JPH03285869A - Grain boundary insulation type semiconductor porcelain composition and production thereof - Google Patents
Grain boundary insulation type semiconductor porcelain composition and production thereofInfo
- Publication number
- JPH03285869A JPH03285869A JP2085248A JP8524890A JPH03285869A JP H03285869 A JPH03285869 A JP H03285869A JP 2085248 A JP2085248 A JP 2085248A JP 8524890 A JP8524890 A JP 8524890A JP H03285869 A JPH03285869 A JP H03285869A
- Authority
- JP
- Japan
- Prior art keywords
- grain boundary
- semiconductor porcelain
- composition
- present
- range
- 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
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000009413 insulation Methods 0.000 title description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 3
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 230000014509 gene expression Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 9
- 239000003985 ceramic capacitor Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910002616 GeOx Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、磁器コンデンサ等に用いるための粒界絶縁型
半導体磁器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a grain boundary insulated semiconductor ceramic composition for use in ceramic capacitors and the like.
［従来の技術］
従来、小型で容量の大きいコンデンサとして、粒界絶縁
型半導体磁器コンデンサが知られている。[Prior Art] Grain-boundary insulated semiconductor ceramic capacitors have been known as small-sized, large-capacity capacitors.
粒界絶縁型半導体磁器コンデンサは、結晶粒界を絶縁化
することにより実効誘電率を大きくしたものである。A grain boundary insulated semiconductor ceramic capacitor has a large effective dielectric constant by insulating the grain boundaries.
粒界絶縁型半導体磁器コンデンサに用いられる磁器組成
物としては、主成分に、チタン酸ストロンチウムまたは
チタン酸バリウムを用い、原子価制御用助剤として、Ｎ
ｂ２ｏ３、Ｙ２Ｏ５、Ｄｙ２０、等を添加し、さらに、
焼結助剤として、Ｍｎｏｉ 、Ｂｉ２０ｉ 、Ｃｕｂ、
５ｉ０２等が用いられる。The ceramic composition used in grain boundary insulated semiconductor ceramic capacitors uses strontium titanate or barium titanate as the main component, and N as an auxiliary agent for valence control.
b2o3, Y2O5, Dy20, etc. are added, and further,
As a sintering aid, Mnoi, Bi20i, Cub,
5i02 etc. are used.
例えば、特開昭５６−５４０２６には、（Ｓｒ１−ｘ
Ｂａｘ）Ｔｉｌｔ （ｘ＝０．３０〜０．５０）を主
体とし、その他にチタン酸塩、ジルコン酸塩を含んだ主
成分に対してＬａ、Ｙなどの希土類元素、Ｎｂ、Ｔａ、
Ｗなどのような半導体化剤とＭｎを含有し、結晶粒界が
Ｍｎ、Ｂ ｉ 、Ｃｕ、Ｐｂ、ＢおよびＳＬのうちの少
なくとも１種（ただし、Ｂ、Ｂｉのいづれか１種のみは
除く）により絶縁体化されてなる最大粒径が１００ＪＪ
、ｍ以上の粒界絶縁型半導体磁器組成物である。For example, in JP-A-56-54026, (Sr1-x
Bax) Tilt (x = 0.30 to 0.50), and other main components including titanate and zirconate, rare earth elements such as La and Y, Nb, Ta,
Contains a semiconducting agent such as W and Mn, and has crystal grain boundaries of at least one of Mn, B i , Cu, Pb, B, and SL (excluding only one of B and Bi) The maximum particle size made into an insulator is 100JJ.
, m or more is a grain boundary insulated semiconductor ceramic composition.
近年、磁器コンデンサの小型化の要求に伴い、粒界絶縁
型半導体磁器コンデンサにおいても、より小型化、薄形
化の要求が高まっている。In recent years, with the demand for smaller ceramic capacitors, there has also been an increasing demand for smaller and thinner grain boundary insulated semiconductor ceramic capacitors.
［発明が解決しようとする課題］
従来の粒界絶縁型半導体磁器では、見掛は誘電率を大き
くする必要から粒径を比較的大きくしていた。しかしな
がら、近年の要求に従い、磁器組成物の層を薄くした場
合には、厚み当りの結晶粒子の数が少なくなってしまう
。そのため、単位厚さ当りの絶縁破壊電圧が小さくなり
、その結果、誘電率と絶縁破壊電圧との積が小さくなっ
てしまっていた。その結果、粒界絶縁型半導体磁器コン
デンサの薄型化、小型化が困難であった。[Problems to be Solved by the Invention] In conventional grain boundary insulated semiconductor porcelain, the grain size has been made relatively large because it is necessary to increase the apparent dielectric constant. However, when the layer of the ceramic composition is made thinner in accordance with recent demands, the number of crystal grains per thickness becomes smaller. Therefore, the dielectric breakdown voltage per unit thickness becomes small, and as a result, the product of dielectric constant and dielectric breakdown voltage becomes small. As a result, it has been difficult to reduce the thickness and size of grain boundary insulated semiconductor ceramic capacitors.
本発明は、最大粒径を４０〜７０μｍに制御可能であり
、かつ、厚み当りの誘電率と絶縁破壊電圧との積が大き
い粒界絶縁型半導体磁器組成物およびその製造方法を提
供することを目的とする。The present invention aims to provide a grain-boundary insulated semiconductor ceramic composition whose maximum grain size can be controlled to 40 to 70 μm and which has a large product of dielectric constant per thickness and dielectric breakdown voltage, and a method for producing the same. purpose.
［課題を解決するための手段］
本発明は、上記目的を達成するために、以下の組成゛の
粒界絶縁型半導体磁器組成物を提供する。[Means for Solving the Problems] In order to achieve the above object, the present invention provides a grain boundary insulated semiconductor ceramic composition having the following composition.
すなわち、一般式（Ｓｒｌ−ｘ−ｓ Ｂａ、ＣａｓＭｙ
） Ｔ １ ｓ Ｏ３＋ｍ Ｎ ＋ ｎ Ｚ （但、
Ｍは、Ｎｂ、Ｔａ、Ｗ、及び希土類元素のうち少なくと
も１種類、Ｎは、Ｍｎ、Ａｌ、及びＳｉのうち少なくと
も１種類、２は、Ｇｅ、Ｆｅの一方又は両方）で表され
、ｘ、ｙ、ｚ、ｊ 、ｍ、ｎがそれぞれ、０゜０００１
≦ｘ≦０．０５．０．００１≦ｙ≦０゜０３、Ｏ＜ｚ≦
０．３０．０．９９０≦１≦１゜０１０．０．０００１
≦ｍ≦０．０１．０．００１≦ｎ≦０．０３、の範囲に
ある半導体磁器の結晶粒界が、Ｃｕ、Ｂｉ、、Ｐｂ、Ｂ
、及びＳｉのうち少なくともＩＮを含む化合物により絶
縁された粒界絶縁型半導体磁器組成物である。That is, the general formula (Srl-x-s Ba, CasMy
) T 1 s O3+m N + n Z (However,
M is at least one of Nb, Ta, W, and a rare earth element, N is at least one of Mn, Al, and Si, and 2 is one or both of Ge and Fe; y, z, j, m, n are each 0°0001
≦x≦0.05.0.001≦y≦0゜03, O<z≦
0.30.0.990≦1≦1゜010.0.0001
The crystal grain boundaries of semiconductor porcelain in the range of ≦m≦0.01.0.001≦n≦0.03 are Cu, Bi, Pb, B
, and a grain boundary insulated semiconductor ceramic composition insulated by a compound containing at least IN among Si.
また、一般式（Ｓｒｉ−ｘ−＊ Ｂａ、Ｃａ、Ｍｙ ）
Ｔ ｉ ｓ○、＋ｍＮ＋ｎＺ （但、Ｍは、Ｎｂ、Ｔａ
、Ｗ、及び希土類元素のうち少なくとも１種類、Ｎは、
Ｍｎ、Ａｌ、及びＳｉのうち少なくとも１種類、Ｚは、
Ｇｅ、Ｆｅの一方又は両方）で表され、ｘ、ｙ、ｚ、ｊ
、ｍ、ｎがそれぞれ、ｏ、ｏｏ。In addition, the general formula (Sri-x-*Ba, Ca, My)
T i s○, +mN+nZ (However, M is Nb, Ta
, W, and at least one rare earth element, N is
At least one of Mn, Al, and Si, Z is
Ge, Fe, or both), x, y, z, j
, m, and n are o and oo, respectively.
ｌ≦ｘ≦０，０５．０．００１≦ｙ≦０．０３．０＜ｚ
≦０．３０．０．９９０≦ｐ≦１．０１０．０．０００
１≦ｍ≦０．０１．０．００１≦ｎ≦０．０３、の範囲
になるように配合した後、焼成することによって半導体
磁器を得る工程と、前記工程によって得られた半導体磁
器の結晶粒界をＣｕ、Ｂｉ、Ｐｂ、Ｂ、及びＳｉのうち
少なくとも１種を含む化合物を用いて絶縁化する工程と
を有する粒界絶縁型半導体磁器組成物の製造方法である
。l≦x≦0, 05.0.001≦y≦0.03.0<z
≦0.30.0.990≦p≦1.010.0.000
1≦m≦0.01.0.001≦n≦0.03, and then firing the mixture to obtain semiconductor porcelain, and crystal grains of the semiconductor porcelain obtained by the step. A method for producing a grain boundary insulated semiconductor ceramic composition comprising the step of insulating the grain boundary using a compound containing at least one of Cu, Bi, Pb, B, and Si.
以下、本発明の数値範囲の限定理由について説明する。The reason for limiting the numerical range of the present invention will be explained below.
本発明のＸの範囲は、０．０００１≦ｘ≦０゜０５であ
る。すなわち、０．０００１未満では、原材料の精製が
困難であり実用上問題がある。また、０．０５よりも大
きいと、見掛は誘電率が低下してしまい、本発明の目的
を達成することができない。The range of X in the present invention is 0.0001≦x≦0°05. That is, if it is less than 0.0001, it is difficult to purify the raw material and there is a practical problem. On the other hand, if it is larger than 0.05, the apparent dielectric constant will decrease, making it impossible to achieve the object of the present invention.
本発明のＺの範囲は、Ｏ＜ｚ≦０．３０である。The range of Z in the present invention is O<z≦0.30.
すなわち、Ｃａを含ませることにより、静電容量の温度
変化率を制御することが可能になる。しかし、０．３０
よりも大きいと、見掛は誘電率が低下してしまい、本発
明の目的を達成することができない。That is, by including Ca, it becomes possible to control the rate of change in capacitance with temperature. However, 0.30
If it is larger than , the apparent dielectric constant will decrease and the object of the present invention cannot be achieved.
一般式中Ｍとして用いられるＮｂ、Ｔａ、Ｗ、及び希土
類元素のうち少なくとも１種類の含有範囲を示すｙの範
囲は、０．００１≦ｙ≦０．０３である。０．００１未
満であっても、０，０３よりも大きくても、結晶の半導
体化が困難になり本発明の目的を達成することができな
い。The range of y, which indicates the content range of at least one of Nb, Ta, W, and rare earth elements used as M in the general formula, is 0.001≦y≦0.03. Even if it is less than 0.001 or larger than 0.03, it becomes difficult to convert the crystal into a semiconductor, and the object of the present invention cannot be achieved.
一般式中のＴｉの含有範囲を示す１の範囲は、０．９９
０≦１≦１．０１０である。０．９９０未満では、粒径
７０μｍよりも大きい結晶粒子が生じてしまう。また、
１．０１０よりも太きくなると、結晶粒子の平均粒径が
４０μｍ以下になってしまい、十分な見掛は誘電率を得
ることができなくなり、本発明の目的を達成することが
できない
一般式中Ｎとして用いられるＭｎ、Ａｌ、及びＳｉのう
ち少なくとも１種類の含有範囲を示すｍの範囲は、０．
０００１≦ｍ≦０．０１である。The range of 1 indicating the content range of Ti in the general formula is 0.99
0≦1≦1.010. If it is less than 0.990, crystal grains with a grain size larger than 70 μm will be produced. Also,
If it becomes thicker than 1.010, the average grain size of the crystal grains becomes 40 μm or less, making it impossible to obtain a sufficient apparent dielectric constant, and the purpose of the present invention cannot be achieved. The range of m indicating the content range of at least one of Mn, Al, and Si used as N is 0.
0001≦m≦0.01.
０．０００１未満では、見掛は誘電率が低くなり、本発
明の目的を達成することができない。また、０．０１よ
りも大きいと、見掛は誘電率が低下してしまい、また、
誘電体損失（ｔａｎδ）も悪くなり、本発明の目的を達
成することができない。If it is less than 0.0001, the apparent dielectric constant becomes low and the object of the present invention cannot be achieved. Moreover, if it is larger than 0.01, the apparent dielectric constant will decrease, and
The dielectric loss (tan δ) also deteriorates, making it impossible to achieve the object of the present invention.
一般式中２として用いられるＧｅ、Ｆｅの一方又は両方
を含有させることにより、結晶粒子の制御が可能になる
。その範囲を示すｎの範囲は、０゜００１≦ｎ≦０．０
３である。Ｏ，００１未満では、７０μｍよりも大きい
結晶粒子が生じ、絶縁破壊電圧が低くなる。味な、０．
０３よりも大きいと、焼成温度が高くなり、また絶縁破
壊電圧も低くなり、本発明の目的を達成することができ
ない。By containing one or both of Ge and Fe used as 2 in the general formula, it becomes possible to control crystal grains. The range of n that indicates the range is 0°001≦n≦0.0
It is 3. If it is less than O,001, crystal grains larger than 70 μm are produced and the dielectric breakdown voltage becomes low. The taste is 0.
If it is larger than 03, the firing temperature will be high and the dielectric breakdown voltage will also be low, making it impossible to achieve the object of the present invention.
なお、本発明の一般式中、ｍ及びｎは、酸化物の形で含
まれる場合には、例えば一般式Ｘａ Ｏｂとして示され
るものをＸ Ｏｂ／ａの形に直したときのＸの元素の量
で表される。In addition, in the general formula of the present invention, when m and n are included in the form of an oxide, for example, when the general formula XaOb is changed to the form XOb/a, the element of X is expressed in quantity.
また、本発明に用いられている数値は、すべてモル（ｌ
Ｒｏ ｌ ）で示した値である。Furthermore, all numerical values used in the present invention are in moles (l
This is the value indicated by Ro l ).
Ｅ実施例コ 以下、実施例により本発明を具体的に説明する。E Example Hereinafter, the present invention will be specifically explained with reference to Examples.
まず、第１表の試料番号１の調製方法とその電気的特性
について説明する。First, the preparation method of sample number 1 in Table 1 and its electrical properties will be explained.
５ｒｃｏ） 、ＢａＣＣ）３ 、ＣａＣ０，、Ｔｉ ０
２ 、Ｙ２０３、ＭｎＯ２、ＧｅＯｘの化合物を第１表
に示す組成比になるように配合し、ｘ５０℃で２時間仮
焼を行った。5rco), BaCC)3, CaC0,, Ti0
2, Y203, MnO2, and GeOx were mixed in the composition ratio shown in Table 1, and calcined at 50°C for 2 hours.
これを粉砕し、アクリル系バインダを１０ｗｔ％加え、
攪拌した後、５０メツシユのふるいで造粒し、成形圧力
１ ｔｏｎ／Ｃ１、直径１２．５ｍｍ、肉厚０．３ｍｍ
の円板に成形した。Grind this, add 10wt% of acrylic binder,
After stirring, the mixture was granulated using a 50-mesh sieve, with a molding pressure of 1 ton/C1, a diameter of 12.5 mm, and a wall thickness of 0.3 mm.
It was formed into a disc.
得られた円板状成形体を、窒素９８ｖｏ１％、水素２Ｖ
ＯＨからなる還元雰囲気にて１４００℃で３時間焼成し
、半導体磁器を得た。The obtained disk-shaped molded body was heated with 98 vol. of nitrogen and 2 V of hydrogen.
It was fired at 1400° C. for 3 hours in a reducing atmosphere consisting of OH to obtain semiconductor porcelain.
得られた半導体磁器の表面に金属酸化物ペースト、具体
的には、Ｂｉ２Ｏ，を４０ｗｔ％、ｐｂ３０４を４６
ｗ ｔ％、Ｂ２０．を７ ｗ ｔ％、ＣｕＯを６ ｗ
ｔ％、Ｓｉｎ、を１ｗｔ％および樹脂を溶剤に添加した
ペーストを塗布し、ｘ５０℃で２時間熱拡散させ、結晶
粒界を絶縁化した。A metal oxide paste, specifically 40wt% Bi2O and 46% pb304, was applied to the surface of the obtained semiconductor ceramic.
wt%, B20. 7 wt%, CuO 6 wt%
A paste containing 1 wt % of t%, Sin, and a resin added to a solvent was applied and thermally diffused at x50° C. for 2 hours to insulate the grain boundaries.
さらに、この粒界絶縁型半導体磁器の表面に銀ペースト
を印刷することによって塗布し、８００℃で１時間焼き
付けることによってコンデンサを作成した。Furthermore, a capacitor was fabricated by applying a silver paste to the surface of this grain boundary insulated semiconductor porcelain by printing and baking it at 800° C. for 1 hour.
（以下余白）
第１表
第２表
得られたコンデンサの電気的特性を測定したところ、第
２表の試料番号１に示す結果を得ることができた。(Left below) Table 1 Table 2 The electrical characteristics of the obtained capacitors were measured, and the results shown in sample number 1 in Table 2 were obtained.
試料番号２以降の組成物についても、同様の条件にてコ
ンデンサを作成し、同様の条件にて電気的特性を測定し
た。Concerning the compositions of Sample No. 2 and subsequent samples, capacitors were also produced under the same conditions, and the electrical characteristics were measured under the same conditions.
表中、見掛は誘電率（ε）、誘電体損失（ｔａｎδ）は
、温度２５℃にて周波数１ ｋＨｚ、電圧１Ｖ７１ｓで
測定した値であり、絶縁抵抗（ＩＲ＞は、温度２５℃に
て２５Ｖの直流電圧を印加した１５秒後の値であり、温
度特性（ＴＣ）は、温度２０℃を基準とし、−２５℃〜
８５℃の温度範囲における最大容量変化率の値であり、
表中、上段は、最大容量増加率を示し、下段は、最大容
量減少率を示す。また、誘電率と絶縁破壊電圧との積（
ｇＸＢＤＶ）は、１ｍｍ当りの誘電率と絶縁破壊電圧と
の積を示す。In the table, the apparent dielectric constant (ε), the dielectric loss (tan δ) are the values measured at a temperature of 25°C, a frequency of 1 kHz, and a voltage of 1 V for 71 seconds, and the insulation resistance (IR>) is a value measured at a temperature of 25°C. This is the value 15 seconds after applying a DC voltage of 25V, and the temperature characteristics (TC) are based on a temperature of 20°C, and range from -25°C to
It is the value of the maximum capacity change rate in the temperature range of 85 ° C.
In the table, the upper row shows the maximum capacity increase rate, and the lower row shows the maximum capacity decrease rate. Also, the product of permittivity and dielectric breakdown voltage (
gXBDV) indicates the product of dielectric constant and dielectric breakdown voltage per mm.
なお、表中、試料番号の右上に示される＊は、本発明の
範囲外の試料、すなわち、比較例であることを示す。In addition, in the table, * shown in the upper right corner of the sample number indicates that it is a sample outside the scope of the present invention, that is, a comparative example.
本実施例の試料番号１〜４．６〜９．１２〜１４．１７
〜１９．２２〜２４及び２７〜２つに示されるように、
本発明によれば、最大粒径が４０〜７０μｍであり、誘
電体損失が０．５％以下であり、絶縁抵抗が１５００Ｍ
Ω以上であり、温度特性が土１５％の範囲内であり、か
つ、厚み当りの誘を率と絶縁破壊電圧との積が７．０Ｘ
ＩＯ’以上の粒界絶縁型半導体磁器組成物を得ることが
できる。Sample numbers 1-4.6-9.12-14.17 of this example
~19. As shown in 22-24 and 27-2,
According to the present invention, the maximum grain size is 40 to 70 μm, the dielectric loss is 0.5% or less, and the insulation resistance is 1500 M.
Ω or more, the temperature characteristics are within the range of 15% of soil, and the product of dielectric constant per thickness and dielectric breakdown voltage is 7.0X
It is possible to obtain a grain boundary insulated semiconductor ceramic composition of IO' or higher.
一方、本発明の範囲外の試料番号５．１０．ｘ．１５．
１６．２０．２１．２５．２６．３０においては、本発
明の目的を達成することができない。On the other hand, sample number 5.10. outside the scope of the present invention. x. 15.
16.20.21.25.26.30, the object of the present invention cannot be achieved.
なお、本発明者らは、表中に示される実施例の組成に限
られず、特許請求の範囲に記載された組成範囲であれば
、本発明の範囲内の他の物質であっても本発明の効果を
得ることができることがわかっている。The present inventors believe that the present invention is not limited to the compositions of the examples shown in the table, and even other substances within the scope of the present invention can be used as long as they are within the composition range described in the claims. It is known that this effect can be obtained.
［効果コ
本発明によれば、最大粒径を４０〜７０Ｊｉｍに制御可
能であり、かつ、厚み当りの誘電率と絶縁破壊電圧との
積が大きい粒界絶縁型半導体磁器組成物およびその製造
方法を提供することができる。[Effects] According to the present invention, a grain boundary insulated semiconductor ceramic composition in which the maximum grain size can be controlled to 40 to 70Jim and a product of the dielectric constant per thickness and the dielectric breakdown voltage is large, and a method for producing the same can be provided.
Claims (1)
＿ｚＭ＿ｙ）Ｔｉ＿ｌＯ＿３＋ｍＮ＋ｎＺ（但、Ｍは、
Ｎｂ、Ｔａ、Ｗ、及び希土類元素のうち少なくとも１種
類、Ｎは、Ｍｎ、Ａｌ、及びＳｉのうち少なくとも１種
類、Ｚは、Ｇｅ、Ｆｅの一方又は両方）で表され、ｘ、
ｙ、ｚ、ｌ、ｍ、ｎがそれぞれ ０．０００１≦ｘ≦０．０５ ０．００１≦ｙ≦０．０３ ０＜ｚ≦０．３０ ０．９９０≦ｌ≦１．０１０ ０．０００１≦ｍ≦０．０１ ０．００１≦ｎ≦０．０３ の範囲にある半導体磁器の結晶粒界が、Ｃｕ、Ｂｉ、Ｐ
ｂ、Ｂ、及びＳｉのうち少なくとも１種を含む化合物に
より絶縁された粒界絶縁型半導体磁器組成物。 （２）一般式（Ｓｒ＿１＿−＿ｘ＿−＿ｚＢａ＿ｘＣａ
＿ｚＭ＿ｙ）Ｔｉ＿ｌＯ＿３＋ｍＮ＋ｎＺ（但、Ｍは、
Ｎｂ、Ｔａ、Ｗ、及び希土類元素のうち少なくとも１種
類、Ｎは、Ｍｎ、Ａｌ、及びＳｉのうち少なくとも１種
類、Ｚは、Ｇｅ、Ｆｅの一方又は両方）で表され、ｘ、
ｙ、ｚ、ｌ、ｍ、ｎがそれぞれ ０．０００１≦ｘ≦０．０５ ０．００１≦ｙ≦０．０３ ０＜ｚ≦０．３０ ０．９９０≦ｌ≦１．０１０ ０．０００１≦ｍ≦０．０１ ０．００１≦ｎ≦０．０３ の範囲になるように配合した後、焼成することによって
半導体磁器を得る工程と、 前記工程によって得られた半導体磁器の結晶粒界をＣｕ
、Ｂｉ、Ｐｂ、Ｂ、及びＳｉのうち少なくとも１種を含
む化合物を用いて絶縁化する工程とを有する粒界絶縁型
半導体磁器組成物の製造方法。[Claims] (1) General formula (Sr_1_-_x_-_zBa_xCa
_zM_y) Ti_lO_3+mN+nZ (However, M is
Nb, Ta, W, and at least one of rare earth elements, N is at least one of Mn, Al, and Si, Z is one or both of Ge and Fe, x,
y, z, l, m, n are each 0.0001≦x≦0.05 0.001≦y≦0.03 0<z≦0.30 0.990≦l≦1.010 0.0001≦m The grain boundaries of semiconductor ceramics in the range of ≦0.01 0.001≦n≦0.03 are Cu, Bi, P
A grain boundary insulated semiconductor ceramic composition insulated by a compound containing at least one of B, B, and Si. (2) General formula (Sr_1_-_x_-_zBa_xCa
_zM_y) Ti_lO_3+mN+nZ (However, M is
Nb, Ta, W, and at least one of rare earth elements, N is at least one of Mn, Al, and Si, Z is one or both of Ge and Fe, x,
y, z, l, m, n are each 0.0001≦x≦0.05 0.001≦y≦0.03 0<z≦0.30 0.990≦l≦1.010 0.0001≦m ≦0.01 0.001≦n≦0.03 and then firing to obtain semiconductor porcelain; and Cu
, a step of insulating using a compound containing at least one of Bi, Pb, B, and Si.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2085248A JPH0761895B2 (en) | 1990-03-30 | 1990-03-30 | Grain boundary insulating semiconductor ceramic composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2085248A JPH0761895B2 (en) | 1990-03-30 | 1990-03-30 | Grain boundary insulating semiconductor ceramic composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03285869A true JPH03285869A (en) | 1991-12-17 |
| JPH0761895B2 JPH0761895B2 (en) | 1995-07-05 |
Family
ID=13853271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2085248A Expired - Fee Related JPH0761895B2 (en) | 1990-03-30 | 1990-03-30 | Grain boundary insulating semiconductor ceramic composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761895B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52147800A (en) * | 1976-06-03 | 1977-12-08 | Matsushita Electric Ind Co Ltd | Semiconductor ceramic capacitor composite and its method of manufacturing |
| JPS5654026A (en) * | 1979-10-09 | 1981-05-13 | Murata Manufacturing Co | Grain boundary insulating type semiconductor porcelain composition |
-
1990
- 1990-03-30 JP JP2085248A patent/JPH0761895B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52147800A (en) * | 1976-06-03 | 1977-12-08 | Matsushita Electric Ind Co Ltd | Semiconductor ceramic capacitor composite and its method of manufacturing |
| JPS5654026A (en) * | 1979-10-09 | 1981-05-13 | Murata Manufacturing Co | Grain boundary insulating type semiconductor porcelain composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761895B2 (en) | 1995-07-05 |
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