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JPH09134613A - Dielectric thin film and thin film capacitor and manufacture of dielectric thin film - Google Patents

Dielectric thin film and thin film capacitor and manufacture of dielectric thin film

Info

Publication number
JPH09134613A
JPH09134613A JP8138432A JP13843296A JPH09134613A JP H09134613 A JPH09134613 A JP H09134613A JP 8138432 A JP8138432 A JP 8138432A JP 13843296 A JP13843296 A JP 13843296A JP H09134613 A JPH09134613 A JP H09134613A
Authority
JP
Japan
Prior art keywords
thin film
mgnb
precursor solution
alkoxide
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP8138432A
Other languages
Japanese (ja)
Other versions
JP3485417B2 (en
Inventor
Naokane Nagakari
尚謙 永仮
Yasuyo Kamigaki
耕世 神垣
Shinji Nanbu
信次 南部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
Original Assignee
Kyocera Corp
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Filing date
Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to JP13843296A priority Critical patent/JP3485417B2/en
Publication of JPH09134613A publication Critical patent/JPH09134613A/en
Application granted granted Critical
Publication of JP3485417B2 publication Critical patent/JP3485417B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric thin film composed of a prescribed compound which has a large specific dielectric constant not less than 2500 and has a film thickness not more than 2μm. SOLUTION: This dielectric thin film is composed of Pb(Mg1/3 Nb2/3 ) O3 which has a film thickness not more than 2μm and has a specific dielectric constant not less than 2500 at a room temperature. In a thin film capacitor, this thin film is sandwiched by a pair of electrodes. This thin film is manufactured by using a Pb(Mg1/3 Nb2/3 ) O3 precursor solution obtained by synthesizing them by mixing an MgNb precursor solution composed of MgNb composite alkoxide having absorption in the vicinity of 658cm<-1> in an infrared absorption spectrum and a Pb precursor solution. It is manufacture by using an MgNb precursor solution composed of MgNb sol obtained by partially hydrolyzing this MgNb composite alkoxide.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明はゾルゲル法により作
製された誘電体薄膜およびこの誘電体薄膜を用いた薄膜
コンデンサ並びに誘電体薄膜の製法に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric thin film produced by a sol-gel method, a thin film capacitor using this dielectric thin film, and a method for producing a dielectric thin film.

【0002】[0002]

【従来技術】2種以上の金属からなる複合ペロブスカイ
ト酸化物、特にPb(Mg1/3 Nb2/3 )O3 (以下P
MNという)は室温で大きな比誘電率、良好な温度特性
を有するため、コンデンサ材料として有用であることが
知られている。
2. Description of the Related Art A composite perovskite oxide composed of two or more metals, especially Pb (Mg 1/3 Nb 2/3 ) O 3 (hereinafter P
It is known that MN) is useful as a capacitor material because it has a large relative dielectric constant at room temperature and good temperature characteristics.

【0003】このようなPMN焼結体として、従来、P
bO粉末とMgCO3 粉末とNb25 粉末とを一括し
て混合粉砕し、焼結する固相焼結法が知られている。し
かしながら、このような一括して混合粉砕する固相焼結
によるPMN焼結体の作製では、ほぼペロブスカイト単
相からなる焼結体を得るのは困難であり、低温で安定な
パイロクロア相が生成し易く、また生成したパイロクロ
ア相は誘電率が低いため、結果として焼結体の比誘電率
が低くなり、コンデンサ材料として不適当な場合が多
い。このため、固相焼結法では、MgNb酸化物(Mg
Nb2 6 )とPb原料を反応させるコランバイト法に
よる合成が行われている。この方法によれば、ほぼペロ
ブスカイト単相の焼結体を得ることが可能となり、比誘
電率を15000以上とすることができる。
[0003] As such a PMN sintered body, conventionally,
There is known a solid phase sintering method in which bO powder, MgCO 3 powder, and Nb 2 O 5 powder are collectively mixed, pulverized, and sintered. However, in the production of a PMN sintered body by solid-state sintering in which the particles are collectively mixed and pulverized, it is difficult to obtain a sintered body having a single perovskite single phase, and a stable pyrochlore phase is formed at a low temperature. In addition, the pyrochlore phase generated is low in permittivity, and as a result, the relative permittivity of the sintered body is low, which is often unsuitable as a capacitor material. Therefore, in the solid phase sintering method, MgNb oxide (Mg
Nb 2 O 6 ) and a Pb raw material are reacted by the Columbite method. According to this method, it is possible to obtain a substantially single-phase perovskite sintered body, and the relative dielectric constant can be 15,000 or more.

【0004】一方、近年、電子機器の小型化に伴い、電
子部品の小型化,薄膜化が要求されており、PMN等の
高誘電率材料を薄膜化し、薄膜コンデンサに応用しよう
とされているが、従来の固相焼結法では膜厚はせいぜい
10μm程度であった。また、薄膜においても固相焼結
法による焼結体と同様、低温で安定なパイロクロア相が
生成し易く、ほぼペロブスカイト単相からなる膜を得る
のが困難となり、コンデンサ材料として不適当な場合が
多い。特に薄膜化する場合、下部電極との格子の不整合
及び化学結合の相違等でパイロクロア相が生成し易いと
いう問題があると言われており(例えば、特開平6−5
7437号公報参照)、パイロクロア相の少ないペロブ
スカイト単相のPMN薄膜を得るのが困難であった。
On the other hand, in recent years, along with the miniaturization of electronic equipment, there has been a demand for miniaturization and thinning of electronic parts, and it has been attempted to thin a high dielectric constant material such as PMN and apply it to a thin film capacitor. In the conventional solid-phase sintering method, the film thickness was at most about 10 μm. Similar to the sintered body obtained by the solid phase sintering method, a thin film is likely to form a stable pyrochlore phase at a low temperature, which makes it difficult to obtain a film composed of almost a single perovskite phase, and thus may be unsuitable as a capacitor material. Many. Especially when the film is thinned, it is said that there is a problem that a pyrochlore phase is easily generated due to a lattice mismatch with the lower electrode and a difference in chemical bond (for example, JP-A-6-5).
No. 7437), it was difficult to obtain a perovskite single-phase PMN thin film with a small amount of pyrochlore phase.

【0005】これらのパイロクロア相生成の問題を解決
する手法として、ゾルゲル法で作製されたPMN薄膜に
おいては、急速昇温焼成(特開平2−177521号公
報)やシーディング法(特開平6−57437号公報)
等の種々の手法が提案されており、ペロブスカイト単相
に近いPMN薄膜が得られている。
As a method for solving these problems of pyrochlore phase formation, in a PMN thin film produced by the sol-gel method, rapid temperature rising firing (JP-A-2-177521) and seeding method (JP-A-6-57437). Issue)
Have been proposed, and PMN thin films close to a perovskite single phase have been obtained.

【0006】[0006]

【発明が解決しようとする課題】しかしながら、急速昇
温焼成法,シーディング法によるPMN薄膜では、ほぼ
ペロブスカイト単相からなる膜が得られているが、未だ
比誘電率がせいぜい2000程度と低く、PMN本来の
特性が発揮されていないのが現状であった。
However, in the PMN thin film formed by the rapid temperature rising firing method and the seeding method, a film which is almost composed of a perovskite single phase is obtained, but the relative dielectric constant is still as low as about 2000, It was the current situation that the original characteristics of PMN were not exhibited.

【0007】[0007]

【課題を解決するための手段】本発明者等は、上記課題
の解決方法を鋭意検討した結果、ゾルゲル法によるPM
N薄膜の合成の際、他の求核性を有する有機金属化合物
の存在下においても安定なMg−O−Nb結合を有する
MgNb複合アルコキシド分子をMgNb前駆体として
用いること、或いはこのMgNb複合アルコキシド分子
を部分的に加水分解したゾルをMgNb前駆体として用
いることにより、室温での比誘電率が2500以上のP
MN薄膜を作製でき、さらにこれを用いて薄膜コンデン
サとして使用可能であることを見い出した。
Means for Solving the Problems The inventors of the present invention have made extensive studies as to how to solve the above problems.
When synthesizing an N thin film, a MgNb composite alkoxide molecule having a Mg—O—Nb bond that is stable even in the presence of another organometallic compound having a nucleophilicity is used as a MgNb precursor, or this MgNb composite alkoxide molecule is used. By using a sol partially hydrolyzed as a MgNb precursor, P having a relative dielectric constant of 2500 or more at room temperature can be obtained.
It has been found that an MN thin film can be produced and that it can be used as a thin film capacitor.

【0008】即ち、本発明の誘電体薄膜は、膜厚が2μ
m以下のPb(Mg1/3 Nb2/3 )O3 からなる誘電体
薄膜であって、室温での比誘電率が2500以上の優れ
た特性を有するものである。また、本発明の薄膜コンデ
ンサは、膜厚が2μm以下のPb(Mg1/3 Nb2/3
3 からなる誘電体薄膜であって、室温での比誘電率が
2500以上の誘電体薄膜を、一対の電極により挟持し
てなるものである。
That is, the dielectric thin film of the present invention has a thickness of 2 μm.
It is a dielectric thin film made of Pb (Mg 1/3 Nb 2/3 ) O 3 of m or less, and has excellent properties of a relative dielectric constant of 2500 or more at room temperature. The thin film capacitor of the present invention is made of Pb (Mg 1/3 Nb 2/3 ) having a film thickness of 2 μm or less.
A dielectric thin film made of O 3 and having a relative dielectric constant of 2,500 or more at room temperature sandwiched by a pair of electrodes.

【0009】本発明の誘電体薄膜は、ゾルゲル法により
調製されたPb(Mg1/3 Nb2/3)O3 前駆体溶液を塗
布し、焼成する誘電体薄膜の製法であって、前記Pb
(Mg1/3 Nb2/3 )O3 前駆体溶液を、赤外吸収スペ
クトルにおいて、658cm-1付近に吸収を有するMg
Nb複合アルコキシドからなるMgNb前駆体溶液と、
Pb前駆体溶液とを混合して合成することにより得られ
る。ここで、MgNb複合アルコキシドは、Mgのカル
ボン酸塩とNbのアルコキシドとの還流操作により合成
されることが望ましい。
The dielectric thin film of the present invention is a method for producing a dielectric thin film in which a Pb (Mg 1/3 Nb 2/3 ) O 3 precursor solution prepared by a sol-gel method is applied and fired.
In the infrared absorption spectrum of the (Mg 1/3 Nb 2/3 ) O 3 precursor solution, Mg having absorption near 658 cm -1
MgNb precursor solution consisting of Nb complex alkoxide,
It is obtained by synthesizing by mixing with a Pb precursor solution. Here, the MgNb composite alkoxide is preferably synthesized by a reflux operation of a carboxylate of Mg and an alkoxide of Nb.

【0010】また、ゾルゲル法により調製されたPb
(Mg1/3 Nb2/3 )O3 前駆体溶液を塗布し、焼成す
る誘電体薄膜の製法であって、前記Pb(Mg1/3 Nb
2/3 )O3 前駆体溶液を、赤外吸収スペクトルおいて、
658cm-1付近に吸収を有するMgNb複合アルコキ
シドを部分的に加水分解して得られたMgNbゾルから
なるMgNb前駆体溶液と、Pb前駆体溶液とを混合し
て合成することにより得られる。ここで、MgNb複合
アルコキシドは、Mgのカルボン酸塩とNbのアルコキ
シドとの還流操作により合成されることが望ましい。
Pb prepared by the sol-gel method
A method for producing a dielectric thin film, comprising applying a (Mg 1/3 Nb 2/3 ) O 3 precursor solution and baking the solution, said Pb (Mg 1/3 Nb
2/3 ) O 3 precursor solution in the infrared absorption spectrum,
It is obtained by mixing a MgNb precursor solution composed of a MgNb sol obtained by partially hydrolyzing a MgNb composite alkoxide having an absorption near 658 cm −1 and a Pb precursor solution to synthesize the mixture. Here, the MgNb composite alkoxide is preferably synthesized by a reflux operation of a carboxylate of Mg and an alkoxide of Nb.

【0011】[0011]

【作用】従来の方法で得られるMgNb複合アルコキシ
ド分子は、Mg〔Nb(OR)6 2 で示され、Mgと
Nbの複合化はアルコキシ基の配位結合によることが知
られている。しかしながら、配位結合によるMgNb複
合アルコキシド分子に酢酸鉛等の求核性有機金属化合物
を混合すると、複合化が崩れ不安定であることが報告さ
れている(日本セラミックス協会誌,102〔4〕P3
93〜396(1994))。
The MgNb composite alkoxide molecule obtained by the conventional method is represented by Mg [Nb (OR) 6 ] 2 , and it is known that the composite of Mg and Nb is due to the coordination bond of the alkoxy group. However, it has been reported that when a nucleophilic organometallic compound such as lead acetate is mixed with a MgNb complex alkoxide molecule having a coordinate bond, the complexation is broken and unstable (Journal of Japan Ceramic Society, 102 [4] P3).
93-396 (1994)).

【0012】本発明では、MgNb複合アルコキシド分
子を合成する際、Mg及びNbの金属化合物間の反応促
進、及び複合アルコキシド分子を安定化する手法を用
い、他の求核性有機金属化合物の存在下においても、安
定なMg−O−Nb結合を有するMgNb複合アルコキ
シドを合成させ、このMgNb複合アルコキシド分子を
含む溶液とPb前駆体溶液とを混合してPb(Mg1/3
Nb2/3 )O3 前駆体溶液を合成する点に特徴があり、
この様な手法で得られたMgNb前駆体溶液は、赤外吸
収スペクトル(以下IRスペクトル)において、658
cm-1付近に吸収を有し、溶液の段階で既にコランバイ
ト(MgNb2 6 )に近い構造を持つ、強固なMg−
O−Nb結合を有するMgNb複合アルコキシド分子が
形成されているため、他の求核性有機金属化合物(例え
ば酢酸鉛)に対して安定であり、Mg−O−Nb結合が
破壊されることなく、Pb(Mg1/3 Nb2/3 )O3
駆体を形成し、膜厚が2μm以下で室温での比誘電率が
2500以上の高い誘電率を有するPb(Mg1/3 Nb
2/3 )O3 薄膜が作製される。この作用効果は、特に、
Mgのカルボン酸塩とNbのアルコキシドとの還流操作
により合成されたMgNb複合アルコキシドを用いた場
合に顕著であり、比誘電率および誘電損失をさらに向上
することができる。
In the present invention, when synthesizing a MgNb complex alkoxide molecule, a method of promoting the reaction between the metal compounds of Mg and Nb and stabilizing the complex alkoxide molecule is used in the presence of another nucleophilic organometallic compound. Also, a MgNb composite alkoxide having a stable Mg—O—Nb bond is synthesized, and a solution containing the MgNb composite alkoxide molecule is mixed with a Pb precursor solution to prepare Pb (Mg 1/3
Nb 2/3 ) O 3 precursor solution is characterized in that
The MgNb precursor solution obtained by such a method has an infrared absorption spectrum (hereinafter, IR spectrum) of 658.
Strong Mg- having absorption near cm -1 and already having a structure close to that of corambite (MgNb 2 O 6 ) at the solution stage.
Since the MgNb complex alkoxide molecule having an O—Nb bond is formed, it is stable against other nucleophilic organometallic compounds (for example, lead acetate), and the Mg—O—Nb bond is not destroyed, A Pb (Mg 1/3 Nb 2/3 ) O 3 precursor is formed, and a Pb (Mg 1/3 Nb) having a high dielectric constant of 2 μm or less and a relative dielectric constant of 2500 or more at room temperature is formed.
2/3 ) O 3 thin film is produced. This effect is
This is remarkable when the MgNb composite alkoxide synthesized by the reflux operation of the carboxylate of Mg and the alkoxide of Nb is used, and the relative permittivity and the dielectric loss can be further improved.

【0013】即ち、MgNb複合アルコキシド分子を合
成する際、Mgのカルボン酸塩を原料として使用し、N
bのアルコキシドとの還流操作により、カルボン酸塩と
アルコキシド間のエステル脱離反応を促進することによ
って、赤外吸収スペクトルにおいて、658cm-1付近
にMg−O−Nb結合を有するMgNb複合アルコキシ
ド分子を合成し、このMgNb複合アルコキシド分子を
含む溶液とPb前駆体溶液とを混合してPb(Mg1/3
Nb2/3 )O3 前駆体溶液を合成することが望ましい。
That is, when synthesizing the MgNb complex alkoxide molecule, Mg carboxylate is used as a raw material, and N
By promoting the ester elimination reaction between the carboxylic acid salt and the alkoxide by the reflux operation with the alkoxide of b, in the infrared absorption spectrum, a MgNb composite alkoxide molecule having a Mg—O—Nb bond near 658 cm −1 was obtained. The solution containing the MgNb complex alkoxide molecule was mixed with the Pb precursor solution to synthesize Pb (Mg 1/3
It is desirable to synthesize a Nb 2/3 ) O 3 precursor solution.

【0014】前述のMgのカルボン酸塩(酢酸Mg)と
Nbアルコキシドとの還流操作によっておこる反応を下
記化1に示す。
The reaction which occurs by the reflux operation of the above-mentioned Mg carboxylate (Mg acetate) and Nb alkoxide is shown in the following chemical formula 1.

【0015】[0015]

【化1】 Embedded image

【0016】上記化1に示される様に、酢酸Mgの酢酸
基とNbアルコキシドのアルコキシ基が反応し、エステ
ルを形成し、複合体分子内から脱離することによって、
Mg−O−Nbの結合を有するMgNb複合アルコキシ
ド分子を得ることができる。
As shown in Chemical Formula 1, the acetic acid group of Mg acetate and the alkoxy group of Nb alkoxide react to form an ester, which is eliminated from the inside of the complex molecule.
A MgNb composite alkoxide molecule having a Mg-O-Nb bond can be obtained.

【0017】複合体の合成は、赤外吸収(以下IR)ス
ペクトルから、エステルの生成、COO- の減少、Mg
−O−Nb結合に起因した新たな吸収の発現に着目する
ことにより、確認できる。
Synthesis of the composite is carried out from the infrared absorption (hereinafter IR) spectrum by formation of ester, reduction of COO , Mg
This can be confirmed by paying attention to the expression of new absorption due to the —O—Nb bond.

【0018】図1に、酢酸Mg溶液(a)、Nbアルコ
キシド溶液(b)、及び還流1時間後のMgNb複合体
溶液(c)、還流24時間後のMgNb複合体溶液
(d)、還流48時間後のMgNb複合体溶液(e)、
還流67時間後のMgNb複合体溶液(f)のIRスペ
クトルを示す。酢酸Mg溶液(a)のIRスペクトルに
おいて、669cm-1付近にMg−OOCCH3 (Mg−
OAc)、1450cm-1、1550cm-1付近にCOO-
の吸収、Nbアルコキシド溶液(b)のIRスペクトル
において、580cm-1付近にNb−Oの吸収が存在して
おり、原料固有の吸収がみられる。(c)から(f)の
ように還流時間が増加すると、1450cm-1、1550
cm-1のCOO- の吸収が減少すると共に、1740cm-1
にエステルの吸収が発現し、また656cm-1付近に新た
な吸収が発現する。このIRスペクトルの変化から、還
流時間の増加と共に、上記化1の反応が進行しているの
がわかる。つまり、656cm-1付近に現れた新たな吸収
はMg−O−Nb結合に起因する吸収である。溶液の段
階で既にコランバイト(MgNb2 6 )に近い構造を
持つ、強固なMg−O−Nb結合を有するMgNb複合
アルコキシド分子が形成されていることを示している。
In FIG. 1, Mg acetate solution (a), Nb alkoxide solution (b), MgNb complex solution (c) after 1 hour of reflux, MgNb complex solution (d) after reflux of 24 hours and reflux 48. MgNb complex solution (e) after hours,
The IR spectrum of the MgNb complex solution (f) after 67 hours of reflux is shown. In IR spectrum of the Mg-acetate solution (a), Mg-OOCCH 3 around 669cm -1 (Mg-
OAc), COO near 1450 cm −1 and 1550 cm −1
In the IR spectrum of the Nb alkoxide solution (b), the absorption of Nb-O exists near 580 cm -1 , and the absorption peculiar to the raw material is observed. When the reflux time is increased from (c) to (f), 1450 cm −1 , 1550
COO, cm -1 - with the absorption is decreased, 1740 cm -1
The absorption of the ester is expressed in and the new absorption is expressed in the vicinity of 656 cm -1 . From this change in IR spectrum, it can be seen that the reaction of the above chemical formula 1 is proceeding with the increase of the reflux time. That is, the new absorption that appeared near 656 cm −1 is the absorption due to the Mg—O—Nb bond. It is shown that MgNb complex alkoxide molecules having a strong Mg—O—Nb bond having a structure close to that of corumbite (MgNb 2 O 6 ) have already been formed at the solution stage.

【0019】このため、他の求核性有機金属化合物(例
えば酢酸鉛)に対して安定であり、Mg−O−Nb結合
が破壊されることなく、Pb(Mg1/3 Nb2/3 )O3
前駆体が形成される。
Therefore, it is stable against other nucleophilic organometallic compounds (for example, lead acetate), Pb (Mg 1/3 Nb 2/3 ) is not destroyed, and the Mg—O—Nb bond is not destroyed. O 3
A precursor is formed.

【0020】また、例えば、MgNb複合アルコキシド
溶液に水と溶媒の混合溶液を滴下し、部分的に加水分解
処理することにより、MgNb複合アルコキシドが重縮
合した数nmオーダーのMgNbゾルが形成され、この
数nmオーダーのMgNbゾルを含むPb(Mg1/3
2/3 )O3 前駆体が形成されているため、膜厚が2μ
m以下で室温での比誘電率が2500以上の高い誘電率
を有するPb(Mg1/ 3 Nb2/3 )O3 薄膜が作製され
る。
Further, for example, a mixed solution of water and a solvent is added dropwise to the MgNb composite alkoxide solution and partially hydrolyzed to form a MgNb sol of several nm order in which the MgNb composite alkoxide is polycondensed. Pb (Mg 1/3 N containing a few nm order MgNb sol
b 2/3 ) O 3 precursor is formed, so the film thickness is 2μ
relative dielectric constant at room temperature or less m is Pb (Mg 1/3 Nb 2/3 ) with 2500 or more high dielectric constant O 3 thin film is produced.

【0021】そして、このように、膜厚が2μm以下で
比誘電率が2500以上の高い誘電率を有するPb(M
1/3 Nb2/3 )O3 薄膜を一対の電極により挟持する
ことにより、高誘電率のコンデンサを得ることができ
る。
As described above, Pb (M having a high dielectric constant of not less than 2 μm and a relative dielectric constant of 2500 or more is used.
A high dielectric constant capacitor can be obtained by sandwiching the g 1/3 Nb 2/3 ) O 3 thin film between a pair of electrodes.

【0022】[0022]

【発明の実施の形態】本発明の誘電体薄膜作製において
は、まず塗布溶液としてPb、Mg、Nbの有機金属化
合物が均一に溶解した前駆体溶液を調製する。
BEST MODE FOR CARRYING OUT THE INVENTION In the production of the dielectric thin film of the present invention, a precursor solution in which an organometallic compound of Pb, Mg or Nb is uniformly dissolved is first prepared as a coating solution.

【0023】まず鉛(Pb)の有機酸塩、無機塩、アル
コキシドから選択される少なくとも1種の鉛化合物をR
1 OH、R2 OC2 4 OH、R3 COOH(R1 、R
2 、R3 :炭素数1以上のアルキル基)で示される溶媒
に混合する。この時、鉛化合物が結晶水を含む場合に
は、作製したPb前駆体溶液中に水が存在しないように
脱水処理する。
First, at least one lead compound selected from an organic acid salt of lead (Pb), an inorganic salt, and an alkoxide is added to R.
1 OH, R 2 OC 2 H 4 OH, R 3 COOH (R 1 , R
2 , R 3 : an alkyl group having 1 or more carbon atoms). At this time, if the lead compound contains water of crystallization, dehydration treatment is performed so that water does not exist in the produced Pb precursor solution.

【0024】次にMg、及びNbの有機酸塩、無機塩、
アルコキシドから選択される少なくとも1種のMg化合
物、Nb化合物をMg:Nb=1:2のモル比でR1
H、R2 OC2 4 OH、R3 COOH(R1 、R2
3 :炭素数1以上のアルキル基)で示される溶媒に混
合する。混合後、溶媒の沸点まで溶液の温度を上昇さ
せ、還流操作を行い、MgNb複合アルコキシドを合成
する。
Next, organic acid salts and inorganic salts of Mg and Nb,
At least one Mg compound or Nb compound selected from alkoxides is used as R 1 O in a molar ratio of Mg: Nb = 1: 2.
H, R 2 OC 2 H 4 OH, R 3 COOH (R 1 , R 2 ,
R 3 : an alkyl group having 1 or more carbon atoms). After mixing, the temperature of the solution is raised to the boiling point of the solvent and reflux operation is performed to synthesize the MgNb composite alkoxide.

【0025】特に、Mgのカルボン酸塩から選ばれる少
なくとも1種のMg化合物とNbのアルコキシドをM
g:Nb=1:2のモル比でR1 OH、R2 OC2 4
OH、R3 COOH(R1 、R2 、R3 :炭素数1以上
のアルキル基)で示される溶媒に混合した後、溶媒の沸
点まで溶液の温度を上昇させ、還流操作を行い、MgN
b複合アルコキシドを合成することが、比誘電率向上の
点から望ましい。
In particular, at least one Mg compound selected from Mg carboxylates and Nb alkoxide are M
R 1 OH and R 2 OC 2 H 4 in a molar ratio of g: Nb = 1: 2.
OH, R 3 COOH: After mixing in a solvent represented by (R 1, R 2, R 3 having 1 or more alkyl group having a carbon), the temperature of the solution was raised to the boiling point of the solvent, subjected to reflux operation, MgN
Synthesis of the b-composite alkoxide is desirable from the viewpoint of improving the relative dielectric constant.

【0026】Mgのカルボン酸塩としては、酢酸塩、安
息香酸塩、オレイン酸塩等があるが、Nbアルコキシド
との反応性、残留有機物の問題の点から、炭化水素基の
小さい酢酸塩が望ましい。
Examples of Mg carboxylates include acetates, benzoates and oleates, but acetates having a small hydrocarbon group are preferable from the viewpoints of reactivity with Nb alkoxide and residual organic matter. .

【0027】Nbのアルコキシドとしては、メトキシ
ド、エトキシド、イソプロキシド等があるが、特に限定
されるものではない。
The alkoxide of Nb includes methoxide, ethoxide, isoproxide and the like, but is not particularly limited.

【0028】Mgのカルボン酸塩、例えば、酢酸Mgと
Nbアルコキシドとの還流時間は24時間以上が特に望
ましく、IRスペクトルにおいて、658cm-1付近に
吸収を有するMgNb複合アルコキシドが合成できれば
よい。蒸留下で反応を促進させてもよい。
It is particularly desirable that the reflux time of Mg carboxylate, for example, Mg acetate and Nb alkoxide, is 24 hours or more, and it is sufficient that a MgNb complex alkoxide having an absorption near 658 cm −1 in the IR spectrum can be synthesized. The reaction may be promoted under distillation.

【0029】IRスペクトルにおいて、658cm-1
近に吸収を有し、他の求核性の有機金属化合物の存在下
においても安定なMg−O−Nb結合を有するMgNb
複合アルコキシド分子を合成する手法としては、例え
ば、アルコキシド原料を用いた場合、酸等の触媒の共存
下で還流操作を行う事により、分子内での脱エーテル反
応を促進する。あるいは、還流操作による複合化を行っ
た後、無水酢酸、エタノールアミン等に代表される安定
化剤を添加する。あるいは、カルボン酸塩とアルコキシ
ドの還流操作により、分子内での脱エステル反応を促進
する。あるいは、水酸化物とアルコキシドの還流操作に
より、分子内での脱アルコール反応を促進する。あるい
は逆に鉛前駆体の求核性を小さくする為、前述の安定化
剤を添加する。以上のいずれかの手法を用いる事によ
り、他の求核性有機金属化合物の存在下においても安定
なMg−O−Nb結合を有するMgNb複合アルコキシ
ド分子を合成できる。特に、MgNb複合アルコキシド
は、Mgのカルボン酸塩とNbのアルコキシドとの還流
操作により合成することが望ましい。
In the IR spectrum, MgNb having an absorption near 658 cm −1 and having a stable Mg—O—Nb bond even in the presence of another nucleophilic organometallic compound.
As a method for synthesizing a complex alkoxide molecule, for example, when an alkoxide raw material is used, refluxing operation is carried out in the coexistence of a catalyst such as an acid to accelerate the deetherification reaction in the molecule. Alternatively, a stabilizing agent typified by acetic anhydride, ethanolamine and the like is added after the complexation is performed by the reflux operation. Alternatively, the deesterification reaction in the molecule is promoted by refluxing the carboxylate and alkoxide. Alternatively, the dealcohol reaction in the molecule is promoted by the reflux operation of the hydroxide and the alkoxide. On the contrary, in order to reduce the nucleophilicity of the lead precursor, the above-mentioned stabilizer is added. By using any of the above methods, it is possible to synthesize a MgNb complex alkoxide molecule having a stable Mg—O—Nb bond even in the presence of another nucleophilic organometallic compound. In particular, the MgNb composite alkoxide is preferably synthesized by refluxing Mg carboxylate and Nb alkoxide.

【0030】また、合成した上記MgNb複合アルコキ
シド溶液に水と溶媒の混合溶液を適下し、部分加水分解
を行い、前述のMgNb複合アルコキシドが重縮合した
MgNbゾルを形成させる。部分加水分解とは、分子内
のアルコキシル基の一部を水酸基と置換し、置換された
分子内での脱水、あるいは脱アルコール反応により重縮
合させる方法である。MgNb複合体の部分加水分解を
行う場合は、還流時間は1時間以上であれば特に限定さ
れない。
Further, a mixed solution of water and a solvent is appropriately added to the above-mentioned synthesized MgNb composite alkoxide solution and partial hydrolysis is carried out to form a MgNb sol in which the above-mentioned MgNb composite alkoxide is polycondensed. Partial hydrolysis is a method in which part of an alkoxyl group in a molecule is substituted with a hydroxyl group, and polycondensation is performed by dehydration or dealcoholation reaction in the substituted molecule. When performing partial hydrolysis of the MgNb complex, the reflux time is not particularly limited as long as it is 1 hour or more.

【0031】作製したPb前駆体溶液と、MgNb複合
アルコキシド溶液あるいはMgNbゾルをPb:(Mg
+Nb)=1:1のモル比で混合し、塗布溶液とする。
The prepared Pb precursor solution and the MgNb composite alkoxide solution or MgNb sol were mixed with Pb: (Mg
+ Nb) = 1: 1 in a molar ratio to prepare a coating solution.

【0032】作製した塗布溶液を基板上にスピンコート
法、ディップコート法、スプレー法等の手法により、成
膜する。
The prepared coating solution is formed on the substrate by a method such as a spin coating method, a dip coating method or a spraying method.

【0033】成膜後、300℃〜400℃の温度で1分
間熱処理を行い、膜中に残留した有機物を燃焼させ、ゲ
ル膜とする。1回の塗布膜厚は0.1μm以下が望まし
い。
After the film formation, a heat treatment is performed at a temperature of 300 ° C. to 400 ° C. for 1 minute to burn the organic substances remaining in the film to form a gel film. It is desirable that the coating thickness per application is 0.1 μm or less.

【0034】成膜−熱処理を所定の膜厚になるまで繰り
返した後、750℃〜850℃で焼成を行い、本発明の
結晶質の誘電体薄膜が作製される。誘電体薄膜の膜厚は
2μm以下であるが、これ以上になると工程数が増加
し、また、コンデンサを構成した場合における容量が小
さくなるからである。誘電体薄膜の膜厚は、製造の容易
性,膜質劣化の点で1μm以下が望ましく、さらに膜の
絶縁性を考慮すると特に0.3〜1μmが望ましい。
After repeating film formation-heat treatment until a predetermined film thickness is reached, firing is carried out at 750 ° C. to 850 ° C. to produce the crystalline dielectric thin film of the present invention. This is because the film thickness of the dielectric thin film is 2 μm or less, but if the film thickness is more than 2 μm, the number of steps is increased and the capacitance in the case of forming a capacitor is reduced. The film thickness of the dielectric thin film is preferably 1 μm or less from the viewpoint of ease of production and deterioration of film quality, and further preferably 0.3 to 1 μm in consideration of the insulating property of the film.

【0035】本発明の誘電体薄膜は、Pb(Mg1/3
2/3 )O3 からなる誘電体薄膜であるが、少々パイロ
クロア相が存在する場合がある。
The dielectric thin film of the present invention is made of Pb (Mg 1/3 N
Although it is a dielectric thin film made of b 2/3 ) O 3, there may be some pyrochlore phase.

【0036】本発明の薄膜コンデンサは、例えば、P
t,Au,Cr等を基板上にスパッタ法,蒸着法,グラ
ビア印刷法等により成膜して下部電極を形成し、この下
部電極膜の表面に、上記誘電体薄膜を上記方法で成膜し
て形成し、この後に誘電体薄膜の表面に下部電極と同様
にして上部電極を成膜することにより得られる。また、
積層コンデンサは誘電体膜と電極とを交互に積層するこ
とにより得られる。
The thin film capacitor of the present invention is, for example, P
A lower electrode is formed by depositing t, Au, Cr or the like on the substrate by a sputtering method, a vapor deposition method, a gravure printing method or the like, and the dielectric thin film is formed on the surface of the lower electrode film by the above method. Then, the upper electrode is formed on the surface of the dielectric thin film in the same manner as the lower electrode. Also,
A multilayer capacitor is obtained by alternately stacking dielectric films and electrodes.

【0037】[0037]

【実施例】【Example】

実施例1 MgエトキシドとNbエトキシドを1:2のモル比で秤
量し、2−メトキシエタノ−ル中で還流操作(124℃
で24時間)を行い、MgNb複合アルコキシド溶液
(Mg=4.95mmol、Nb10.05mmol、
2−メトキシエタノール150mmol)を合成した。
その後、無水酢酸を7.50mmol添加し、安定化さ
せた。図2にこの溶液のIRスペクトルを示す。658
cm-1付近にMg−O−Nb結合による吸収が見られ
た。次に酢酸鉛(無水物)15mmolと150mmo
lの2−メトキシエタノールを混合し、120℃での蒸
留操作により、Pb前駆体溶液を合成した。
Example 1 Mg ethoxide and Nb ethoxide were weighed in a molar ratio of 1: 2 and refluxed in 2-methoxyethanol (124 ° C.).
For 24 hours) to prepare a MgNb complex alkoxide solution (Mg = 4.95 mmol, Nb10.05 mmol,
2-Methoxyethanol 150 mmol) was synthesized.
Then, 7.50 mmol of acetic anhydride was added and stabilized. The IR spectrum of this solution is shown in FIG. 658
Absorption due to the Mg—O—Nb bond was observed near cm −1 . Next, lead acetate (anhydrous) 15 mmol and 150 mmo
l of 2-methoxyethanol was mixed, and a Pb precursor solution was synthesized by a distillation operation at 120 ° C.

【0038】MgNb前駆体溶液とPb前駆体溶液をモ
ル比Pb:(Mg+Nb)=1:1になるよう混合し、
室温で十分撹拌し、Pb(Mg1/3 Nb2/3 )O3 前駆
体溶液を合成した。
The MgNb precursor solution and the Pb precursor solution were mixed so that the molar ratio was Pb: (Mg + Nb) = 1: 1.
After sufficiently stirring at room temperature, a Pb (Mg 1/3 Nb 2/3 ) O 3 precursor solution was synthesized.

【0039】この溶液の濃度を2−メトキシエタノール
で約3倍に希釈し、塗布溶液とした。電極となるPt
(111)が650℃でスパッタ蒸着されたサファイア
単結晶基板上の上記Pt電極の表面に、前記塗布溶液を
スピンコーターで塗布し、乾燥させた後、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
−熱処理の操作を繰り返した後、830℃で1分間(大
気中)の焼成を行い、膜厚0.5μm、1μm、2μm
のPb(Mg1/3 Nb2/3 )O3 薄膜を得た。得られた
薄膜のX線回折結果より、ペロブスカイト生成率を計算
するといずれも約95%であった。
The concentration of this solution was diluted about 3-fold with 2-methoxyethanol to prepare a coating solution. Pt to be an electrode
The coating solution was applied by a spin coater to the surface of the Pt electrode on a sapphire single crystal substrate on which (111) was sputter-deposited at 650 ° C., dried, and then heat-treated at 300 ° C. for 1 minute to form a gel film. Was prepared. After repeating the operation of applying the coating solution and the heat treatment, baking is performed at 830 ° C. for 1 minute (in the air) to obtain a film thickness of 0.5 μm, 1 μm, 2 μm.
A Pb (Mg 1/3 Nb 2/3 ) O 3 thin film was obtained. From the X-ray diffraction results of the obtained thin films, the perovskite formation rate was calculated to be about 95% in all cases.

【0040】この薄膜表面に厚み0.2μm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4284
A)を用いて、室温(25℃)、10kHz(Ac10
0mV)の条件で比誘電率、誘電損失を求めた結果、い
ずれの場合も比誘電率が2500、誘電損失が0.03
6であった。
A gold electrode having a thickness of 0.2 μm was formed on the surface of this thin film by sputtering deposition to prepare a thin film capacitor.
LCR meter (4284 manufactured by Hewlett Packard)
Room temperature (25 ° C.), 10 kHz (Ac10)
(0 mV), the relative permittivity and the dielectric loss were calculated. As a result, the relative permittivity was 2500 and the dielectric loss was 0.03
It was 6.

【0041】実施例2 MgエトキシドとNbエトキシドを1:2のモル比で秤
量し、2−メトキシエタノール中で還流操作(124℃
で24時間)を行い、MgNb複合アルコキシド溶液
(Mg=4.95mmol、Nb10.05mmol、
2−メトキシエタノール150mmol)を合成した。
Example 2 Mg ethoxide and Nb ethoxide were weighed in a molar ratio of 1: 2 and refluxed in 2-methoxyethanol (124 ° C.).
For 24 hours) to prepare a MgNb complex alkoxide solution (Mg = 4.95 mmol, Nb10.05 mmol,
2-Methoxyethanol 150 mmol) was synthesized.

【0042】この溶液に全金属量(Mg+Nb)に対
し、2倍量の水と2−メトキシエタノール、及び無水酢
酸7.5mmolの均一混合溶液を撹拌しながら滴下
し、部分加水分解を行い、MgNbゾル溶液を合成し
た。28℃での溶液粘度は1.82cPから2.06c
Pに増加しており、加水分解重縮合が起こっている事を
確認した。溶液のIRスペクトルを測定した結果、65
8cm-1付近に吸収が見られた。
A homogeneous mixed solution of water, 2-methoxyethanol, and 7.5 mmol of acetic anhydride was added dropwise to this solution with stirring, with respect to the total amount of metal (Mg + Nb), and the mixture was partially hydrolyzed to obtain MgNb. A sol solution was synthesized. Solution viscosity at 28 ° C is from 1.82 cP to 2.06 c
It was increased to P, and it was confirmed that hydrolysis polycondensation had occurred. The IR spectrum of the solution was measured and found to be 65
Absorption was observed near 8 cm -1 .

【0043】次に酢酸鉛(無水物)15mmolと15
0mmolの2−メトキシエタノールを混合し、120
℃での蒸留操作により、Pb前駆体溶液を合成した。
Next, 15 mmol of lead acetate (anhydride) and 15
Mix 0 mmol of 2-methoxyethanol, 120
A Pb precursor solution was synthesized by a distillation operation at ° C.

【0044】MgNbゾル溶液とPb前駆体溶液とをモ
ル比Pb:(Mg+Nb)=1:1になるよう混合し、
室温で十分撹拌し、Pb(Mg1/3 Nb2/3 )O3 前駆
体溶液を合成した。
The MgNb sol solution and the Pb precursor solution were mixed in a molar ratio Pb: (Mg + Nb) = 1: 1,
After sufficiently stirring at room temperature, a Pb (Mg 1/3 Nb 2/3 ) O 3 precursor solution was synthesized.

【0045】この溶液の濃度を2−メトキシエタノール
で約2倍に希釈し、塗布溶液とした。電極となるPt
(111)が650℃でスパッタ蒸着されたサファイア
単結晶基板上の上記Pt電極の表面に、前記塗布溶液を
スピンコーターで塗布し、乾燥させた後、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
−熱処理の操作を繰り返した後、830℃で1分間(大
気中)の焼成を行い、膜厚0.5μm、1μm、2μm
のPb(Mg1/3 Nb2/3 )O3 薄膜を得た。得られた
薄膜のX線回折結果より、ペロブスカイト生成率を計算
するといずれも約95%であった。
The concentration of this solution was diluted about 2-fold with 2-methoxyethanol to prepare a coating solution. Pt to be an electrode
The coating solution was applied by a spin coater to the surface of the Pt electrode on a sapphire single crystal substrate on which (111) was sputter-deposited at 650 ° C., dried, and then heat-treated at 300 ° C. for 1 minute to form a gel film. Was prepared. After repeating the operation of applying the coating solution and the heat treatment, baking is performed at 830 ° C. for 1 minute (in the air) to obtain a film thickness of 0.5 μm, 1 μm, 2 μm.
A Pb (Mg 1/3 Nb 2/3 ) O 3 thin film was obtained. From the X-ray diffraction results of the obtained thin films, the perovskite formation rate was calculated to be about 95% in all cases.

【0046】この薄膜表面に厚み0.2μm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4284
A)を用いて、室温(25℃)、10kHz(Ac10
0mV)の条件で比誘電率、及び誘電損失を求めたとこ
ろ、比誘電率及び誘電損失はいずれも2800、0.0
23であった。
A gold electrode having a thickness of 0.2 μm was formed on the surface of this thin film by sputtering deposition to prepare a thin film capacitor.
LCR meter (4284 manufactured by Hewlett Packard)
Room temperature (25 ° C.), 10 kHz (Ac10)
When the relative permittivity and the dielectric loss were obtained under the condition of 0 mV), both the relative permittivity and the dielectric loss were 2800 and 0.0
23.

【0047】実施例3 酢酸Mg4水和物4.95mmolを溶媒の2−メトキ
シエタノール中に混合した。混合後、125℃まで加熱
し、溶媒との共沸蒸留により、脱水処理を行った。濃度
調整を行った後、Nbエトキシドを10.05mmol
秤量し、2−メトキシエタノール中で還流操作(124
℃で48時間)を行い、MgNb複合アルコキシド溶液
(Mg=4.95mmol、Nb10.05mmol、
2−メトキシエタノール150mmol)を合成した。
IRスペクトルを図1(e)に示した。
Example 3 4.95 mmol of Mg acetate tetrahydrate was mixed in the solvent 2-methoxyethanol. After mixing, the mixture was heated to 125 ° C. and dehydrated by azeotropic distillation with a solvent. After adjusting the concentration, 10.05 mmol of Nb ethoxide
Weigh and reflux in 2-methoxyethanol (124
At 48 ° C. for 48 hours, and the MgNb composite alkoxide solution (Mg = 4.95 mmol, Nb10.05 mmol,
2-Methoxyethanol 150 mmol) was synthesized.
The IR spectrum is shown in Fig. 1 (e).

【0048】次に酢酸鉛(無水物)15mmolと15
0mmolの2−メトキシエタノールを混合し、120
℃での蒸留操作により、Pb前駆体溶液を合成した。
Next, lead acetate (anhydrous) 15 mmol and 15
Mix 0 mmol of 2-methoxyethanol, 120
A Pb precursor solution was synthesized by a distillation operation at ° C.

【0049】MgNb前駆体溶液とPb前駆体溶液をモ
ル比Pb:(Mg+Nb)=1:1になるよう混合し、
室温で十分撹拌し、Pb(Mg1/3 Nb2/3 )O3 (P
MN)前駆体溶液を合成した。
The MgNb precursor solution and the Pb precursor solution were mixed in a molar ratio Pb: (Mg + Nb) = 1: 1,
Stir well at room temperature to remove Pb (Mg 1/3 Nb 2/3 ) O 3 (P
MN) precursor solution was synthesized.

【0050】この溶液の濃度を2−メトキシエタノール
で約3倍に希釈し、塗布溶液とした。電極となるPt
(111)が650℃でスパッタ蒸着されたサファイア
単結晶基板上の上記Pt電極の表面に、前記塗布溶液を
スピンコーターで塗布し、乾燥させた後、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
−熱処理の操作を繰り返した後、830℃で1分間(大
気中)の焼成を行い、膜厚0.50μm、1.0μm、
2.0μmのPb(Mg1/3 Nb2/3 )O3 薄膜を得
た。得られた薄膜のX線回折結果より、ペロブスカイト
生成率を計算するとそれぞれ約96%であった。
The concentration of this solution was diluted about 3-fold with 2-methoxyethanol to prepare a coating solution. Pt to be an electrode
The coating solution was applied by a spin coater to the surface of the Pt electrode on a sapphire single crystal substrate on which (111) was sputter-deposited at 650 ° C., dried, and then heat-treated at 300 ° C. for 1 minute to form a gel film. Was prepared. After repeating the operation of applying the coating solution and the heat treatment, baking was performed at 830 ° C. for 1 minute (in the air) to obtain a film thickness of 0.50 μm, 1.0 μm,
A 2.0 μm Pb (Mg 1/3 Nb 2/3 ) O 3 thin film was obtained. From the X-ray diffraction results of the obtained thin film, the perovskite production rate was calculated to be about 96%.

【0051】作製した全ての薄膜表面に直径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
4284A)を用いて、25℃、1kHz(Ac100
mV)の条件で比誘電率、誘電損失を求めた結果、それ
ぞれ比誘電率が3100、誘電損失が0.005であっ
た。
0.2 mm diameter on the surface of all thin films prepared
Of the gold electrode of No. 1 was formed by sputter deposition to prepare a thin film capacitor, and an LCR meter (4284A manufactured by Hulett Packard) was used to obtain 25 ° C., 1 kHz (Ac100
As a result of obtaining the relative permittivity and the dielectric loss under the condition of (mV), the relative permittivity was 3100 and the dielectric loss was 0.005, respectively.

【0052】図3に比誘電率の温度特性(−40から+
85℃)を示す。室温(25℃)の比誘電率を基準とし
た時の比誘電率の変化率は−12%から+7.5%であ
り、±15%以内であった。
FIG. 3 shows the temperature characteristic of relative permittivity (from −40 to +
85 ° C.). The rate of change of the relative permittivity based on the relative permittivity at room temperature (25 ° C.) was −12% to + 7.5%, which was within ± 15%.

【0053】比較例 MgエトキシドとNbエトキシドを1:2のモル比で秤
量し、2−メトキシエタノール中で還流操作(124℃
で5時間)を行い、MgNb複合アルコキシド溶液(M
g=4.95mmol、Nb10.05mmol、2−
メトキシエタノール150mmol)を合成した。図4
にこの溶液のIRスペクトルを示す。600cm-1付近
に配位結合による複合アルコキシド形成による吸収が見
られたが、658cm-1付近の吸収は見られなかった。
Comparative Example Mg ethoxide and Nb ethoxide were weighed in a molar ratio of 1: 2 and refluxed in 2-methoxyethanol (124 ° C.).
For 5 hours), and the MgNb complex alkoxide solution (M
g = 4.95 mmol, Nb10.05 mmol, 2-
Methoxyethanol 150 mmol) was synthesized. FIG.
The IR spectrum of this solution is shown in FIG. Absorption due to the formation of a complex alkoxide by a coordinate bond was observed near 600 cm -1 , but no absorption was observed around 658 cm -1 .

【0054】次に酢酸鉛(無水物)15mmolと15
0mmolの2−メトキシエタノールを混合し、120
℃での蒸留操作により、Pb前駆体溶液を合成した。
Next, lead acetate (anhydrous) 15 mmol and 15
Mix 0 mmol of 2-methoxyethanol, 120
A Pb precursor solution was synthesized by a distillation operation at ° C.

【0055】MgNb前駆体溶液とPb前駆体溶液をモ
ル比Pb:(Mg+Nb)=1:1になるよう混合し、
室温で十分撹拌し、Pb(Mg1/3 Nb2/3 )O3 前駆
体溶液を合成した。
The MgNb precursor solution and the Pb precursor solution were mixed in a molar ratio Pb: (Mg + Nb) = 1: 1,
After sufficiently stirring at room temperature, a Pb (Mg 1/3 Nb 2/3 ) O 3 precursor solution was synthesized.

【0056】この溶液の濃度を2−メトキシエタノール
で約5倍に希釈し、塗布溶液とした。電極となるPt
(111)が650℃でスパッタ蒸着されたサファイア
単結晶基板上の上記Pt電極の表面に、前記塗布溶液を
スピンコーターで塗布し、乾燥させた後、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
−熱処理の操作を繰り返した後、830℃で1分間(大
気中)の焼成を行い、膜厚0.50μm、1μm、2μ
mのPb(Mg1/3 Nb2/3 )O3 薄膜を得た。
The concentration of this solution was diluted about 5-fold with 2-methoxyethanol to prepare a coating solution. Pt to be an electrode
The coating solution was applied by a spin coater to the surface of the Pt electrode on a sapphire single crystal substrate on which (111) was sputter-deposited at 650 ° C., dried, and then heat-treated at 300 ° C. for 1 minute to form a gel film. Was prepared. After repeating the operation of applying the coating solution and the heat treatment, baking is performed at 830 ° C. for 1 minute (in the air) to obtain a film thickness of 0.50 μm, 1 μm, 2 μm.
m Pb (Mg 1/3 Nb 2/3 ) O 3 thin film was obtained.

【0057】薄膜のX線回折結果より、ペロブスカイト
生成率を計算するといずれも約95%であった。
From the X-ray diffraction results of the thin films, the perovskite production rate was calculated to be about 95% in all cases.

【0058】この薄膜表面に厚み0.2μm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4284
A)を用いて、室温(25℃)、10kHz(Ac10
0mV)の条件で比誘電率および誘電損失を求めたとこ
ろ、比誘電率および誘電損失はいずれも1800、0.
017であった。
A gold electrode having a thickness of 0.2 μm was formed on the surface of this thin film by sputtering deposition to prepare a thin film capacitor,
LCR meter (4284 manufactured by Hewlett Packard)
Room temperature (25 ° C.), 10 kHz (Ac10)
When the relative permittivity and the dielectric loss were determined under the condition of 0 mV), the relative permittivity and the dielectric loss were 1800, 0.
017.

【0059】よって、IRスペクトルにおいて658c
-1付近に吸収を有するMgNb複合アルコキシドから
なるMgNb前駆体溶液を用いた実施例1〜3は、室温
における比誘電率が2500以上、誘電損失が0.03
6以下であり、比較例よりも比誘電率が大幅に向上して
いることが判る。さらに、実施例1と実施例2との比較
により、MgNb複合アルコキシド溶液を部分加水分解
した実施例2の方が比誘電率が高いことが判る。さら
に、Mgのカルボン酸塩とNbのアルコキシドとの還流
操作により合成したMgNb複合アルコキシドを用いた
実施例3では、特に比誘電率が3100と実施例1,2
に比べると優れていることが判る。
Therefore, in the IR spectrum, 658c
Examples 1 to 3 using the MgNb precursor solution composed of the MgNb composite alkoxide having absorption around m −1 have a relative dielectric constant of 2500 or more at room temperature and a dielectric loss of 0.03.
It is 6 or less, and it can be seen that the relative permittivity is significantly improved as compared with the comparative example. Further, comparison between Example 1 and Example 2 reveals that Example 2 in which the MgNb composite alkoxide solution is partially hydrolyzed has a higher relative dielectric constant. Furthermore, in Example 3 using the MgNb composite alkoxide synthesized by the reflux operation of the Mg carboxylate and the Nb alkoxide, the relative dielectric constant was 3100,
It turns out that it is superior to.

【0060】[0060]

【発明の効果】以上詳述した様に、本発明によれば、I
Rスペクトルにおいて658cm-1付近に吸収を有する
強固なMg−O−Nb結合を有するMgNb複合アルコ
キシドからなるMgNb前駆体溶液を用いて、誘電体薄
膜を作製することにより、膜厚が2μm以下で室温での
比誘電率が2500以上の高誘電率のPb(Mg1/3
2/3 )O3 薄膜が得られ、このような薄膜を一対の電
極により挟持してコンデンサを作製することにより、高
誘電率の薄膜コンデンサを得ることができる。
As described above in detail, according to the present invention, I
By preparing a dielectric thin film using a MgNb precursor solution composed of a MgNb composite alkoxide having a strong Mg—O—Nb bond having an absorption near 658 cm −1 in the R spectrum, a film thickness of 2 μm or less is obtained at room temperature. Of high dielectric constant Pb (Mg 1/3 N)
A b 2/3 ) O 3 thin film is obtained, and a thin film capacitor having a high dielectric constant can be obtained by sandwiching such a thin film with a pair of electrodes to produce a capacitor.

【図面の簡単な説明】[Brief description of the drawings]

【図1】酢酸MgとNbアルコキシドとの還流操作によ
り合成したMgNb複合アルコキシドのIRスペクトル
を示す図である。
FIG. 1 is a diagram showing an IR spectrum of a MgNb composite alkoxide synthesized by a reflux operation of Mg acetate and Nb alkoxide.

【図2】実施例1で使用したMgNb複合アルコキシド
のIRスペクトルを示す図である。
2 is a diagram showing an IR spectrum of the MgNb composite alkoxide used in Example 1. FIG.

【図3】実施例3の誘電体薄膜の比誘電率の温度特性を
示す図である。
FIG. 3 is a diagram showing temperature characteristics of relative permittivity of a dielectric thin film of Example 3.

【図4】比較例で使用したMgNb複合アルコキシドの
IRスペクトルを示す図である。
FIG. 4 is a diagram showing an IR spectrum of a MgNb composite alkoxide used in a comparative example.

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】膜厚が2μm以下のPb(Mg1/3 Nb
2/3 )O3 からなる誘電体薄膜であって、室温での比誘
電率が2500以上であることを特徴とする誘電体薄
膜。
1. A Pb (Mg 1/3 Nb) film having a thickness of 2 μm or less.
2/3 ) A dielectric thin film made of O 3 , having a relative dielectric constant of 2500 or more at room temperature.
【請求項2】膜厚が2μm以下のPb(Mg1/3 Nb
2/3 )O3 からなる誘電体薄膜であって、室温での比誘
電率が2500以上の誘電体薄膜を、一対の電極により
挟持してなることを特徴とする薄膜コンデンサ。
2. Pb (Mg 1/3 Nb having a film thickness of 2 μm or less
2/3 ) A dielectric thin film composed of O 3 , wherein a dielectric thin film having a relative dielectric constant of 2500 or more at room temperature is sandwiched by a pair of electrodes, and a thin film capacitor.
【請求項3】ゾルゲル法により調製されたPb(Mg
1/3 Nb2/3 )O3 前駆体溶液を塗布し、焼成する誘電
体薄膜の製法であって、前記Pb(Mg1/3 Nb2/3
3 前駆体溶液を、赤外吸収スペクトルにおいて、65
8cm-1付近に吸収を有するMgNb複合アルコキシド
からなるMgNb前駆体溶液と、Pb前駆体溶液とを混
合して合成することを特徴とする誘電体薄膜の製法。
3. Pb (Mg prepared by sol-gel method
A method for producing a dielectric thin film, comprising applying a 1/3 Nb 2/3 ) O 3 precursor solution and firing the solution, wherein said Pb (Mg 1/3 Nb 2/3 )
In the infrared absorption spectrum, the O 3 precursor solution was
A method for producing a dielectric thin film, which comprises synthesizing by mixing a MgNb precursor solution composed of a MgNb composite alkoxide having absorption around 8 cm −1 and a Pb precursor solution.
【請求項4】MgNb複合アルコキシドが、Mgのカル
ボン酸塩とNbのアルコキシドとの還流操作により合成
されることを特徴とする請求項3記載の誘電体薄膜の製
法。
4. The method for producing a dielectric thin film according to claim 3, wherein the MgNb composite alkoxide is synthesized by refluxing an Mg carboxylate and an Nb alkoxide.
【請求項5】ゾルゲル法により調製されたPb(Mg
1/3 Nb2/3 )O3 前駆体溶液を塗布し、焼成する誘電
体薄膜の製法であって、前記Pb(Mg1/3 Nb2/3
3 前駆体溶液を、赤外吸収スペクトルにおいて、65
8cm-1付近に吸収を有するMgNb複合アルコキシド
を部分的に加水分解して得られたMgNbゾルからなる
MgNb前駆体溶液と、Pb前駆体溶液とを混合して合
成することを特徴とする誘電体薄膜の製法。
5. Pb (Mg prepared by the sol-gel method
A method for producing a dielectric thin film, comprising applying a 1/3 Nb 2/3 ) O 3 precursor solution and firing the solution, wherein said Pb (Mg 1/3 Nb 2/3 )
In the infrared absorption spectrum, the O 3 precursor solution was
A dielectric material characterized by being synthesized by mixing a MgNb precursor solution composed of a MgNb sol obtained by partially hydrolyzing a MgNb composite alkoxide having absorption around 8 cm −1 with a Pb precursor solution. Thin film manufacturing method.
【請求項6】MgNb複合アルコキシドが、Mgのカル
ボン酸塩とNbのアルコキシドとの還流操作により合成
されることを特徴とする請求項5記載の誘電体薄膜の製
法。
6. The method for producing a dielectric thin film according to claim 5, wherein the MgNb composite alkoxide is synthesized by refluxing an Mg carboxylate and an Nb alkoxide.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256377A (en) * 2003-02-27 2004-09-16 Nippon Shokubai Co Ltd Method of manufacturing metal oxide film
JP2015207725A (en) * 2014-04-23 2015-11-19 株式会社リコー Precursor sol-gel solution, electromechanical conversion element, droplet discharge head, and ink-jet recording device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04321521A (en) * 1991-04-19 1992-11-11 Colloid Res:Kk Production of multiple oxide precursor powder
JPH0551755A (en) * 1991-03-26 1993-03-02 Murata Mfg Co Ltd Production of lead-based multi component perovskite type oxide thin film
JPH06333772A (en) * 1993-03-25 1994-12-02 Matsushita Electric Ind Co Ltd Thin film capacitor and manufacture thereof
JPH07283069A (en) * 1994-04-07 1995-10-27 Murata Mfg Co Ltd Dielectric thin film and production thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0551755A (en) * 1991-03-26 1993-03-02 Murata Mfg Co Ltd Production of lead-based multi component perovskite type oxide thin film
JPH04321521A (en) * 1991-04-19 1992-11-11 Colloid Res:Kk Production of multiple oxide precursor powder
JPH06333772A (en) * 1993-03-25 1994-12-02 Matsushita Electric Ind Co Ltd Thin film capacitor and manufacture thereof
JPH07283069A (en) * 1994-04-07 1995-10-27 Murata Mfg Co Ltd Dielectric thin film and production thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004256377A (en) * 2003-02-27 2004-09-16 Nippon Shokubai Co Ltd Method of manufacturing metal oxide film
JP2015207725A (en) * 2014-04-23 2015-11-19 株式会社リコー Precursor sol-gel solution, electromechanical conversion element, droplet discharge head, and ink-jet recording device
US9969651B2 (en) 2014-04-23 2018-05-15 Ricoh Company, Ltd. Precursor sol-gel solution, electromechanical transducer element, liquid droplet discharge head, and inkjet recording apparatus

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