックスを得ている。
For example, Non-Patent Document 1 utilizes the fact that particles of a bismuth layer-structured ferroelectric material grow in a plate shape, and fine particle orientation in the c-axis direction by a hot forging method (a method of sintering while crushing). I have ceramics.
Further, in Non-Patent Document 2, BiT plate-like particles, which are one of bismuth layered structure ferroelectrics, are synthesized, and a green sheet that has been tape-cast by a doctor blade is sintered, so that the fine c-axis direction can be obtained. Obtained grain oriented ceramics. Here, BiT means bismuth titanate, and the composition formula is Bi 4 Ti 3 O 12 .
Furthermore, in Non-Patent Document 3, BiT uses the fact that the magnetic susceptibility is slightly different between the c-axis direction and the a (b) -axis direction, and deposits BiT in the form of slurry in a strong magnetic field (10T or more). A green sheet in which particles are aligned in the a (b) axial direction is manufactured and sintered, thereby obtaining a dense particle-oriented ceramic in the a (b) axial direction.
しかしながら、これまでの手法はいずれも熱処理を要するものであって、十分に緻密な微細構造を持ったセラミックスを、熱処理することなく配向制御することは実現されていなかった。
これに対して、本発明者等は、ＢｉＴの板状粒子を用いて、エアロゾルデポジション(ＡＤ)法により室温で配向膜を作製できることを見いだしている(非特許文献５)。ＡＤ法は、粉末材料の噴射加工技術の１つであり、セラミック微粒子を高温で焼結することなく常温で固化・緻密化できる方法である。
However, all of the conventional techniques require heat treatment, and it has not been possible to control the orientation of a ceramic having a sufficiently fine microstructure without heat treatment.
On the other hand, the present inventors have found that an alignment film can be produced at room temperature by an aerosol deposition (AD) method using BiT plate-like particles (Non-patent Document 5). The AD method is one of powder material injection processing techniques, and is a method in which ceramic fine particles can be solidified and densified at room temperature without sintering at high temperature.
圧電セラミックスは、強誘電体セラミックスに電界を印加し、強誘電体の分域の方向を一定の方向にそろえる、いわゆる分極処理を施したものである。圧電セラミックスにおいて、分極処理により自発分極を一定方向にそろえるためには、自発分極の方向が三次元的に取りうる等方性ペロブスカイト型の結晶構造が有利である。そのため、実用化されている圧電セラミックスの大部分は、等方性ペロブスカイト型強誘電体セラミックスである。等方性ペロブスカイト型強誘電体セラミックスとしては、例えばＰＺＴ，ＢＴＯ，ＢＮＴ等が知られている。ここでＰＺＴとはチタン酸ジルコン酸鉛のことであり、組成式はＰｂ(Ｚｒ，Ｔｉ)Ｏ3である。ＢＴＯはチタン酸バリウムのことであり、組成式はＢａＴｉＯ3である。また、ＢＮＴとは単純ペロブスカイト構造を持つチタン酸ビスマスナトリウムのことであり、組成式はＢｉ0.5Ｎａ0.5ＴｉＯ3である。 Piezoelectric ceramics have been subjected to so-called polarization treatment in which an electric field is applied to ferroelectric ceramics to align the direction of the domain of the ferroelectric material in a certain direction. In piezoelectric ceramics, an isotropic perovskite-type crystal structure in which the direction of spontaneous polarization can be taken three-dimensionally is advantageous in order to align spontaneous polarization in a certain direction by polarization treatment. For this reason, most of the piezoelectric ceramics in practical use are isotropic perovskite ferroelectric ceramics. As isotropic perovskite ferroelectric ceramics, for example, PZT, BTO, BNT and the like are known. Here, PZT means lead zirconate titanate, and the composition formula is Pb (Zr, Ti) O 3 . BTO is barium titanate, and the composition formula is BaTiO 3 . BNT is bismuth sodium titanate having a simple perovskite structure, and the composition formula is Bi 0.5 Na 0.5 TiO 3 .
これらの中で、ＰＺＴに代表される鉛系の圧電セラミックスは、他の圧電セラミックスに比較して高い圧電特性を有しており、現在実用化されている圧電セラミックスの大部分を占めている。しかしながら、蒸気圧の高い酸化鉛(ＰｂＯ)を含んでいるために、環境に対する負荷が大きいという問題がある。そのため、低鉛あるいは無鉛でＰＺＴと同等の圧電特性を有する圧電セラミックスが求められている。
しかしながらＢＮＴ、ＢＴＯなどの非鉛圧電体材料は、これまで置換や固溶などの組成制御による機能性向上が試みられてきたが、圧電定数が低い、キュリー温度が低いなどの理由から代替が実現できていない。
Among these, lead-based piezoelectric ceramics represented by PZT have higher piezoelectric properties than other piezoelectric ceramics, and occupy most of the piezoelectric ceramics currently in practical use. However, since lead oxide (PbO) having a high vapor pressure is contained, there is a problem that the load on the environment is large. Therefore, there is a demand for piezoelectric ceramics that have low or no lead and have piezoelectric properties equivalent to PZT.
However, lead-free piezoelectric materials such as BNT and BTO have been tried to improve their functionality by composition control such as substitution and solid solution, but they can be replaced because of their low piezoelectric constant and low Curie temperature. Not done.
例えば、非特許文献５、特許文献１等では、組成がＢＮＴ−ＢＴＯになるようＢｉＴ板状粒子のテンプレート周辺へ原料粉末を混ぜ、テープキャスティングして焼結することで、板状粒子が得にくい組成系(ＢＮＴ−ＢＴＯ)でも緻密な(１００)c粒子配向セラミックスを得ている。
しかしながら、キュリー温度については、検討されておらず、また、ビスマス等の低融点の元素を含む材料では、熱処理温度が高いと酸素欠陥を生成してしまい、絶縁性の劣化などを引き起こす。
For example, in Non-Patent Document 5, Patent Document 1, etc., it is difficult to obtain plate-like particles by mixing raw material powder around the template of BiT plate-like particles so as to have a composition of BNT-BTO, and tape casting and sintering. Even in the composition system (BNT-BTO), a dense (100) c grain oriented ceramic is obtained.
However, the Curie temperature has not been studied, and a material containing a low melting point element such as bismuth generates oxygen defects when the heat treatment temperature is high, which causes deterioration of insulation.
さらに、２５０〜３００℃の環境下でも比誘電率が低下しない誘電体材料は「高温高耐圧コンデンサ」としてハイブリッド車や電気自動車での応用が期待されている。現在、電子デバイスに搭載されている積層セラミックコンデンサなどで用いられている誘電体材料のＢＴＯはキュリー温度が１３０℃程度であり、それより高い温度環境下で利用できない。これまでＢＴＯのキュリー温度を上げるための研究が盛んに行われているが、組成制御では十分な特性改善に至っていない。
また、近年、ガソリン自動車のノックセンサーやインジェクターに圧電体材料を用いることで低燃費化をはかる研究開発が進められており、高温環境下で利用できる圧電体の開発が求められているなか、ＢＴＯのキュリー温度は１３０℃程度であり、ＢＮＴも１８０℃程度までしか利用できない。
Furthermore, a dielectric material whose relative dielectric constant does not decrease even under an environment of 250 to 300 ° C. is expected to be applied as a “high temperature high voltage capacitor” in hybrid vehicles and electric vehicles. At present, BTO, which is a dielectric material used in multilayer ceramic capacitors mounted on electronic devices, has a Curie temperature of about 130 ° C. and cannot be used in a temperature environment higher than that. So far, extensive research has been conducted to raise the Curie temperature of BTO, but the composition control has not yet improved the characteristics sufficiently.
In recent years, research and development for reducing fuel consumption has been promoted by using piezoelectric materials for knock sensors and injectors in gasoline vehicles, and there is a need for the development of piezoelectric materials that can be used in high-temperature environments. The Curie temperature is about 130 ° C, and BNT can only be used up to about 180 ° C.
近年、薄膜作製技術の進化により結晶方位に対して特定の方向から大きな応力を印加することで、等方的もしくは擬等方的な結晶構造を持つ物質の組成を変えることなく、結晶構造を制御する方法が注目を集めている。
例えば、非特許文献６では、擬等方的な結晶構造を持つＢＴＯを単結晶基板上へエピタキシャル成長させることで、基板から膜に働く内部応力によってＢＴＯの結晶構造を変化させ、ＢＴＯの単結晶が示す本来の物性よりも大幅な機能性改善(高相転移温度化)を導いている。
該方法は、ＢＴＯ膜の堆積を終え、膜と基板を冷却するものであり、基板の線膨張係数がＢＴＯよりも大きいと、室温に戻った際、基板の方が縮んでいるため、ＢＴＯ膜には大きな内部圧縮応力が働き、この内部応力によって、ＢＴＯのａ軸とｂ軸が縮むかわりにｃ軸が伸び、これにより、組成を変更することなく大きな強誘電体性の発現と高いキュリー温度変化を実現するものである。
しかしながら、非特許文献６のＢＴＯを利用する上で問題点であった低相転移温度も、基板からの応力印加による結晶構造の制御で解決が図られつつも、特定の基板を利用しなければならないことや高い合成温度など、作製条件に大きな制約があり実用化の域には達していない。
In recent years, with the evolution of thin film fabrication technology, by applying a large stress from a specific direction to the crystal orientation, the crystal structure can be controlled without changing the composition of materials with isotropic or quasi-isotropic crystal structures. How to do is attracting attention.
For example, in Non-Patent Document 6, BTO having a pseudo-isotropic crystal structure is epitaxially grown on a single crystal substrate, thereby changing the BTO crystal structure by internal stress acting on the film from the substrate. This leads to a significant improvement in functionality (higher phase transition temperature) than the original physical properties shown.
The method finishes the deposition of the BTO film and cools the film and the substrate. If the linear expansion coefficient of the substrate is larger than that of the BTO, the substrate shrinks when returning to room temperature. A large internal compressive stress acts on this, and this internal stress causes the c-axis to expand instead of shrinking the a-axis and b-axis of the BTO. This makes it possible to develop a large ferroelectricity and a high Curie temperature without changing the composition. Realize change.
However, the low phase transition temperature, which has been a problem in using BTO of Non-Patent Document 6, can be solved by controlling the crystal structure by applying stress from the substrate, but a specific substrate must be used. There are significant restrictions on the production conditions such as incompatibility and high synthesis temperature, and it has not yet reached practical use.
このように、応力によって結晶構造を制御しやすい擬等方的な結晶構造を持つ物質に対して、配向化と内部応力の印加を可能にすることにより、特性の向上が期待されるが、基板の種類や膜の合成方法(低スループット、高コスト)、高温での熱処理温度などが課題とされてきた。 As described above, improvement in characteristics is expected by enabling orientation and application of internal stress to a substance having a pseudo-isotropic crystal structure in which the crystal structure is easily controlled by stress. The type of film, the method of synthesizing the film (low throughput, high cost), the heat treatment temperature at high temperature, and the like have been problems.
本発明は、こうした現状を鑑みてなされたものであって、応力の影響を受けやすい結晶異方性の小さい(等方性の比較的高い)物質を用いて、熱処理なく、緻密かつ微細な構造を持った粒子配向膜を作製し、必要に応じて低い熱処理温度をかけ、膜に働く内部応力を利用し結晶構造を制御することを提供することを目的とするものである。 The present invention has been made in view of such a situation, and uses a substance having a small crystal anisotropy (relatively high isotropic property) that is easily affected by stress, and has a dense and fine structure without heat treatment. It is an object of the present invention to provide a grain orientation film having a thickness, to apply a low heat treatment temperature as required, and to control the crystal structure using internal stress acting on the film.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、ＡＤ法に用いる原料粒子の形状を制御することで、等方性の高い結晶構造を持った物質の粒子配向化膜を作製できることを見いだした。すなわち、ＢＮＴ等の等方性の高い結晶構造を持つものは、通常、球状か立法体もしくは直方体の粒子に成長するが、本発明では、板状形状に作製された粒子を用いることで、上記目的を達成するという知見を得た。 As a result of intensive research to achieve the above object, the present inventors have controlled the shape of the raw material particles used in the AD method, and thereby have a particle orientation film of a substance having a highly isotropic crystal structure. I found out that it can be made. That is, those having a highly isotropic crystal structure, such as BNT, usually grow into spherical, cubic or cuboid particles, but in the present invention, by using particles prepared in a plate shape, I gained the knowledge to achieve my goal.
本発明はこれらの知見に基づいて完成に至ったものであり、本発明によれば、以下の発明が提供される。
［１］エアロゾルデポジション法により粒子配向膜を製造する方法であって、原料粉末として、等方性の高い結晶構造を持った物質の板状形状に作製された粒子を用いて粒子配向させるとともに、該等方性の高い結晶構造を持った物質の結晶構造を制御することを特徴とする粒子配向膜の製造方法。
［２］前記等方性の高い結晶構造を持った物質が、単純ペロブスカイト構造のチタン酸ビスマスナトリウムであることを特徴とする請求項１に記載の粒子配向膜の製造方法。
［３］エアロゾルデポジション法による粒子配向膜であって、等方性の高い結晶構造を持った物質の板状形状に作製された粒子が配向するとともに、該等方性の高い結晶構造を持った物質の結晶構造が制御されていることを特徴とする粒子配向膜。
［４］前記等方性の高い結晶構造を持った物質が、単純ペロブスカイト構造のチタン酸ビスマスナトリウムであることを特徴とする請求項３に記載の粒子配向膜。
The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] A method for producing a particle alignment film by an aerosol deposition method, in which particles are oriented using, as a raw material powder, particles prepared in a plate shape of a substance having a highly isotropic crystal structure. A method for producing a grain alignment film, comprising controlling a crystal structure of a substance having a highly isotropic crystal structure.
[2] The method for producing a grain oriented film according to [1], wherein the substance having a highly isotropic crystal structure is bismuth sodium titanate having a simple perovskite structure.
[3] A particle orientation film by the aerosol deposition method, in which particles produced in a plate-like shape of a substance having a highly isotropic crystal structure are oriented and have a highly isotropic crystal structure. A grain alignment film characterized in that the crystal structure of the substance is controlled.
[4] The grain alignment film according to [3], wherein the substance having a highly isotropic crystal structure is bismuth sodium titanate having a simple perovskite structure.
本発明によれば、ＡＤ法に用いる原料粒子として板状形状を有するものを用いることで、等方性の高い結晶構造を持った物質でも十分に緻密で熱処理することなく配向制御でき、低温で基板を選ぶことなく効果的にその物質の結晶構造を応力によって制御することができる。 According to the present invention, by using particles having a plate-like shape as raw material particles used in the AD method, even a substance having a highly isotropic crystal structure can be sufficiently densely controlled without being heat-treated, and at a low temperature. The crystal structure of the substance can be effectively controlled by stress without selecting a substrate.
本発明は、ＡＤ法に用いる原料粒子の形状を制御することで、等方性の高い結晶構造を持った物質を配向するものである。
すなわち、ＢＮＴ等の等方性の高い結晶構造を持つものは、通常、球状か立法体もしくは直方体の粒子に成長するが、本発明では、ＡＤ法に用いる原料粒子として板状形状に作製されたＢＮＴ粒子を用いることを特徴とするものである。
In the present invention, a material having a highly isotropic crystal structure is oriented by controlling the shape of raw material particles used in the AD method.
That is, a material having a highly isotropic crystal structure such as BNT usually grows into a spherical, cubic or cuboidal particle, but in the present invention, it was produced in a plate shape as a raw material particle used in the AD method. BNT particles are used.
本発明におけるエアロゾルデポジション法(以下ＡＤ法)は、あらかじめ他の手法で準備された微粒子、超微粒子原料をガスと混合してエアロゾル化し、ノズルを通して基板に噴射して被膜を形成する方法である。このＡＤ法でセラミックス原料粉末を用い、その粒子径、機械的強度等を調製し適切な成膜条件を選ぶと、常温衝撃固化現象(Room Temperature Impact Consolidation)により、基板に噴射する際の基板の加熱処理や成膜後の熱処理をすることなく、高密度かつ透明なセラミックス被膜が常温で高速形成できるものである。 The aerosol deposition method (hereinafter referred to as AD method) in the present invention is a method of forming a film by mixing fine particles and ultrafine particle raw material prepared in advance with other methods with a gas to form an aerosol and spraying it onto a substrate through a nozzle. . When ceramic raw material powder is used in this AD method, the particle diameter, mechanical strength, etc. are adjusted and appropriate film forming conditions are selected, the room temperature impact consolidation phenomenon (Room Temperature Impact Consolidation) causes the substrate A high-density and transparent ceramic film can be formed at high speed at room temperature without heat treatment or heat treatment after film formation.
本発明に基づき、板状ＢＴＯ粒子をＡＤ法で常温にて成膜すると、板状粒子の面垂直方向の結晶方位と基板の面垂直方向が揃い、一軸配向膜を得ることができる。ＡＤ法は基板へ粒子を衝突させて膜を堆積させるため、得られた膜には基板から大きな圧縮内部応力が働く(ショットピーニング効果)。この圧縮内部応力によってＢＴＯの結晶構造が変化し、ＢＴＯを高キュリー温度化させることができる。
また、非鉛圧電体材料の板状粒子を用いてＡＤ法により一軸配向化した膜を常温で形成することで、内部圧縮応力により結晶構造を制御し、高い圧電定数、高いキュリー温度を示す非鉛圧電体材料を開発することが可能となる。
さらに、２種類以上の異なる無機材料を緻密に積層することは、それぞれの材料が緻密になる熱処理温度が異なる為、困難であり、組み合わせが限られていたが、ＡＤ法はあらゆる無機材料を常温で緻密な膜に形成できるため、２種類以上の異なる無機材料を緻密に積層することが容易である。この際、板状の粒子を用いて一軸配向化させた層を積み重ねて低温で熱処理すると、内部圧縮応力がセラミックス内に閉じ込められる。この閉じ込められた内部圧縮応力により、結晶構造を制御し、高い圧電定数、高いキュリー温度を示す非鉛圧電体材料を開発することが可能となる。
When the plate-like BTO particles are formed at room temperature by the AD method based on the present invention, the crystal orientation in the plane perpendicular direction of the plate-like particles is aligned with the plane perpendicular to the substrate, and a uniaxially oriented film can be obtained. Since the AD method deposits a film by colliding particles with the substrate, a large internal compression stress acts on the obtained film from the substrate (shot peening effect). This compressive internal stress changes the crystal structure of the BTO, and the BTO can be raised to a high Curie temperature.
Also, by forming a uniaxially oriented film by AD method using plate-like particles of lead-free piezoelectric material at room temperature, the crystal structure is controlled by internal compressive stress, and a high piezoelectric constant and high Curie temperature are exhibited. Lead piezoelectric material can be developed.
Furthermore, it is difficult to densely laminate two or more different inorganic materials because the heat treatment temperatures at which the materials become dense differ, and the combinations are limited. Thus, it is easy to densely stack two or more different inorganic materials. At this time, when layers uniaxially oriented using plate-like particles are stacked and heat-treated at a low temperature, the internal compressive stress is confined in the ceramic. This confined internal compressive stress makes it possible to control a crystal structure and develop a lead-free piezoelectric material exhibiting a high piezoelectric constant and a high Curie temperature.
以下、本発明を実施例に基づいて説明するが、本発明はこの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this Example.
〈ＸＲＤによる構造解析〉
最初に、本発明において用いた、Ｘ線回折(ＸＲＤ)による無配向膜と一軸配向膜の評価方法について記載する。
図１は、無配向膜と一軸配向膜について、Ｘ線回折による評価を行った際の違いを示すものである。
図１に示すとおり、無配向膜は結晶の向きがそろっていないため、すべての回折ピークが観察されるため、Ｘ線回折結果によるそれぞれのピーク強度比は、粉末を測定した場合と同一となる。
一方で、一軸配向膜は、基板の面垂直方向に結晶方向がそろっており、その結晶方位に起因した回折ピーク強度が強くなり、他のピークは小さくなる。
<Structural analysis by XRD>
First, a method for evaluating a non-oriented film and a uniaxial oriented film by X-ray diffraction (XRD) used in the present invention will be described.
FIG. 1 shows the difference between an unoriented film and a uniaxially oriented film when evaluated by X-ray diffraction.
As shown in FIG. 1, since the crystal orientation of the non-oriented film is not aligned, all diffraction peaks are observed, so that the respective peak intensity ratios based on the X-ray diffraction results are the same as when the powder is measured. .
On the other hand, the uniaxially oriented film has crystal directions aligned in the direction perpendicular to the plane of the substrate, the diffraction peak intensity resulting from the crystal orientation becomes stronger, and the other peaks become smaller.
〈結晶異方性の小さい材料を用いたＡＤ法による配向膜の作製〉
結晶異方性の小さい物質として、単純ペロブスカイト構造を持ったＢＮＴを用い、原料粉末に板状粒子を用いたＡＤ膜と、原料粉末に通常の球状粒子を用いたＡＤ膜について配向性の違いを確認した。
<Preparation of alignment film by AD method using material with small crystal anisotropy>
As a substance having a small crystal anisotropy, BNT having a simple perovskite structure is used, and there is a difference in orientation between an AD film using plate-like particles as raw material powder and an AD film using normal spherical particles as raw material powder. confirmed.
図２は、比較試料として固相法８００℃２時間で作製した球形形状のＢＮＴ粒子(左側)と、本発明で用いた板状のＢＮＴ原料粒子(右側)の電子顕微鏡(ＳＥＭ)による粒子の形状の観察結果を示す図である。 FIG. 2 shows a comparison of the spherical BNT particles (left side) prepared in a solid phase method at 800 ° C. for 2 hours as comparative samples and the plate-like BNT raw material particles (right side) used in the present invention by an electron microscope (SEM). It is a figure which shows the observation result of a shape.
この板状粒子の作製方法は次のとおりである。Ｂｉ2Ｏ3(粒子サイズ約２〜３μｍで純度は99.99％)、ＴｉＯ2(粒子サイズは約２μｍで純度は99.99％)、Ｎａ2ＣＯ3(純度は99％)の出発原料をＮＢＴiの化学量論比になるように秤量し、プラスチック製の容器にエタノールとジルコニアボールと共に入れ、１時間、遊星ボールミル(２００ｒｐｍ)により粉砕、混合した。ここでＮＢＴiとはビスマス層状構造強誘電体のチタン酸ビスマスナトリウムのことであり、組成式はＮａ0.5Ｂｉ4.5Ｔｉ4Ｏ15である。得られた試料は約６０℃のトレイに移しエタノールを揮発させた。この試料をアルミナ坩堝に入れて大気中で８００℃２時間熱処理し、ＮＢＴｉの粉末を得た。得られたＮＢＴｉの粉末は、ジルコニア製の容器にアセトン、ジルコニアボールと共に、ＮＢＴｉと等量のＮａＣｌ(粒子径サイズはおよそ１００μｍ)を入れ1時間、遊星ボールミル(２００ｒｐｍ)により粉砕混合した。得られた混合体は、およそ６０℃のトレイに移し、十分アセトンを揮発させた。ＮＢＴｉとＮａＣｌの混合体はアルミナ坩堝に移し、１０００℃２時間の熱処理を行った。得られた試料を純水で洗浄し、ＮａＣｌを取り除いてＮＢＴiの板状粒子を得た。この板状ＮＢＴｉ粒子に次の式に則ってＢＮＴが得られるようにアセトン中でＮａＮＯ3を加え、さらにその混合物に３ｍｏｌ％過剰のＮａＮＯ3を加え、さらにそれらの重量と等量のＮａＣｌを加えて撹拌し、そのまま、エバポレーターで乾燥させた。得られた混合体は６７０℃で１０時間の熱処理を加えた。
Ｎａ0.5Ｂｉ4.5Ｔｉ4Ｏ15＋1.5ＮａＮＯ3 →
4(Ｂｉ0.5Ｎａ0.5)ＴｉＯ3＋1.25Ｂｉ2Ｏ3＋1.5ＮＯ2＋0.375Ｏ2
The method for producing the plate-like particles is as follows. The starting materials of Bi 2 O 3 (particle size is about 2 to 3 μm and purity is 99.99%), TiO 2 (particle size is about 2 μm and purity is 99.99%), Na 2 CO 3 (purity is 99%) are used as starting materials for NBTi They were weighed so as to have a stoichiometric ratio, placed in a plastic container together with ethanol and zirconia balls, and ground and mixed with a planetary ball mill (200 rpm) for 1 hour. Here, NBTi is bismuth sodium titanate, which is a bismuth layer structure ferroelectric, and its composition formula is Na 0.5 Bi 4.5 Ti 4 O 15 . The obtained sample was transferred to a tray at about 60 ° C. to evaporate ethanol. This sample was put in an alumina crucible and heat-treated in the atmosphere at 800 ° C. for 2 hours to obtain NBTi powder. The obtained NBTi powder was mixed with acetone and zirconia balls together with NBTi in an amount equal to NBTi (particle size is about 100 μm) in a zirconia container for 1 hour by a planetary ball mill (200 rpm). The obtained mixture was transferred to a tray at about 60 ° C., and acetone was volatilized sufficiently. The mixture of NBTi and NaCl was transferred to an alumina crucible and heat-treated at 1000 ° C. for 2 hours. The obtained sample was washed with pure water, and NaCl was removed to obtain NBTi plate-like particles. To this plate-like NBTi particles, NaNO 3 was added in acetone so that BNT was obtained according to the following formula, 3 mol% excess NaNO 3 was added to the mixture, and NaCl equivalent to their weight was added. The mixture was stirred and dried with an evaporator. The obtained mixture was heat-treated at 670 ° C. for 10 hours.
Na 0.5 Bi 4.5 Ti 4 O 15 + 1.5NaNO 3 →
4 (Bi 0.5 Na 0.5 ) TiO 3 + 1.25Bi 2 O 3 + 1.5NO 2 + 0.375O 2
合成された試料を３Ｍ塩酸で、ＮａＣｌ、過剰ＮａＮＯ3、Ｂｉ2Ｏ3を溶解し、さらに純水で洗浄することで板状のＢＮＴ粒子を得た。板状粒子は、形状が四角く、厚さが５００〜１０００ｎｍ程度の板状であった。 The synthesized sample was dissolved in NaCl, excess NaNO 3 and Bi 2 O 3 with 3M hydrochloric acid, and further washed with pure water to obtain plate-like BNT particles. The plate-like particle was a plate having a square shape and a thickness of about 500 to 1000 nm.
ＡＤ法の原料粉末として、これらの２種の粒子形状が異なる粒子を用いて、前述と同様の方法により、ＡＤ法による成膜をおこなった。
図３は、左から順に、固相法で作製した球状粒子のＢＮＴ粉末、固相法で作製したＢＮＴ粉末によるＡＤ膜、及び板状ＢＮＴ粉末によるＡＤ膜、下の図は板状ＢＮＴ粒子をガラス板に押し付けた試料のＸ線回折パターンを示す図である。
Using these two kinds of particles having different particle shapes as the raw material powder for the AD method, a film was formed by the AD method by the same method as described above.
FIG. 3 shows, from the left, a spherical BNT powder prepared by a solid phase method, an AD film using a BNT powder prepared by a solid phase method, and an AD film using a plate-like BNT powder, and the lower figure shows a plate-like BNT particle. It is a figure which shows the X-ray-diffraction pattern of the sample pressed on the glass plate.
固相法で作製した球状粒子のＢＮＴ粉末のＸ線回折パターンと板状ＢＮＴ粒子をガラス板に押し付けた試料のＸ線回折パターンの図を比較する。ガラス板がＸ線回折しないことは事前に確認しているため、板状ＢＮＴ粒子をガラス板に押し付けた試料のＸ線回折パターンは板状粒子に対して面垂直方向の結晶構造の状態を示している。従って、１００ｃに起因したピークが強くなっていることから、ＢＮＴ結晶の１００ｃの方位と板状粒子の面垂直方向が一致していることが確認できる。また、格子定数を確認したところ、固相法で作製した球状粒子のＢＮＴ粉末と板状ＢＮＴ粉末のどちらも格子定数が一致していることを確認した。 The X-ray diffraction pattern of the spherical BNT powder produced by the solid phase method is compared with the X-ray diffraction pattern of the sample in which the plate-like BNT particles are pressed against a glass plate. Since it has been confirmed in advance that the glass plate does not diffract X-rays, the X-ray diffraction pattern of the sample in which the plate-like BNT particles are pressed against the glass plate shows the state of the crystal structure perpendicular to the plate-like particles. ing. Therefore, since the peak due to 100c is strong, it can be confirmed that the orientation of 100c of the BNT crystal coincides with the plane perpendicular direction of the plate-like particles. Further, when the lattice constant was confirmed, it was confirmed that both the spherical BNT powder and the plate-like BNT powder produced by the solid phase method had the same lattice constant.
固相法で作製した球状粒子のＢＮＴ粉末、固相法で作製したＢＮＴ粉末によるＡＤ膜、及び板状ＢＮＴ粉末によるＡＤ膜を比較すると、固相法で作製した球状粒子のＢＮＴ粉末、固相法で作製したＢＮＴ粉末によるＡＤ膜はピーク強度比が一致しているため、固相法で作製したＢＮＴ粉末によるＡＤ膜は無配向であることが確認できる。固相法で作製した球状粒子のＢＮＴ粉末と板状ＢＮＴ粉末によるＡＤ膜のＸ線回折パターンを比較すると、板状ＢＮＴ粉末によるＡＤ膜のＸ線回折パターンは１００ｃに起因したピーク強度が強くなっていることから、一軸粒子配向膜化していることが確認できる。 A comparison between the spherical BNT powder produced by the solid phase method, the AD film produced by the BNT powder produced by the solid phase method, and the AD film produced by the plate-like BNT powder. Since the peak intensity ratio of the AD film made of the BNT powder produced by the method is the same, it can be confirmed that the AD film produced by the solid phase method is non-oriented. Comparing the X-ray diffraction pattern of the AD film with the spherical BNT powder and the plate-like BNT powder produced by the solid phase method, the peak intensity due to 100c is stronger in the X-ray diffraction pattern of the AD film with the plate-like BNT powder. Therefore, it can be confirmed that the film is a uniaxial particle alignment film.
球状粒子のＢＮＴ粉末を用いて作製したＡＤ膜と、板状粒子のＢＮＴ粉末を用いて作製したＡＤ膜を比較すると、若干、板状ＢＮＴ粉末を用いたほうが、１００ｃ由来のピーク強度が強くなっていることが確認された。
これらの結果から、原料粒子形状を制御することで、ＡＤ法により配向制御できる可能性が示唆された。
また、ＡＤ膜の１００ｃ由来のピークから算出された格子定数では、a軸長が０.３９１５ナノメートルであり焼結体の値(０.３８８ナノメートル)より大きく、特定の方位に対して結晶構造を変えることができた。
Comparing the AD film produced using the BNT powder of spherical particles and the AD film produced using the BNT powder of plate-like particles, the peak intensity derived from 100c is slightly stronger when the plate-like BNT powder is used. It was confirmed that
From these results, it was suggested that the orientation can be controlled by the AD method by controlling the raw material particle shape.
Moreover, in the lattice constant calculated from the peak derived from 100c of the AD film, the a-axis length is 0.3915 nanometers, which is larger than the value of the sintered body (0.388 nanometers), and the crystal is in a specific orientation. I was able to change the structure.
〈板状粒子の配向メカニズム〉
図４は、以上の結果より、想定される板状粒子の配向メカニズムを示すものである。
板状粒子はエアロゾルの状態で凝集しているものと考えられる。つまり、板状粒子が基板に衝突する際、そのほとんどが基板に対して垂直から外れているものと考えられる。基板に衝突すると、その衝突の際の力の影響で、粒子の面と基板の面が平行になる状態が安定である。これにより、配向したものと考えられる。
<Orientation mechanism of plate-like particles>
FIG. 4 shows an assumed orientation mechanism of plate-like particles based on the above results.
The plate-like particles are considered to be aggregated in an aerosol state. That is, when the plate-like particles collide with the substrate, most of them are considered to be out of perpendicular to the substrate. When it collides with the substrate, the surface of the particle and the surface of the substrate are stable due to the influence of the force at the time of the collision. This is considered to be oriented.
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