JP2006124212A - Dielectric ceramic, method of manufacturing the same and laminated ceramic capacitor - Google Patents
Dielectric ceramic, method of manufacturing the same and laminated ceramic capacitor Download PDFInfo
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本発明は、積層セラミックコンデンサ等に用いられる誘電体磁器およびその製法に関する。 The present invention relates to a dielectric ceramic used for a multilayer ceramic capacitor or the like and a method for manufacturing the dielectric ceramic.
近年、携帯電話などモバイル機器の普及やパソコンなどの主要部品である半導体素子の高速高周波化に伴い、このような電子機器に搭載される積層セラミックコンデンサは、小型、高容量化の要求がますます高まっている。 In recent years, with the widespread use of mobile devices such as mobile phones and the high speed and high frequency of semiconductor elements, which are the main parts of personal computers, multilayer ceramic capacitors mounted on such electronic devices are required to be smaller and have higher capacities. It is growing.
そのため積層セラミックコンデンサを構成する誘電体層は、薄層化と高積層化が図られているが、誘電体層における上記した薄層化および高積層化の要求に応えるために、誘電体磁器を構成する誘電体粉末について微粒化と比誘電率の向上が図られている（例えば、特許文献１）。 For this reason, the dielectric layers constituting the multilayer ceramic capacitor have been reduced in thickness and increased in thickness, but in order to meet the above-mentioned demands for thinning and increasing the number of layers in the dielectric layer, dielectric ceramics are used. An attempt is made to atomize the dielectric powder and to improve the dielectric constant (for example, Patent Document 1).
上記特許文献１によれば、例えば、誘電体粉末の代表例であるチタン酸バリウムは、水酸化バリウム水溶液とＴｉアルコキシド溶液とを混合し、その混合容器内で所定時間熟成した後、脱水、乾燥させることにより、微粒のチタン酸バリウムが得られると記載されている。
しかしながら、上記した液相法により得られるチタン酸バリウム粉末は、混合、熟成後の乾燥が１１０℃、３時間の条件であり、単に、混合液に含まれる水分を除くだけの条件しか採用していないことから、得られたチタン酸バリウム粉末中には、多くの結晶水や粉末中にも水酸化物のような不純物が存在したものとなっており、そのために、得られたチタン酸バリウム粉末は平均粒径が５０ｎｍと小さく形成されているものの、格子定数が本来単結晶から導かれる値よりも大きくなり（ａ＝０．４０３２ｎｍ、Ｖ＝０．０６５５４８ｎｍ３）、結晶構造的にも立方晶が主体となり、得られた誘電体粉末を用いて作製した誘電体磁器は比誘電率が低いという問題があった。 However, the barium titanate powder obtained by the liquid phase method described above is mixed and aged after drying at 110 ° C. for 3 hours, and only employs conditions that remove the moisture contained in the mixed solution. Therefore, in the obtained barium titanate powder, many crystal waters and impurities such as hydroxide existed in the powder. For this reason, the obtained barium titanate powder Although the average grain size is formed as small as 50 nm, the lattice constant is larger than the value originally derived from the single crystal (a = 0.40332 nm, V = 0.065548 nm 3 ), and the crystal structure is also cubic. The dielectric porcelain produced using the obtained dielectric powder has a problem of low relative dielectric constant.
従って本発明は、微粒化しても比誘電率の高い結晶粒子により構成される誘電体磁器およびその製法、並びに積層セラミックコンデンサを提供することである。 Accordingly, an object of the present invention is to provide a dielectric ceramic composed of crystal grains having a high relative dielectric constant even when atomized, a manufacturing method thereof, and a multilayer ceramic capacitor.
本発明の誘電体磁器は、（１）チタン酸バリウムを主成分とする結晶粒子の平均径が１５０ｎｍ以下であり、かつ前記結晶粒子のＸ線回折パターンから求められる格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖが０．０６４３ｎｍ３以下であることを特徴とする。 In the dielectric ceramic of the present invention, (1) the crystal grains mainly composed of barium titanate have an average diameter of 150 nm or less and the lattice constants (a, b, c) determined from the X-ray diffraction pattern of the crystal grains. ), The volume V per unit cell represented by the product of 0.0643 nm 3 or less.
即ち本発明にかかる誘電体磁器は、磁器を構成する結晶粒子の平均径が１５０ｎｍ以下であっても、結晶粒子のＸ線回折パターンから求められる格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖを０．０６４３ｎｍ３以下にしたものとすると高い比誘電率が得られる。また、本発明の誘電体磁器では（２）結晶粒子は、立方晶と正方晶とが共存していること、（３）格子定数のｃ／ａ比が１．００５〜１．０１であること、誘電体磁器表面のＸ線回折で得られた回折パターンの、チタン酸バリウム単結晶のＸ線回折パターンとの比較におけるピーク位置のずれから求められる応力が絶対値で１ＭＰａ以上であることが、高誘電率化という点で好ましい。 That is, the dielectric ceramic according to the present invention is represented by the product of the lattice constants (a, b, c) obtained from the X-ray diffraction pattern of the crystal particles even when the average diameter of the crystal particles constituting the ceramic is 150 nm or less. When the volume V per unit cell is set to 0.0643 nm 3 or less, a high relative dielectric constant can be obtained. Further, in the dielectric ceramic according to the present invention, (2) the crystal particles have cubic and tetragonal coexistence, and (3) the lattice constant c / a ratio is from 1.005 to 1.01. The stress obtained from the shift of the peak position in the comparison of the diffraction pattern obtained by X-ray diffraction on the surface of the dielectric ceramic with the X-ray diffraction pattern of the barium titanate single crystal is 1 MPa or more in absolute value. This is preferable in terms of increasing the dielectric constant.
また本発明の積層セラミックコンデンサは、上記の誘電体磁器からなる誘電体層と内部電極層とを交互に積層して構成されたコンデンサ本体を具備してなることを特徴とする。 The multilayer ceramic capacitor of the present invention is characterized in that it comprises a capacitor body formed by alternately laminating dielectric layers made of the above dielectric ceramics and internal electrode layers.
そして、このような誘電体磁器は、（４）（ａ）シュウ酸法、ゾル−ゲル法、水熱合成法等等のうちいずれか１種の液相法によって平均粒径が１００ｎｍ以下の誘電体素粉末を得る工程と、（ｂ）該誘電体素粉末を、大気圧下、温度３００〜５００℃の雰囲気において、ゼオライト系乾燥剤を用いて乾燥熱処理して誘電体粉末を得る工程と、（ｃ）該誘電体粉末を用いて所定形状の成形体に成形し、該成形体を焼成する工程と、を具備する製法により得られる。 Such a dielectric ceramic has a dielectric having an average particle diameter of 100 nm or less by a liquid phase method such as (4) (a) oxalic acid method, sol-gel method, hydrothermal synthesis method, and the like. A step of obtaining a body powder, and (b) a step of obtaining a dielectric powder by subjecting the dielectric powder to a heat treatment using a zeolitic desiccant in an atmosphere at a temperature of 300 to 500 ° C. under atmospheric pressure. (C) The dielectric powder is used to form a molded body having a predetermined shape, and the molded body is fired.
本発明の誘電体磁器は、チタン酸バリウムを主成分とする結晶粒子の平均径が１５０ｎｍ以下であり、かつ前記結晶粒子のＸ線回折パターンから求められる格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖが０．０６４３ｎｍ３以下のであることを特徴とするものである。ここで、体積Ｖはペロブスカイト型結晶構造を形成するという点で０．０６２ｎｍ３以上が好ましく、また、上記格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖは０．０６３〜０．０６４ｎｍ３の範囲がより好ましい。また、結晶粒子の平均径は高い比誘電率を得るという点で３０ｎｍ以上がより好ましい。さらに、本発明にかかる誘電体磁器の磁器密度は５．８〜５．９ｇ／ｃｍ３となり、しかも、結晶粒子中に立方晶と正方晶とが共存し、そのため格子定数のｃ／ａ比が１．００６〜１．００９であることがより望ましい。 The dielectric ceramic according to the present invention has a product of lattice constants (a, b, c) obtained from an X-ray diffraction pattern of crystal grains in which the average diameter of crystal grains mainly composed of barium titanate is 150 nm or less. The volume V per unit cell represented by is 0.0643 nm 3 or less. Here, the volume V is preferably 0.062 nm 3 or more in terms of forming a perovskite crystal structure, and the volume V per unit cell represented by the product of the lattice constants (a, b, c) is 0. A range of 0.063 to 0.064 nm 3 is more preferable. Further, the average diameter of the crystal particles is more preferably 30 nm or more from the viewpoint of obtaining a high relative dielectric constant. Furthermore, the ceramic density of the dielectric ceramic according to the present invention is 5.8 to 5.9 g / cm 3 , and cubic crystals and tetragonal crystals coexist in the crystal grains, so that the c / a ratio of the lattice constant is It is more desirable to be 1.006 to 1.009.
結晶粒子の平均径が１５０ｎｍよりも大きい場合には、積層セラミックコンデンサの誘電体層の単位厚み当たりの粒界の数が少なくなり高い絶縁性が得られなくなる。また、格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖが０．０６４３ｎｍ３より大きいと比誘電率が低下する。 When the average diameter of the crystal grains is larger than 150 nm, the number of grain boundaries per unit thickness of the dielectric layer of the multilayer ceramic capacitor is reduced, and high insulation cannot be obtained. Further, when the volume V per unit cell represented by the product of the lattice constants (a, b, c) is larger than 0.0643 nm 3 , the relative dielectric constant is lowered.
さらに本発明の誘電体磁器は、誘電体磁器表面のＸ線回折で得られた回折パターンの、チタン酸バリウム単結晶のＸ線回折パターンとの比較におけるピーク位置のずれから求められる応力が絶対値で１ＭＰａ以上であることが好ましい。特に、積層セラミックコンデンサにおいては積層数が１００層以上であれば、例えば、ニッケルを主成分とする内部電極層との熱膨張係数差により誘電体層に作用する圧縮応力も付加され、応力は絶対値で５ＭＰａ以上であることがより好ましい。 Furthermore, the dielectric ceramic according to the present invention has an absolute value of the stress obtained from the shift of the peak position in comparison with the X-ray diffraction pattern of the barium titanate single crystal of the diffraction pattern obtained by X-ray diffraction on the surface of the dielectric ceramic. It is preferably 1 MPa or more. In particular, in a multilayer ceramic capacitor, if the number of layers is 100 or more, for example, a compressive stress acting on the dielectric layer is added due to a difference in thermal expansion coefficient from the internal electrode layer mainly composed of nickel, and the stress is absolutely The value is more preferably 5 MPa or more.
次に、本発明にかかる誘電体磁器の製法について説明する。まず、本発明では、（ａ）シュウ酸法、ゾル−ゲル法、水熱合成法等のうちいずれか１種の液相法によって平均粒径が１００ｎｍ以下の誘電体素粉末を得る。上記した製法のうち単分散性が高いという点で特にゾルーゲル法が好ましく、この場合Ｂａ源としてＢａ（ＯＨ）２を用い、Ｔｉ源としてＴｉＯ２を用いる。この場合Ｂａ／Ｔｉ比は０．９９５〜１．００５の範囲が比誘電率の向上および焼結性の点で好ましい。 Next, a method for manufacturing a dielectric ceramic according to the present invention will be described. First, in the present invention, a dielectric elementary powder having an average particle size of 100 nm or less is obtained by any one liquid phase method among (a) oxalic acid method, sol-gel method, hydrothermal synthesis method and the like. Of the above-described production methods, the sol-gel method is particularly preferable in terms of high monodispersibility. In this case, Ba (OH) 2 is used as the Ba source and TiO 2 is used as the Ti source. In this case, the Ba / Ti ratio is preferably in the range of 0.995 to 1.005 from the viewpoint of improvement of relative dielectric constant and sinterability.
次に、ＢａおよびＴｉ源を混合して得られたスラリを大気圧、２００℃の条件で予備乾燥を行う。 Next, the slurry obtained by mixing the Ba and Ti sources is preliminarily dried under conditions of atmospheric pressure and 200 ° C.
次に、（ｂ）誘電体素粉末を、大気圧下、温度３００〜５００℃、特に、３５０〜４５０℃の雰囲気において、ゼオライト系乾燥剤を用いて乾燥熱処理して誘電体粉末を得る。得られる誘電体粉末の粒度のばらつき（ＣＶ値）が５０％以下であることが好ましい。 Next, (b) a dielectric powder is obtained by subjecting the dielectric powder to a dry heat treatment using a zeolitic desiccant in an atmosphere at a temperature of 300 to 500 ° C., particularly 350 to 450 ° C. under atmospheric pressure. It is preferable that variation in the particle size (CV value) of the obtained dielectric powder is 50% or less.
ゼオライト系乾燥剤はモレキュラーシーブ、メタロシリケート、クローバライトなどが好適であるが、特に、耐熱性の点でモレキュラーシーブがより好ましい。また、ゼオライト系乾燥剤の比表面積は４００ｍ２／ｇ以上であればよく、特に、乾燥効率および耐久性の点で５００〜７００ｍ２／ｇが好ましい。また誘電体素粉末１００質量部に対するゼオライト系乾燥剤の量は５〜２０質量部が好ましい。ゼオライト系乾燥剤の比表面積を維持するという点で温度が６００℃より低いことが好ましく、それより高い場合にはゼオライト系乾燥剤が変質し比表面積が小さくなる。 As the zeolitic desiccant, molecular sieve, metallosilicate, cloverite and the like are suitable, but molecular sieve is more preferred from the viewpoint of heat resistance. The specific surface area of the zeolite drying agent should be at 400 meters 2 / g or more, particularly, 500 to 700 m 2 / g is preferable from the viewpoint of drying efficiency and durability. The amount of the zeolitic desiccant with respect to 100 parts by mass of the dielectric powder is preferably 5 to 20 parts by mass. The temperature is preferably lower than 600 ° C. in terms of maintaining the specific surface area of the zeolitic desiccant, and if it is higher, the zeolitic desiccant is altered and the specific surface area is reduced.
次に、（ｃ）該誘電体粉末を主成分として用いて所定形状の成形体に成形し、該成形体を焼成する。成形は上記誘電体粉末をバインダとともに成形して、例えば、単板コンデンサとなる所定形状の（円板状の）成形体を形成する。 Next, (c) the dielectric powder is used as a main component to form a molded body having a predetermined shape, and the molded body is fired. In the molding, the dielectric powder is molded together with a binder to form a molded body having a predetermined shape (disk shape) to be a single plate capacitor, for example.
また、積層セラミックコンデンサを形成する場合には、上記誘電体粉末をバインダおよび溶剤とともに混合してスラリを得、次いで、このスラリをドクターブレード法などのシート成形法により、例えば厚み１μｍのシート状成形体を形成する。この後シート状成形体上に導体パターンを印刷して、導体パターンが形成されたシートを形成し、これらのシートを複数積層して積層成形体を形成した後に、導体パターンの焼結温度付近の温度で焼成することにより積層セラミックコンデンサが得られる。 Also, when forming a multilayer ceramic capacitor, the dielectric powder is mixed with a binder and a solvent to obtain a slurry, and then this slurry is formed into a sheet having a thickness of, for example, 1 μm by a sheet forming method such as a doctor blade method. Form the body. Thereafter, a conductor pattern is printed on the sheet-like molded body to form a sheet on which the conductor pattern is formed. After a plurality of these sheets are laminated to form a laminated molded body, the conductive pattern near the sintering temperature of the conductor pattern is formed. A multilayer ceramic capacitor is obtained by firing at a temperature.
液相法によって得られる誘電体素粉末の平均粒径が１００ｎｍよりも大きい場合には、焼結後に得られる結晶粒子の大きさが大きくなり絶縁抵抗が低くなる原因となる。また、誘電体素粉末の乾燥温度が３００℃以下の場合には、乾燥不足となり、粉末中に依然として水酸基などの液相法に由来する不純物を除くことが困難となりまた粒成長も起こりにくくなる。一方、温度が６００℃より高い場合には誘電体素粉末の平均粒径が大きくなりすぎて所望の大きさの誘電体粉末が得られなくなり、薄層化したグリーンシートが得られなくなる。圧力が大気圧よりも低い場合、あるいは大気圧より高い場合には工業的に高コストの減圧装置や加圧装置が必要となり、原料粉末となる誘電体粉末の低コストでの製造が困難となる。 When the average particle size of the dielectric powder obtained by the liquid phase method is larger than 100 nm, the size of the crystal particles obtained after sintering becomes large, which causes a decrease in insulation resistance. Moreover, when the drying temperature of the dielectric element powder is 300 ° C. or lower, the drying is insufficient, and it is still difficult to remove impurities derived from the liquid phase method such as hydroxyl groups in the powder, and grain growth is less likely to occur. On the other hand, when the temperature is higher than 600 ° C., the average particle diameter of the dielectric powder becomes too large to obtain a desired size of dielectric powder, and a thin green sheet cannot be obtained. When the pressure is lower than atmospheric pressure or higher than atmospheric pressure, an industrially expensive decompression device or pressurization device is required, making it difficult to produce dielectric powder as a raw material powder at low cost. .
つまり、上記工程により得られる誘電体粉末は、従来の単に乾燥しただけの誘電体粉末に比較して、粉末の表層や内部に不純物が除かれた状態であり、そのため欠陥が多くなり、表層部分の格子が縮みやすくなることによって粉末内部に圧縮応力がかかり、全体的に格子定数が小さくなりこのためユニットセル当りの体積が減少する。 In other words, the dielectric powder obtained by the above process is in a state in which impurities are removed from the surface layer and the inside of the powder as compared with the conventional dielectric powder that is simply dried, so that there are more defects and the surface layer portion. Since the lattice of the material tends to shrink, a compressive stress is applied to the inside of the powder, and the lattice constant is reduced as a whole, thereby reducing the volume per unit cell.
先ず、表１に示すゾルーゲル法、水熱合成法、蓚酸塩法、ならびに固相法により得られた誘電体素粉末を用意した。これらの粉末はＢａ／Ｔｉ比が１．００５になるように混合した。 First, dielectric powders obtained by the sol-gel method, hydrothermal synthesis method, oxalate method, and solid phase method shown in Table 1 were prepared. These powders were mixed so that the Ba / Ti ratio was 1.005.
次に、粉末の乾燥は、ゼオライト系乾燥剤を用いない場合は、上記の粉末を大気圧下、温度２００℃の雰囲気の条件で予備乾燥を行った。 Next, when the zeolite-type desiccant was not used, the powder was preliminarily dried under the atmospheric pressure and 200 ° C. atmosphere conditions.
一方、ゼオライト系乾燥剤を用いる場合は、調製した誘電体素粉末を、大気圧下、４００℃にてアルミノ珪酸塩を主成分とし比表面積が６００ｍ２／ｇのゼオライト系乾燥剤を用いて乾燥熱処理を行って誘電体粉末を得た。誘電体素粉末１００質量部に対するゼオライト系乾燥剤の量は１０質量部とした。 On the other hand, when using a zeolitic desiccant, the prepared dielectric powder is dried using a zeolitic desiccant having an aluminosilicate as a main component and a specific surface area of 600 m 2 / g at 400 ° C. under atmospheric pressure. A heat treatment was performed to obtain a dielectric powder. The amount of the zeolitic desiccant with respect to 100 parts by mass of the dielectric powder was 10 parts by mass.
次に、上記に得られた誘電体粉末を用いて、直径１５ｍｍ、厚み１ｍｍの成形体に成形し、温度９００℃、圧力１０７Ｐａの条件でホットプレスを行い、この後に、大気中、８００℃で酸化処理を行った。 Next, the dielectric powder obtained above was molded into a molded body having a diameter of 15 mm and a thickness of 1 mm, and hot-pressed under conditions of a temperature of 900 ° C. and a pressure of 10 7 Pa. Oxidation treatment was performed at ° C.
次に、得られた誘電体磁器について、走査型電子顕微鏡を用いて結晶粒子の平均径を測定した。１試料あたり測定点は１０００点とし平均値として求めた。平均径は１００ｎｍであった。 Next, with respect to the obtained dielectric ceramic, the average diameter of crystal grains was measured using a scanning electron microscope. The number of measurement points per sample was 1000, and the average value was obtained. The average diameter was 100 nm.
次に、得られた試料についてＸ線回折の測定を行い、ユニットセル当りの体積Ｖを算出した。回折角度は４４〜４６°とし、格子定数ａ、ｂ、ｃを求め、それらの値からユニットセルの体積を求めた。また、このＸ線回折ピークについてチタン酸バリウム単結晶について求めた同回折角度のＸ線回折ピークからの差を求め応力を求めた。本発明の試料の応力はいずれも１．５ＭＰａであった。また、ここで作製した本発明の試料の誘電体磁器を構成する結晶粒子は、リートベルト解析によれば、いずれも立方晶と正方晶とが共存していた。また、格子定数比ｃ／ａは１．００８（試料Ｎｏ．６）、１．００９（試料Ｎｏ．６）であった。本発明外の製法で作製した試料の格子定数比ｃ／ａは、立方晶比率は１．００３から１．００７であった。 Next, X-ray diffraction measurement was performed on the obtained sample, and the volume V per unit cell was calculated. The diffraction angle was 44 to 46 °, the lattice constants a, b, and c were determined, and the volume of the unit cell was determined from these values. Moreover, the stress was calculated | required by calculating | requiring the difference from the X-ray diffraction peak of the same diffraction angle calculated | required about the barium titanate single crystal about this X-ray diffraction peak. The stresses of the samples of the present invention were all 1.5 MPa. Further, according to Rietveld analysis, the crystal particles constituting the dielectric ceramic of the sample of the present invention produced here coexisted with cubic crystals and tetragonal crystals. The lattice constant ratio c / a was 1.008 (sample No. 6) and 1.009 (sample No. 6). As for the lattice constant ratio c / a of the sample produced by the production method outside the present invention, the cubic ratio was from 1.003 to 1.007.
次に電極を形成するために、焼成した誘電体磁器を研磨した後寸法と重量を測定した後にＧａ−Ｉｎ電極を対向する表面に塗布した。この後、誘電体磁器の静電容量をＬＣＲメータを用いて、周波数１ｋＨｚ、電圧１Ｖにて、１分間測定し、試料の直径および厚みとその静電容量から比誘電率を算出した。また比誘電率の温度特性（ＴＣＣ）についても評価した。結果を表１に示す。
表１の結果から明らかなように、誘電体粉末を調製する際に、誘電体素粉末をゼオライト系乾燥剤を用いて乾燥熱処理して得られた誘電体素粉末を用い焼成して得られた誘電体磁器では、誘電体素粉末の含水率が０．２１、０．２３％であり、構成する結晶粒子の平均径が１５０ｎｍ以下となり、かつＸ線回折パターンから求められる格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖが０．０６４〜０．０６４３ｎｍ３の範囲となり、比誘電率が１５６５以上、２５℃を基準にした比誘電率に対する変化率としての温度特性が１．２２％、２．１９％であった。 As is apparent from the results in Table 1, when preparing the dielectric powder, the dielectric powder was obtained by firing using the dielectric powder obtained by drying and heat treatment using a zeolite desiccant. In the dielectric ceramic, the moisture content of the dielectric powder is 0.21 and 0.23%, the average diameter of the constituent crystal particles is 150 nm or less, and the lattice constant (a, b) obtained from the X-ray diffraction pattern , C) The volume V per unit cell represented by the product is in the range of 0.064 to 0.0643 nm 3 , the relative dielectric constant is 1565 or more, and the temperature as the rate of change relative to the relative dielectric constant based on 25 ° C. The characteristics were 1.22% and 2.19%.
これに対して、従来の製法により調製した誘電体粉末の場合には、誘電体素粉末の含水率が０．４４〜０．５６％であり、誘電体磁器を構成する結晶粒子の平均径が１５０ｎｍ以下にできたものの、Ｘ線回折パターンから求められる格子定数（ａ、ｂ、ｃ）の積で表されるユニットセル当りの体積Ｖが０．０６４３ｎｍ３より大きくなり、比誘電率が１５００より低く、２５℃を基準にした比誘電率に対する変化率としての温度特性が−３．９２〜−１０．９８％と本発明の試料に比較して絶対値的に大きかった。 In contrast, in the case of a dielectric powder prepared by a conventional manufacturing method, the moisture content of the dielectric powder is 0.44 to 0.56%, and the average diameter of the crystal particles constituting the dielectric ceramic is Although it was made 150 nm or less, the volume V per unit cell represented by the product of the lattice constants (a, b, c) obtained from the X-ray diffraction pattern was larger than 0.0643 nm 3 and the relative dielectric constant was 1500 The temperature characteristic as a change rate with respect to the relative dielectric constant with 25 ° C. as a reference was −3.92 to −10.98%, which was larger in absolute value than the sample of the present invention.
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