JPH09213569A - Multilayer dielectric and capacitor - Google Patents
Multilayer dielectric and capacitorInfo
- Publication number
- JPH09213569A JPH09213569A JP1452496A JP1452496A JPH09213569A JP H09213569 A JPH09213569 A JP H09213569A JP 1452496 A JP1452496 A JP 1452496A JP 1452496 A JP1452496 A JP 1452496A JP H09213569 A JPH09213569 A JP H09213569A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric
- laminated
- thin film
- dielectric thin
- thin films
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は積層誘電体およびコ
ンデンサに関するもので、例えば、コンデンサ等の電子
部品に使用される積層誘電体およびコンデンサに関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated dielectric and a capacitor, and more particularly to a laminated dielectric and a capacitor used for electronic parts such as capacitors.
【０００２】[0002]
【従来技術】従来から、コンデンサ等に代表される誘電
体磁器を用いた電子部品では、その比誘電率の大きさと
ともに、比誘電率の温度特性が重要視されている。そし
て、近年においては、比誘電率の温度特性によって、電
子部品の使用用途が決定されているため、比誘電率の温
度特性を改善する研究が盛んになされている。2. Description of the Related Art Conventionally, in an electronic component using a dielectric ceramic such as a capacitor, the temperature characteristic of the relative permittivity has been emphasized along with the magnitude of the relative permittivity. In recent years, the use of electronic components has been determined by the temperature characteristic of the relative permittivity, and therefore researches for improving the temperature characteristic of the relative permittivity have been actively conducted.
【０００３】従来、比誘電率の温度特性を改善するため
には、誘電体材料中にシフタ−，デプレッサと言われる
添加物を添加し、キュリ−点を変化させたり、あるいは
キュリ−点の異なる２種以上の誘電体材料を混合し、固
溶体を形成する方法が一般的であった。Conventionally, in order to improve the temperature characteristic of the relative dielectric constant, an additive called shifter or depressor is added to the dielectric material to change the Curie point or to change the Curie point. A general method is to mix two or more types of dielectric materials to form a solid solution.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、誘電体
材料中にシフタ−，デプレッサと言われる添加物を添加
する方法や、２種以上の誘電体材料を混合して固溶体を
形成する方法では、比誘電率が減少したり、異相が生成
したりするという問題があった。又、上記方法では、比
誘電率の温度特性を改善することができるが、温度特性
は、デプレッサ等の添加量や２種以上の誘電体材料の混
合比により一義的に決定されるものではなく、その制御
が困難であった。However, in the method of adding an additive called shifter or depressor into the dielectric material and the method of mixing two or more kinds of dielectric materials to form a solid solution, There are problems that the dielectric constant is reduced and a different phase is generated. In addition, the above method can improve the temperature characteristic of the relative dielectric constant, but the temperature characteristic is not uniquely determined by the addition amount of the depressor or the like or the mixing ratio of two or more kinds of dielectric materials. , Its control was difficult.
【０００５】さらに、上記の方法はいずれもバルク体に
ついての方法であり、従来、ゾルゲル法により作製され
た誘電体薄膜の比誘電率の温度特性を制御する方法につ
いては全く知られていなかった。Furthermore, all of the above methods are for bulk bodies, and conventionally, no method has been known for controlling the temperature characteristic of the relative dielectric constant of the dielectric thin film produced by the sol-gel method.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、誘電体薄
膜の温度特性を改善する方法について鋭意検討した結
果、ゾルゲル法により作製された異種セラミック誘電体
薄膜を複数積層することにより、温度特性を改善するこ
とができることを見出し、本発明に至った。Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for improving the temperature characteristics of a dielectric thin film, and as a result, by stacking a plurality of different ceramic dielectric thin films produced by a sol-gel method, The inventors have found that the characteristics can be improved and have reached the present invention.
【０００７】即ち、本発明の積層誘電体は、ゾルゲル法
により形成された異種セラミックからなる誘電体薄膜を
積層してなるものである。That is, the laminated dielectric of the present invention is formed by laminating dielectric thin films made of different ceramics formed by the sol-gel method.
【０００８】また、本発明では、２種類の誘電体薄膜を
交互に積層してなることが望ましい。さらに、誘電体薄
膜は、組成式Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 で表される
薄膜と、組成式０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −
０．１ＰｂＴｉＯ3 で表される薄膜の２種類からなり、
これらの２種類の誘電体薄膜を交互に積層してなること
が望ましい。また、誘電体薄膜は、組成式Ｂａ（Ｔｉ
0.87Ｓｎ0.13）Ｏ3 で表される薄膜と、組成式Ｂａ（Ｔ
ｉ0.9 Ｚｒ0.1 ）Ｏ3 で表される薄膜の２種類からな
り、これらの２種類の誘電体薄膜を交互に積層してなる
ことが望ましい。Further, in the present invention, it is desirable that two kinds of dielectric thin films are alternately laminated. Further, the dielectric thin film includes a thin film represented by the composition formula Pb (Mg 1/3 Nb 2/3 ) O 3 and a composition formula 0.9Pb (Mg 1/3 Nb 2/3 ) O 3 −.
It consists of two kinds of thin film represented by 0.1PbTiO 3 ,
It is desirable that these two kinds of dielectric thin films are alternately laminated. The dielectric thin film has a composition formula of Ba (Ti
0.87 Sn 0.13 ) O 3 and a composition formula Ba (T
i 0.9 Zr 0.1 ) O 3 , which are two kinds of thin films, and these two kinds of dielectric thin films are preferably laminated alternately.
【０００９】本発明のコンデンサは、ゾルゲル法により
形成された異種セラミックからなる誘電体薄膜を積層し
てなる積層誘電体の両面に、一対の電極を形成してなる
ものである。The capacitor of the present invention has a pair of electrodes formed on both surfaces of a laminated dielectric formed by laminating dielectric thin films made of different ceramics by the sol-gel method.
【００１０】[0010]
【作用】本発明の積層誘電体では、ゾルゲル法により形
成された異種セラミックからなる誘電体薄膜を積層する
ことにより、それぞれの誘電体薄膜が有する温度による
比誘電率の変化が相殺され、結果として温度特性が変化
する。本発明においては、特に、ある温度において正の
温度係数を有する誘電体薄膜と、同温度において負の温
度係数を有する誘電体薄膜を積層した場合には特に有効
である。これは、ある温度域における比誘電率の変化が
相殺されることにより、比誘電率の変化が平坦化するか
らであると考えられる。In the laminated dielectric of the present invention, by laminating the dielectric thin films made of different kinds of ceramics formed by the sol-gel method, the change in the relative dielectric constant due to the temperature of each dielectric thin film is offset, and as a result, The temperature characteristics change. The present invention is particularly effective when a dielectric thin film having a positive temperature coefficient at a certain temperature and a dielectric thin film having a negative temperature coefficient at the same temperature are laminated. It is considered that this is because the change in the relative permittivity in a certain temperature range is canceled and the change in the relative permittivity is flattened.
【００１１】誘電体薄膜は、組成式Ｐｂ（Ｍｇ1/3 Ｎｂ
2/3 ）Ｏ3 で表される薄膜と、組成式０．９Ｐｂ（Ｍｇ
1/3 Ｎｂ2/3 ）Ｏ3 −０．１ＰｂＴｉＯ3 で表される薄
膜の２種類、あるいは、組成式Ｂａ（Ｔｉ0.87Ｓ
ｎ0.13）Ｏ3 で表される薄膜と、組成式Ｂａ（Ｔｉ0.9
Ｚｒ0.1 ）Ｏ3 で表される薄膜の２種類からなり、これ
らの２種類の誘電体薄膜を交互に積層することにより、
高誘電率で、しかも比誘電率の温度特性の改善された積
層誘電体を得ることができる。このような積層誘電体を
一対の電極により挟持することにより、比誘電率の温度
特性を改善したコンデンサを得ることができる。The dielectric thin film has a composition formula of Pb (Mg 1/3 Nb
2/3 ) O 3 and a composition formula 0.9Pb (Mg
1/3 Nb 2/3 ) O 3 -0.1PbTiO 3 two kinds of thin film or composition formula Ba (Ti 0.87 S
n 0.13 ) O 3 and a composition formula Ba (Ti 0.9
Zr 0.1 ) O 3 consisting of two kinds of thin films, and by alternately laminating these two kinds of dielectric thin films,
It is possible to obtain a laminated dielectric having a high dielectric constant and improved temperature characteristics of relative dielectric constant. By sandwiching such a laminated dielectric between a pair of electrodes, a capacitor having improved temperature characteristics of relative permittivity can be obtained.
【００１２】[0012]
【発明の実施の形態】本発明の積層誘電体では、ゾルゲ
ル法により形成された異種セラミックからなる誘電体薄
膜を積層してなるものである。BEST MODE FOR CARRYING OUT THE INVENTION The laminated dielectric of the present invention is formed by laminating dielectric thin films made of different kinds of ceramics formed by a sol-gel method.
【００１３】誘電体薄膜をゾルゲル法により作製したの
は、誘電体薄膜を作製するのが容易であるからであり、
しかも、スパッタリング等の物理蒸着法と比較して、Ｐ
ｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 等特定の組成の膜の作製が
容易（組成の制御が容易）であり、膜厚の制御が容易だ
からである。The reason why the dielectric thin film is manufactured by the sol-gel method is that it is easy to manufacture the dielectric thin film.
Moreover, compared to physical vapor deposition methods such as sputtering, P
This is because it is easy to form a film having a specific composition such as b (Mg 1/3 Nb 2/3 ) O 3 (the composition can be easily controlled), and the film thickness can be easily controlled.
【００１４】異種セラミックからなる誘電体薄膜は、一
般的に比誘電率の温度係数が異なるものであり、誘電体
薄膜の種類としては２種以上である必要がある。Dielectric thin films made of different types of ceramics generally have different temperature coefficients of relative permittivity, and it is necessary that the dielectric thin films are of two or more types.
【００１５】異種セラミックからなる誘電体薄膜として
は、例えば、組成式Ｐｂ（Ｍｇ1/3Ｎｂ2/3 ）Ｏ3 で表
される薄膜と、組成式０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）
Ｏ3−０．１ＰｂＴｉＯ3 で表される薄膜の２種類、あ
るいは、組成式Ｂａ（Ｔｉ0. 87Ｓｎ0.13）Ｏ3 で表され
る薄膜と、組成式Ｂａ（Ｔｉ0.9 Ｚｒ0.1 ）Ｏ3 で表さ
れる２種類の薄膜が最適であるが、本発明ではこれに限
定されるものではない。特に、ある温度において正の温
度係数を有する誘電体薄膜と、同温度において負の温度
係数を有する誘電体薄膜であることが望ましい。As the dielectric thin film composed of different ceramics, for example, a thin film represented by the composition formula Pb (Mg 1/3 Nb 2/3 ) O 3 and a composition formula 0.9Pb (Mg 1/3 Nb 2 / 3 )
2 kinds of thin films represented by O 3 -0.1PbTiO 3, or a thin film represented by the composition formula Ba (Ti 0. 87 Sn 0.13) O 3, a composition formula Ba (Ti 0.9 Zr 0.1) O 3 The two types of thin films shown are optimal, but the invention is not so limited. In particular, a dielectric thin film having a positive temperature coefficient at a certain temperature and a dielectric thin film having a negative temperature coefficient at the same temperature are desirable.
【００１６】図１（ａ）〜（ｄ）に本発明の積層誘電体
の断面図を示す。図において、符号１は積層誘電体を示
している。1 (a) to 1 (d) are sectional views of the laminated dielectric material of the present invention. In the figure, reference numeral 1 indicates a laminated dielectric.
【００１７】積層誘電体１は、誘電体薄膜２と誘電体薄
膜３が交互に積層して形成されており、この積層誘電体
１はＰｔからなる電極５の上面に形成されている。図１
（ａ）は誘電体薄膜２の上面に誘電体薄膜３が積層され
た状態、図１（ｂ）は、誘電体薄膜２と誘電体薄膜３が
２層ずつ交互に積層された状態、図１（ｃ）は、誘電体
薄膜２と誘電体薄膜３が５層ずつ交互に積層された状
態、図１（ｄ）は、誘電体薄膜２と誘電体薄膜３が１０
層ずつ交互に積層された状態を示す。The laminated dielectric 1 is formed by alternately laminating the dielectric thin films 2 and the dielectric thin films 3, and the laminated dielectric 1 is formed on the upper surface of the electrode 5 made of Pt. FIG.
1A shows a state in which the dielectric thin film 3 is laminated on the upper surface of the dielectric thin film 2, and FIG. 1B shows a state in which the dielectric thin film 2 and the dielectric thin film 3 are alternately laminated two by two. 1C shows a state in which the dielectric thin film 2 and the dielectric thin film 3 are alternately laminated in five layers, and FIG. 1D shows the dielectric thin film 2 and the dielectric thin film 3 each having 10 layers.
The state where the layers are alternately stacked is shown.
【００１８】特に、誘電体薄膜が、組成式Ｐｂ（Ｍｇ
1/3 Ｎｂ2/3 ）Ｏ3 で表される薄膜と、組成式０．９Ｐ
ｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −０．１ＰｂＴｉＯ3 で表
される薄膜の２種類であり、これらを交互に積層した場
合には、前記誘電体薄膜が０．０１〜０．２μｍ、特に
は０．０２５〜０．１２５μｍの厚みで多数積層する
程、高誘電率となり、比誘電率の温度特性と相まって高
誘電率の積層誘電体、並びにコンデンサを得ることがで
きる。In particular, the dielectric thin film has a composition formula Pb (Mg
1/3 Nb 2/3 ) O 3 thin film and composition formula 0.9P
b (Mg 1/3 Nb 2/3 ) O 3 −0.1PbTiO 3 which are two kinds of thin films, and when these are alternately laminated, the dielectric thin film is 0.01 to 0. The larger the number of laminated layers having a thickness of 2 μm, particularly 0.025 to 0.125 μm, the higher the dielectric constant becomes, and the laminated dielectric having a high dielectric constant and the capacitor can be obtained in combination with the temperature characteristic of the relative dielectric constant.
【００１９】即ち、図１（ａ）〜（ｄ）で説明すると、
これらの図に示される積層誘電体１は同一厚みである
が、その各層の厚みが薄い程（積層数が多い程）比誘電
率を向上することができる。即ち、図１（ａ）の積層体
Ａよりも図１（ｃ）の積層体Ｃの方が比誘電率が高くな
る。特に、比誘電率を高くするという観点から、誘電体
薄膜の厚みが０．０１〜０．２μｍとすることが望まし
い。ここで、誘電体薄膜の厚みを０．０１〜０．２μｍ
の厚みとしたのは、誘電体薄膜の厚みが０．０１μｍよ
りも薄いと、異なる誘電体薄膜を積層した場合に完全固
溶する場合があり．比誘電率が低下したり、温度特性が
劣化するからである。また、０．２μｍよりも厚くなる
と、焼成時に誘電体薄膜にクラックが生じ易いからであ
る。誘電体薄膜の厚みは、０．０２５〜０．１２５μｍ
であることが望ましい。That is, referring to FIGS. 1 (a) to 1 (d),
Although the laminated dielectrics 1 shown in these figures have the same thickness, the thinner the thickness of each layer (the larger the number of laminated layers), the more the relative dielectric constant can be improved. That is, the relative permittivity of the laminated body C of FIG. 1C is higher than that of the laminated body A of FIG. Particularly, from the viewpoint of increasing the relative dielectric constant, it is desirable that the thickness of the dielectric thin film be 0.01 to 0.2 μm. Here, the thickness of the dielectric thin film is 0.01 to 0.2 μm.
The reason for the thickness is that, if the thickness of the dielectric thin film is less than 0.01 μm, it may cause a complete solid solution when different dielectric thin films are laminated. This is because the relative dielectric constant is lowered and the temperature characteristics are deteriorated. Also, if the thickness is more than 0.2 μm, cracks are likely to occur in the dielectric thin film during firing. The thickness of the dielectric thin film is 0.025 to 0.125 μm
It is desirable that
【００２０】本発明の図１（ａ）の積層誘電体は、誘電
体薄膜の表面に、異なる誘電体薄膜を形成することによ
り得られ、図１（ｂ）〜（ｄ）の場合には、再度上記工
程を繰り返すことにより得られる。即ち、例えば、ある
温度で正の温度係数を有する誘電体材料Ａの誘電体薄膜
を基板上に形成した後、その誘電体薄膜上に同温度で負
の温度係数を有する誘電体材料Ｂの薄膜を形成する。そ
の後、８００℃以上１２００℃以下の高温で一括焼成
し、結晶化させ、積層体を作製する。The laminated dielectric of FIG. 1 (a) of the present invention is obtained by forming different dielectric thin films on the surface of the dielectric thin film. In the case of FIGS. 1 (b) to 1 (d), It is obtained by repeating the above steps again. That is, for example, after forming a dielectric thin film of a dielectric material A having a positive temperature coefficient at a certain temperature on a substrate, a thin film of a dielectric material B having a negative temperature coefficient at the same temperature on the dielectric thin film. To form. After that, they are collectively fired at a high temperature of 800 ° C. or more and 1200 ° C. or less and crystallized to produce a laminate.
【００２１】本発明の積層誘電体は、例えば、先ず、ゾ
ルゲル法によりＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 前駆体溶
液と、０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −０．１Ｐ
ｂＴｉＯ3 前駆体溶液を合成し、これらの合成溶液を塗
布溶液とする。The laminated dielectric of the present invention is prepared, for example, by first using a sol-gel method to prepare a Pb (Mg 1/3 Nb 2/3 ) O 3 precursor solution and 0.9 Pb (Mg 1/3 Nb 2/3 ) O. 3 -0.1P
bTiO 3 precursor solutions are synthesized, and these synthetic solutions are used as coating solutions.
【００２２】そして、基板上にＰｂ（Ｍｇ1/3 Ｎ
ｂ2/3 ）Ｏ3 前駆体溶液を塗布し、乾燥した後、熱処理
しゲル膜を作製し、この溶液塗布−熱処理の操作を所定
回数繰り返し、所定厚みのＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ
3 からなるゲル膜を形成する。Then, Pb (Mg 1/3 N
b 2/3 ) O 3 precursor solution is applied, dried and then heat-treated to form a gel film, and this solution application-heat treatment operation is repeated a predetermined number of times to obtain a predetermined thickness of Pb (Mg 1/3 Nb 2 / 3 ) O
A gel film consisting of 3 is formed.
【００２３】この後、前記誘電体薄膜の上面に、０．９
Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −０．１ＰｂＴｉＯ3 前
駆体溶液を塗布し、乾燥した後、熱処理を行い、ゲル膜
を作製し、この溶液塗布−熱処理の操作を所定回数繰り
返し、所定厚みの０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3
−０．１ＰｂＴｉＯ3 からなるゲル膜を形成し、所定温
度で焼成し、図１（ａ）に示すような積層誘電体を作製
する。Then, 0.9 is formed on the upper surface of the dielectric thin film.
Pb (Mg 1/3 Nb 2/3 ) O 3 -0.1PbTiO 3 precursor solution is applied, dried and then heat-treated to form a gel film, and this solution application-heat treatment operation is repeated a predetermined number of times. , 0.9Pb (Mg 1/3 Nb 2/3 ) O 3 with a predetermined thickness
Gel film is formed consisting -0.1PbTiO 3, and calcined at a predetermined temperature to produce a laminate dielectric, as shown in FIG. 1 (a).
【００２４】コンデンサを作製する場合には、基板上
に、例えばＰｔ電極を形成した後、このＰｔ電極の表面
に、前述したようにＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 から
なるゲル膜と０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −
０．１ＰｂＴｉＯ3 からなるゲル膜を形成し、所定温度
で焼成し、さらに、０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ
3−０．１ＰｂＴｉＯ3 からなる誘電体薄膜の表面に、
例えば、金電極を形成し、本発明のコンデンサを得る。
また、上記積層誘電体と電極とを交互に積層して積層コ
ンデンサを形成しても良い。あるいは、異種の誘電体薄
膜を積層して積層誘電体が形成されるが、異種の誘電体
薄膜の間に電極を形成して積層コンデンサを構成しても
良い。In the case of producing a capacitor, for example, a Pt electrode is formed on a substrate and then a gel containing Pb (Mg 1/3 Nb 2/3 ) O 3 is formed on the surface of the Pt electrode as described above. Membrane and 0.9Pb (Mg 1/3 Nb 2/3 ) O 3 −
A gel film made of 0.1PbTiO 3 is formed, baked at a predetermined temperature, and further 0.9Pb (Mg 1/3 Nb 2/3 ) O.
On the surface of the dielectric thin film made of 3-0.1PbTiO 3 ,
For example, a gold electrode is formed to obtain the capacitor of the present invention.
Further, the laminated dielectric and the electrodes may be alternately laminated to form a laminated capacitor. Alternatively, a laminated dielectric is formed by laminating different kinds of dielectric thin films, but electrodes may be formed between different kinds of dielectric thin films to form a laminated capacitor.
【００２５】[0025]
【実施例】 実施例１ ゾルゲル法を用いてＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 （以
下ＰＭＮ）前駆体溶液と０．９Ｐｂ（Ｍｇ1/3 Ｎ
ｂ2/3 ）Ｏ3 −０．１ＰｂＴｉＯ3 （以下９０ＰＭＮ
Ｔ）前駆体溶液を合成した。これらの溶液の濃度を２−
メトキシエタノ−ルで約３倍に希釈し、塗布溶液とし
た。Example 1 A Pb (Mg 1/3 Nb 2/3 ) O 3 (hereinafter PMN) precursor solution and 0.9 Pb (Mg 1/3 N) were prepared by using a sol-gel method.
b 2/3 ) O 3 -0.1PbTiO 3 (hereinafter 90 PMN
T) A precursor solution was synthesized. Adjust the concentration of these solutions to 2-
It was diluted about 3 times with methoxyethanol to obtain a coating solution.
【００２６】サファイア単結晶基板上に電極となるＰｔ
（１１１）を６５０℃でスパッタ蒸着して厚さ０．２ｍ
ｍのＰｔ電極を形成し、該Ｐｔ電極の表面に、まずＰＭ
Ｎ塗布溶液をスピンコ−タ−で塗布し、３００℃で熱処
理を１分間行い、ゲル膜を作製した。塗布溶液の塗布−
熱処理の操作を１０回繰り返し、厚み０．２５μｍのＰ
ＭＮゲル膜を形成した。Pt serving as an electrode on a sapphire single crystal substrate
(111) is sputter deposited at 650 ° C to a thickness of 0.2 m.
m Pt electrode is formed, and PM is first formed on the surface of the Pt electrode.
The N coating solution was applied by a spin coater and heat-treated at 300 ° C. for 1 minute to form a gel film. Application of coating solution −
The operation of heat treatment is repeated 10 times to obtain P of 0.25 μm thickness.
An MN gel film was formed.
【００２７】このＰＭＮゲル膜の上に９０ＰＭＮＴ塗布
溶液を同様に塗布、乾燥、熱処理を行い、ゲル膜を作製
した。塗布溶液の塗布−熱処理を１０回繰り返し、厚み
０．２５μｍの９０ＰＭＮＴゲル膜を形成した。A 90 PMNT coating solution was similarly coated on this PMN gel film, dried and heat-treated to form a gel film. The application of the application solution and the heat treatment were repeated 10 times to form a 90 PMNT gel film having a thickness of 0.25 μm.
【００２８】０．２５μｍのＰＭＮゲルと０．２５μｍ
の９０ＰＭＮＴゲルからなる膜厚約０．５μｍの積層ゲ
ル膜を８４０℃で３０秒間焼成し、結晶化させ、Ｐｔ電
極の上面に、図１（ａ）に示すような、ＰＭＮからなる
厚み０．２５μｍの誘電体薄膜２と９０ＰＭＮＴ薄膜３
からなる厚み０．２５μｍの積層誘電体１を形成した。
この積層誘電体１の上面に厚み０．２ｍｍの金電極をス
パッタ蒸着により形成し、薄膜コンデンサを作製した。0.25 μm PMN gel and 0.25 μm
Of 90 PMNT gel having a thickness of about 0.5 μm was fired at 840 ° C. for 30 seconds to be crystallized, and the Pn electrode was formed on the upper surface of the Pt electrode with a thickness of 0. 25 μm dielectric thin film 2 and 90 PMNT thin film 3
A laminated dielectric 1 having a thickness of 0.25 μm was formed.
A gold electrode having a thickness of 0.2 mm was formed on the upper surface of this laminated dielectric 1 by sputter deposition to manufacture a thin film capacitor.
【００２９】そして、ＬＣＲメータ（ヒュウレットパッ
カード社製４２８４Ａ）を用いて、２５℃、１ｋＨｚ
（Ａｃ１００ｍＶ）の条件で比誘電率を求めたところ、
３０００であった。また、−４０℃から＋７０℃の温度
範囲での比誘電率の温度変化を調べ、結果を図２に示
す。Then, using an LCR meter (4284A manufactured by Hulett Packard), 25 ° C., 1 kHz
When the relative permittivity was calculated under the condition of (Ac 100 mV),
3000. Further, the temperature change of the relative permittivity in the temperature range of −40 ° C. to + 70 ° C. was examined, and the result is shown in FIG.
【００３０】比較例として実施例１の積層体と同様に、
Ｐｔ膜が形成された基板上に、０．５μｍのＰＭＮ薄膜
（比較例ａ）、または０．５μｍの９０ＰＭＮＴ薄膜
（比較例ｂ）を作製し、比誘電率の温度特性を評価し
た。図２にそれぞれの結果を示す。この図２より、比誘
電率の温度係数が正であるＰＭＮと、比誘電率の温度係
数が負である９０ＰＭＮＴを積層することにより、比誘
電率の温度特性が向上していることが判る。As a comparative example, similarly to the laminate of Example 1,
A 0.5 μm PMN thin film (Comparative Example a) or a 0.5 μm 90 PMNT thin film (Comparative Example b) was formed on the substrate on which the Pt film was formed, and the temperature characteristics of the relative dielectric constant were evaluated. The respective results are shown in FIG. It can be seen from FIG. 2 that the temperature characteristics of the relative permittivity are improved by stacking PMN having a positive temperature coefficient of the relative permittivity and 90 PMNT having a negative temperature coefficient of the relative permittivity.
【００３１】また、本発明者等は、積層誘電体の厚みを
図１（ａ）（積層体Ａ）と同じにして、ＰＭＮゲルと９
０ＰＭＮＴゲルの膜厚を種々変化させるとともに、積層
数を変化させ、図１（ｂ）（積層体Ｂ）、図１（ｃ）
（積層体Ｃ）、図１（ｄ）（積層体Ｄ）に示すような積
層誘電体を形成し、上記と同様にして焼成して電極を形
成し、コンデンサを形成した。そして、上記と同様にし
て比誘電率の温度特性を測定し、この結果を図３に示し
た。また、２５℃における比誘電率と、各誘電体薄膜の
厚みとの関係を図４に示す。Further, the present inventors set the thickness of the laminated dielectric to be the same as that of FIG.
By changing the film thickness of the 0 PMNT gel in various ways and changing the number of laminated layers, FIG. 1 (b) (laminated body B), FIG.
(Laminate C), a laminated dielectric as shown in FIG. 1 (d) (laminate D) was formed and fired in the same manner as above to form electrodes, thereby forming a capacitor. Then, the temperature characteristic of the relative dielectric constant was measured in the same manner as above, and the result is shown in FIG. Further, FIG. 4 shows the relationship between the relative dielectric constant at 25 ° C. and the thickness of each dielectric thin film.
【００３２】図３，図４より、積層誘電体の厚みを同一
とした場合には、誘電体薄膜が薄い程（積層数が多い
程）比誘電率が高いことが判る。しかしながら、誘電体
薄膜の厚みが０．０５μｍ以下になると、両者が固溶し
はじめ、比誘電率が若干減少する傾向があることが判
る。From FIGS. 3 and 4, it can be seen that, when the laminated dielectrics have the same thickness, the thinner the dielectric thin film (the greater the number of laminated layers), the higher the relative dielectric constant. However, when the thickness of the dielectric thin film is 0.05 μm or less, both of them start to form a solid solution, and the relative permittivity tends to slightly decrease.
【００３３】実施例２ ゾルゲル法を用いてＢａ（Ｔｉ0.87Ｓｎ0.13）Ｏ3 （以
下ＢＴＳ１３）前駆体溶液とＢａ（Ｔｉ0.9 Ｚｒ0.1 ）
Ｏ3 （以下ＢＴＺ０１）前駆体溶液を合成し、これらの
溶液の濃度を２−メトキシエタノ−ルで約３倍に希釈
し、塗布溶液とした。Example 2 Ba (Ti 0.87 Sn 0.13 ) O 3 (hereinafter BTS 13) precursor solution and Ba (Ti 0.9 Zr 0.1 ) were prepared by the sol-gel method.
O 3 (hereinafter BTZ01) precursor solution was synthesized and the concentration of these solutions 2 Metokishietano - diluted about 3-fold with Le, and a coating solution.
【００３４】サファイア単結晶基板上に電極となるＰｔ
（１１１）を６５０℃でスパッタ蒸着して厚さ０．２ｍ
ｍのＰｔ電極を形成し、該Ｐｔ電極の表面に、まずＢＴ
Ｓ１３塗布溶液をスピンコ−タ−で塗布し、乾燥させた
後、３００℃と７５０℃で熱処理を１分間行い、ゲル膜
を作製した。塗布溶液の塗布−熱処理の操作を１０回繰
り返し、厚み０．５μｍのＢＴＳ１３ゲル膜を形成し
た。Pt serving as an electrode on a sapphire single crystal substrate
(111) is sputter deposited at 650 ° C to a thickness of 0.2 m.
m Pt electrode is formed, and BT is first formed on the surface of the Pt electrode.
The S13 coating solution was applied with a spin coater, dried, and then heat-treated at 300 ° C. and 750 ° C. for 1 minute to form a gel film. The operation of applying the coating solution and the heat treatment was repeated 10 times to form a BTS13 gel film having a thickness of 0.5 μm.
【００３５】ＢＴＳ１３ゲル膜の上にＢＴＺ０１塗布溶
液を同様に塗布し、乾燥させた後、３００℃と７５０℃
で熱処理を１分間行い、ゲル膜を作製した。塗布溶液の
塗布−熱処理を１０回繰り返し、厚み０．５μｍのＢＴ
Ｚ０１ゲル膜を形成した。The BTZ01 coating solution was similarly coated on the BTS13 gel film, dried, and then dried at 300 ° C. and 750 ° C.
A heat treatment was performed for 1 minute to prepare a gel film. BT with a thickness of 0.5 μm is obtained by repeating the application of the application solution and heat treatment 10 times
A Z01 gel film was formed.
【００３６】０．５μｍのＢＴＳ１３ゲルと０．５μｍ
のＢＴＺ０１ゲルからなる膜厚約１．０μｍの積層ゲル
膜を１１００℃で３０分間焼成し、結晶化させ、積層誘
電体を作製した。0.5 μm BTS13 gel and 0.5 μm
A laminated gel film of BTZ01 gel having a thickness of about 1.0 μm was baked at 1100 ° C. for 30 minutes to be crystallized to produce a laminated dielectric.
【００３７】この積層誘電体表面に厚み０．２ｍｍの金
電極をスパッタ蒸着により形成し、薄膜コンデンサを作
製し、ＬＣＲメータ（ヒュウレットパッカード社製４２
８４Ａ）により、２５℃、１ｋＨｚ（Ａｃ１００ｍＶ）
の条件で比誘電率を測定したところ、比誘電率は約１５
００であった。また、−４０℃から＋７０℃の温度範囲
での比誘電率の温度変化を調べ、結果を図５に示す。A gold electrode having a thickness of 0.2 mm was formed on the surface of the laminated dielectric material by sputter deposition to prepare a thin film capacitor, and an LCR meter (42 manufactured by Hulet Packard) was manufactured.
84 A), 25 ° C, 1 kHz (Ac100 mV)
When the relative permittivity was measured under the conditions of, the relative permittivity was about 15
It was 00. Further, the temperature change of the relative dielectric constant in the temperature range of −40 ° C. to + 70 ° C. was examined, and the result is shown in FIG.
【００３８】比較例として上記と同様に、Ｐｔ電極表面
に１．０μｍのＢＴＳ１３単層薄膜（比較例ｂ）、また
は１．０μｍのＢＴＺ０１単層薄膜（比較例ａ）を作製
し、比誘電率の温度特性を評価した。図５にそれぞれの
結果を示す。この図５より、積層誘電体を形成すること
により、比誘電率の温度特性が向上していることがわか
る。As a comparative example, a BTS13 single-layer thin film of 1.0 μm (Comparative Example b) or a BTZ01 single-layer thin film of 1.0 μm (Comparative Example a) was prepared on the surface of the Pt electrode in the same manner as described above, and the relative dielectric constant was obtained. Was evaluated for temperature characteristics. The respective results are shown in FIG. It can be seen from FIG. 5 that the temperature characteristics of the relative permittivity are improved by forming the laminated dielectric.
【００３９】[0039]
【発明の効果】以上詳述した様に、本発明によれば、ゾ
ルゲル法により形成された異種セラミックからなる誘電
体薄膜を積層して積層誘電体を作製することにより、そ
れぞれの誘電体薄膜が有する温度による比誘電率の変化
が相殺され、結果として温度特性を改善することができ
る。特に、ある温度において正の温度係数を有する誘電
体薄膜と、同温度において負の温度係数を有する誘電体
薄膜を積層した場合に有効である。よって、本発明のコ
ンデンサでは、温度特性が改善されたコンデンサを簡便
に作製することができる。As described above in detail, according to the present invention, the dielectric thin films made of different ceramics formed by the sol-gel method are laminated to form a laminated dielectric, whereby the respective dielectric thin films are formed. The change in the relative dielectric constant due to the temperature possessed is canceled out, and as a result, the temperature characteristic can be improved. Particularly, it is effective when a dielectric thin film having a positive temperature coefficient at a certain temperature and a dielectric thin film having a negative temperature coefficient at the same temperature are laminated. Therefore, with the capacitor of the present invention, it is possible to easily manufacture a capacitor having improved temperature characteristics.
【図１】本発明のＰｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 からな
る誘電体薄膜と０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −
０．１ＰｂＴｉＯ3 からなる誘電体薄膜とを交互に積層
した積層誘電体を示す縦断面図である。FIG. 1 is a dielectric thin film of Pb (Mg 1/3 Nb 2/3 ) O 3 of the present invention and 0.9 Pb (Mg 1/3 Nb 2/3 ) O 3 −
FIG. 6 is a vertical cross-sectional view showing a laminated dielectric in which dielectric thin films made of 0.1PbTiO 3 are alternately laminated.
【図２】Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 からなる誘電体
薄膜と０．９Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 −０．１Ｐ
ｂＴｉＯ3 からなる誘電体薄膜の積層誘電体について、
温度に対する比誘電率の変化を示すグラフである。FIG. 2 is a dielectric thin film made of Pb (Mg 1/3 Nb 2/3 ) O 3 and 0.9Pb (Mg 1/3 Nb 2/3 ) O 3 -0.1P.
Regarding the laminated dielectric of the dielectric thin film made of bTiO 3 ,
It is a graph which shows the change of the relative dielectric constant with respect to temperature.
【図３】図１（ａ）〜（ｄ）の積層誘電体の温度に対す
る比誘電率の変化を示すグラフである。FIG. 3 is a graph showing changes in relative dielectric constant with respect to temperature of the laminated dielectrics of FIGS. 1 (a) to 1 (d).
【図４】図１（ａ）〜（ｄ）の積層誘電体において、２
５℃における比誘電率と各誘電体薄膜の厚みとの関係を
示すグラフである。FIG. 4 is a schematic view of the laminated dielectrics of FIGS.
It is a graph which shows the relationship between the relative dielectric constant in 5 degreeC, and the thickness of each dielectric thin film.
【図５】Ｂａ（Ｔｉ0.87Ｓｎ0.13）Ｏ3 からなる誘電体
薄膜とＢａ（Ｔｉ0.9 Ｚｒ0.1）Ｏ3 からなる誘電体薄
膜の積層誘電体について、温度に対する比誘電率の変化
を示すグラフである。FIG. 5 is a graph showing a change in relative dielectric constant with respect to temperature for a laminated dielectric of a dielectric thin film made of Ba (Ti 0.87 Sn 0.13 ) O 3 and a dielectric thin film made of Ba (Ti 0.9 Zr 0.1 ) O 3. is there.
１・・・積層誘電体 ２，３・・・誘電体薄膜 ５・・・電極 1 ... Laminated dielectric 2, 3 ... Dielectric thin film 5 ... Electrode
Claims (5)
クからなる誘電体薄膜を積層してなることを特徴とする
積層誘電体。1. A laminated dielectric material comprising laminated dielectric thin films made of different ceramics formed by a sol-gel method.
ことを特徴とする請求項１記載の積層誘電体。2. A laminated dielectric according to claim 1, wherein two kinds of dielectric thin films are alternately laminated.
2/3 ）Ｏ3 で表される薄膜と、組成式０．９Ｐｂ（Ｍｇ
1/3 Ｎｂ2/3 ）Ｏ3 −０．１ＰｂＴｉＯ3 で表される薄
膜の２種類からなり、これらの２種類の誘電体薄膜を交
互に積層してなることを特徴とする請求項１記載の積層
誘電体。3. The dielectric thin film has a composition formula of Pb (Mg 1/3 Nb
2/3 ) O 3 and a composition formula 0.9Pb (Mg
1/3 Nb 2/3) O 3 consists of two kinds of thin films represented by -0.1PbTiO 3, according to claim 1, characterized in that formed by laminating these two types of dielectric thin films alternately Laminated dielectric.
0.13）Ｏ3 で表される薄膜と、組成式Ｂａ（Ｔｉ0.9 Ｚ
ｒ0.1 ）Ｏ3 で表される薄膜の２種類からなり、これら
の２種類の誘電体薄膜を交互に積層してなることを特徴
とする請求項１記載の積層誘電体。4. The composition of the dielectric thin film is Ba (Ti 0.87 Sn).
0.13 ) O 3 thin film and the composition formula Ba (Ti 0.9 Z
2. The laminated dielectric material according to claim 1, wherein the laminated dielectric material comprises two types of thin films represented by r 0.1 ) O 3 , and these two types of dielectric thin films are alternately laminated.
クからなる誘電体薄膜を積層してなる積層誘電体の両面
に、一対の電極を形成してなることを特徴とするコンデ
ンサ。5. A capacitor comprising a pair of electrodes formed on both sides of a laminated dielectric formed by laminating dielectric thin films made of different kinds of ceramics formed by a sol-gel method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01452496A JP3389398B2 (en) | 1996-01-30 | 1996-01-30 | Capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01452496A JP3389398B2 (en) | 1996-01-30 | 1996-01-30 | Capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09213569A true JPH09213569A (en) | 1997-08-15 |
| JP3389398B2 JP3389398B2 (en) | 2003-03-24 |
Family
ID=11863512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01452496A Expired - Fee Related JP3389398B2 (en) | 1996-01-30 | 1996-01-30 | Capacitor |
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| Country | Link |
|---|---|
| JP (1) | JP3389398B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8218287B2 (en) | 2009-03-27 | 2012-07-10 | Tdk Corporation | Thin-film device |
| US8339766B2 (en) | 2009-03-31 | 2012-12-25 | Tdk Corporation | Method of manufacturing thin film capacitor and thin film capacitor |
| US8498095B2 (en) | 2009-11-30 | 2013-07-30 | Tdk Corporation | Thin-film capacitor with internally hollow through holes |
| JP2016537807A (en) * | 2013-10-02 | 2016-12-01 | エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ | Ceramic multilayer device based on BaTi (1-y) Zry03 |
| CN114974891A (en) * | 2022-05-27 | 2022-08-30 | 德阳三环科技有限公司 | Multilayer ceramic capacitor and preparation method thereof |
| CN114974891B (en) * | 2022-05-27 | 2024-05-14 | 德阳三环科技有限公司 | Multilayer ceramic capacitor and preparation method thereof |
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1996
- 1996-01-30 JP JP01452496A patent/JP3389398B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8218287B2 (en) | 2009-03-27 | 2012-07-10 | Tdk Corporation | Thin-film device |
| US8339766B2 (en) | 2009-03-31 | 2012-12-25 | Tdk Corporation | Method of manufacturing thin film capacitor and thin film capacitor |
| US8498095B2 (en) | 2009-11-30 | 2013-07-30 | Tdk Corporation | Thin-film capacitor with internally hollow through holes |
| JP2016537807A (en) * | 2013-10-02 | 2016-12-01 | エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ | Ceramic multilayer device based on BaTi (1-y) Zry03 |
| CN114974891A (en) * | 2022-05-27 | 2022-08-30 | 德阳三环科技有限公司 | Multilayer ceramic capacitor and preparation method thereof |
| CN114974891B (en) * | 2022-05-27 | 2024-05-14 | 德阳三环科技有限公司 | Multilayer ceramic capacitor and preparation method thereof |
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