JPH0442501A - Electronic device using barium titanate based semiconductor porcelain - Google Patents
Electronic device using barium titanate based semiconductor porcelainInfo
- Publication number
- JPH0442501A JPH0442501A JP2150517A JP15051790A JPH0442501A JP H0442501 A JPH0442501 A JP H0442501A JP 2150517 A JP2150517 A JP 2150517A JP 15051790 A JP15051790 A JP 15051790A JP H0442501 A JPH0442501 A JP H0442501A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- electrode
- barium titanate
- based semiconductor
- semiconductor porcelain
- 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 31
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 21
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910000679 solder Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 1
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、正の抵抗温度特性を示すチタン酸バリウム系
半導体磁器を用いた電子部品に関し、特に、半導体磁器
上に形成される電極が改良された電子部品に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to electronic components using barium titanate-based semiconductor porcelain that exhibits positive resistance-temperature characteristics, and in particular, to an electronic component using barium titanate-based semiconductor porcelain that exhibits positive resistance-temperature characteristics. related to electronic components.
チタン酸バリウム系半導体磁器はチタン酸バリウムを主
成分とし、これに半導体化剤としてＹ、Ｌａ、Ｃｕ等の
希土類元素、Ｎｂ、Ｂ ｉ、Ｓｂ。Barium titanate-based semiconductor porcelain has barium titanate as its main component, and rare earth elements such as Y, La, and Cu, Nb, Bi, and Sb as semiconducting agents.
Ｔａ、■、ＷまたはＴｈ等のうち少なくとも１種以上を
０．０３〜１．０モル％含有させた組成を有し、抵抗急
変点（キュリー点）を超えると著しい正の抵抗温度変化
を示すという特徴を有する。It has a composition containing 0.03 to 1.0 mol% of at least one of Ta, ■, W, Th, etc., and exhibits a significant positive resistance temperature change when the resistance abrupt change point (Curie point) is exceeded. It has the following characteristics.
通常、主成分であるチタン酸バリウムの影響により、チ
タン酸バリウム系半導体磁器のヰユリ−点は、はぼ１２
０℃付近にある。Normally, due to the influence of barium titanate, which is the main component, the Uri point of barium titanate semiconductor porcelain is around 12
It is around 0℃.
チタン酸バリウム系半導体磁器のキュリー点を高温側に
移行させるために、Ｂａの一部をｐｂで置換することが
知られている。他方、キュリー点を低温側へ移行させる
ために、Ｂａの一部をＳｒで置換したり、Ｔｉの一部を
ＺｒまたはＳｎ等で置換したりすることも知られている
。In order to shift the Curie point of barium titanate-based semiconductor ceramics to a high temperature side, it is known to replace a portion of Ba with Pb. On the other hand, in order to shift the Curie point to a lower temperature side, it is also known to replace a portion of Ba with Sr, or replace a portion of Ti with Zr, Sn, or the like.
さらに、チタン酸バリウム系半導体磁器に、マンガンを
ＭｎＯ，に換算して０．０５〜０．１０モル％添加する
ことにより、キュリー点を超えた温度域における抵抗温
度変化率を著しく大きくし得ることも知られている。ま
た、Ｓｉｎ、を０゜０２〜５モル％添加することにより
、常温における比抵抗を低くすると共に、安定したもの
とし得ることも知られている。Furthermore, by adding 0.05 to 0.10 mol% of manganese (converted to MnO) to barium titanate-based semiconductor porcelain, the rate of change in resistance with temperature in the temperature range exceeding the Curie point can be significantly increased. is also known. It is also known that by adding 0.02 to 5 mol% of Sin, the resistivity at room temperature can be lowered and stabilized.
〔発明が解決しようとする技術的課題〕しかしながら、
上述したようなチタン酸バリウム系半導体磁器において
、１０Ω・口取下の低比抵抗の磁器を得ようとした場合
、耐破壊電圧が著しく低下するという問題があった。ま
た、素子の厚みを薄くした場合には、素子の両生面にＡ
ｇを主体とする電極を形成すると、Ａｇのマイグレーシ
ョン等により特性が劣化するという問題があった。他方
、マイグレーションを防止するために、Ｎｉ −Ａｇの
二層構造の電極を形成した場合には、加工変化が太き（
なるという問題もある。[Technical problem to be solved by the invention] However,
In the barium titanate-based semiconductor porcelain as described above, when attempting to obtain a porcelain with a low specific resistance of 10 Ω/cut, there was a problem in that the breakdown voltage was significantly lowered. In addition, when the thickness of the element is made thinner, A
When an electrode mainly composed of Ag is formed, there is a problem that the characteristics deteriorate due to migration of Ag and the like. On the other hand, when forming an electrode with a Ni-Ag double-layer structure to prevent migration, processing changes are large (
There is also the issue of becoming.
よって、本発明の目的は、より低抵抗であり、かつ優れ
た耐破壊電圧特性を示し、また加工変化が小さく、負荷
寿命試験に対しても優れた特性を示す、チタン酸バリウ
ム系半導体磁器を用いた電子部品を提供することにある
。Therefore, the object of the present invention is to provide barium titanate-based semiconductor porcelain that has lower resistance, exhibits excellent breakdown voltage characteristics, has small processing changes, and exhibits excellent characteristics in load life tests. The objective is to provide electronic components using
〔技術的課題を解決するための手段及び作用〕本発明の
チタン酸バリウム系半導体磁器を用いた電子部品は、主
成分がＢａＴｉ０．を３０〜９５モル％、ＣａＴｉＯ３
を３〜２５モル％、ＳｒＴ ｉ Ｏｘを１〜３０モル％
及びＰ ｂ Ｔ ｉ Ｏｓを１〜５０モル％含む組成か
らなり、半導体化剤として希土類元素またはＮｂ、Ｔａ
、Ｖ、Ｓｂ、Ｂｉ、Ｗ、Ｔｈ、ＭｏもしくはＣｒのうち
少なくとも１種を０．００１〜０．４モル％含み、さら
にＭｎを０．００１〜０．１００モル％、ＳｉＯ□を０
゜０１〜５．０モル％含有する組成のチタン酸バリウム
系半導体磁器と、この半導体磁器の表面にスパッタリン
グにより形成されており、かつＣｒ、Ｔｉもしくは、ｌ
またはこれらの合金からなる第１電極と、第１電極上に
スパッタリングにより付与されており、かつ第１電極を
構成する材料よりも熱膨張係数が高く、はんだよりも熱
膨張係数の小さい金属または合金よりなる第２電極とを
備えることを特徴とする。[Means and effects for solving the technical problems] The electronic component using the barium titanate semiconductor ceramic of the present invention has BaTi0. 30-95 mol%, CaTiO3
3 to 25 mol%, and 1 to 30 mol% of SrT i Ox
and P b TiOs in an amount of 1 to 50 mol %, and a rare earth element or Nb, Ta as a semiconducting agent.
, V, Sb, Bi, W, Th, Mo or Cr at 0.001 to 0.4 mol %, further contains Mn 0.001 to 0.100 mol %, and SiO
It is formed by sputtering on the surface of barium titanate based semiconductor porcelain having a composition of 01 to 5.0 mol% and containing Cr, Ti or l.
or a first electrode made of an alloy thereof, and a metal or alloy that is applied on the first electrode by sputtering and has a coefficient of thermal expansion higher than that of the material constituting the first electrode and a coefficient of thermal expansion lower than that of solder. It is characterized by comprising a second electrode consisting of.
本発明においてチタン酸バリウム主成分中のＢａＴｉｏ
ｓ含有率を３０〜９５モル％の範囲としたのは、３０モ
ル％未満では半導体化が困難となり、かつ比抵抗が高く
なるからであり、他方、９５モル％を超えると電気的特
性が著しく低下するからである。In the present invention, BaTio in the main component of barium titanate
The reason why the s content is set in the range of 30 to 95 mol% is that if it is less than 30 mol%, it will be difficult to convert it into a semiconductor and the specific resistance will become high.On the other hand, if it exceeds 95 mol%, the electrical properties will be significantly deteriorated. This is because it decreases.
同様に、ＣａＴｉＯｓ含有率を３〜２５モル％の範囲と
したのは、３モル％未満ではその含有効果が現われず、
２５モル％を超えると、耐電圧特性及び耐突入電流特性
の低下をもたらすからであ５ｒＴｉＯ＊含有率を１〜３
０モル％としたのは、１モル％未満では、特性改善効果
が少なく、３０モル％を超えると電気的特性が劣化する
からである。Similarly, the reason why the CaTiOs content is set in the range of 3 to 25 mol% is that the effect of its inclusion is not manifested below 3 mol%.
If it exceeds 25 mol%, the withstand voltage characteristics and inrush current characteristics will deteriorate.
The reason for setting it to 0 mol % is because if it is less than 1 mol %, the effect of improving the characteristics is small, and if it exceeds 30 mol %, the electrical characteristics will deteriorate.
Ｐ ｂ Ｔ ｉ Ｏｓ含有率を１〜５０モル％の範囲と
したのは、１モル％未満では特性改善効果が顕著に現れ
ず実用に適さないからであり、５０モル％を超えると半
導体化が困難となるからである。The reason why the P b TiOs content is set in the range of 1 to 50 mol % is that if it is less than 1 mol %, the property improvement effect will not be noticeable and it is not suitable for practical use, and if it exceeds 50 mol %, semiconductor formation This is because it becomes difficult.
なお、主成分を（Ｂａ、Ｃａ、Ｓｒ、Ｐｂ）Ｔ１０、と
して表したとき、（Ｂａ、Ｃａ、Ｓｒ、Ｐｂ）／Ｔｉの
モル比を０．９９〜１．０３の範囲でずらしても、本発
明の目的を達成し得ることを指摘しておく。In addition, when the main components are expressed as (Ba, Ca, Sr, Pb) T10, even if the molar ratio of (Ba, Ca, Sr, Pb)/Ti is shifted in the range of 0.99 to 1.03, It is pointed out that the objectives of the invention can be achieved.
半導体化剤として希土類元素またはＮｂ、Ｔａ、■、Ｓ
ｂ、 Ｂ ｉ、 Ｗ、 Ｔｈ、 ＭｏもしくはＣｒの
うち少なくとも１種を０．００１〜０．４モル％含有さ
せることとしたのは、０．００１モル％以下では磁器が
半導体化せず、逆に０．４モル％を超えて含有させると
比抵抗が高くなり、本発明の目的を達成できないからで
ある。Rare earth elements or Nb, Ta, ■, S as a semiconducting agent
The reason why it was decided to contain 0.001 to 0.4 mol% of at least one of B, Bi, W, Th, Mo, or Cr is that if it is less than 0.001 mol%, the porcelain will not become a semiconductor, and vice versa. This is because if the content exceeds 0.4 mol %, the specific resistance becomes high and the object of the present invention cannot be achieved.
また、Ｍｎの量を０．００１〜０．１００モル％とした
のは、Ｑ、００１モル％未満では抵抗温度特性が劣化し
、０．１００モル％よりも多く含有させると比抵抗が大
きくなるからである。さらに、Ｓ１０ｗ含有量について
０．０１〜５モル％の範囲としたのは、０．０１モル％
未満では焼結し難（，５モル％を超えて含有させた場合
には高抵抗化してしまうからである。In addition, the reason for setting the amount of Mn to 0.001 to 0.100 mol% is that Q: If it is less than 0.001 mol%, the resistance temperature characteristics will deteriorate, and if it is contained more than 0.100 mol%, the specific resistance will increase. It is from. Furthermore, the range of 0.01 to 5 mol% for S10w content is 0.01 mol%.
If the content is less than 5 mol %, sintering is difficult (and if the content exceeds 5 mol %, the resistance becomes high.
上記の組成を有するチタン酸バリウム系半導体磁器以外
では本発明の目的を達成することはできない、しかしな
がら、上記の組成を有する半導体磁器にＮｉをめっきし
、その上にＡｇペーストを焼き付けて電極を形成した場
合には、加工変化が大きくなる。また、素子の厚みを薄
くするとＡｇのマイグレーラン等により特性が劣化する
。The purpose of the present invention cannot be achieved with anything other than barium titanate-based semiconductor porcelain having the above composition. However, electrodes are formed by plating the semiconductor porcelain having the above composition with Ni and baking Ag paste thereon. In this case, processing changes will be large. Furthermore, when the thickness of the element is reduced, the characteristics deteriorate due to migration of Ag and the like.
そこで、本発明では、上記のような問題を解決するため
に、第１電極として、Ｃｒ、ＴｉもしくはＡｌまたはこ
れらの合金をスパッタリングにより付与して第１電極が
形成されており、該第１１！１極上に、スパッタリング
により熱膨張係数が第１電極材料よりも大きく、はんだ
よりも小さい金属または合金を付与することにより第２
電極が形成されている。Therefore, in the present invention, in order to solve the above problems, the first electrode is formed by applying Cr, Ti, Al, or an alloy thereof by sputtering, and the 11th! By sputtering a metal or alloy whose coefficient of thermal expansion is larger than that of the first electrode material and smaller than that of the solder, the second electrode material is formed by sputtering.
Electrodes are formed.
第２１極を構成する材料としては、例えばＮｉまたはＣ
ｕ等のはんだ付は性の良好な金属またはこれらの合金が
好適に用いられる。The material constituting the 21st pole is, for example, Ni or C.
For soldering such as u, metals with good properties or alloys thereof are preferably used.
本発明では、上記した組成のチタン酸バリウム系半導体
磁器に、上述のような第１電極及び第２電極が形成され
ているため、従来の半導体磁器を用いた電子部品に比べ
て素子の抵抗が低く、優れた耐破壊電圧特性を示し、さ
らに加工変化が小さく、負荷寿命に対して優れた特性を
有する電子部品を構成することができる。In the present invention, since the first electrode and the second electrode as described above are formed on the barium titanate-based semiconductor porcelain having the above-mentioned composition, the resistance of the element is lower than that of electronic components using conventional semiconductor porcelain. It is possible to construct an electronic component that exhibits low and excellent breakdown voltage characteristics, has small processing changes, and has excellent characteristics with respect to load life.
以下、本発明を実施例に従って詳細に説明する。 Hereinafter, the present invention will be explained in detail according to examples.
主成分原料としてＢａＣＯ３、ＣａＣ０，，５ｒｃＯｓ
、Ｐｂｓ Ｏａ及びＴｉｅ、を、半導体化剤原料とし
てＹｔ Ｏｓ 、Ｌａｇ Ｏｓ 、Ｃｅ０ｚ、Ｎｄｇ
Ｏｘ 、Ｓｂｔ Ｏｘ 、Ｂ ｉｔ ０３及びＷ２Ｏ３
、添加物原料としてＭｎＣ０，、ＳｉＯ□等を準備した
。これら各原料を第１表に示す比率で含有する半導体磁
器組成物が得られるように、各原料を配合し、さらに湿
式混合した。BaCO3, CaC0,,5rcOs as main component raw materials
, Pbs Oa and Tie, and Yt Os , Lag Os , CeOz, Ndg as semiconductor forming agent raw materials.
Ox , Sbt Ox , B it 03 and W2O3
, MnC0, SiO□, etc. were prepared as additive raw materials. Each raw material was blended and further wet-mixed so as to obtain a semiconductor ceramic composition containing each of these raw materials in the ratios shown in Table 1.
得られた混合原料を脱水乾燥し、１１５０℃で１時間仮
焼した。次に、仮焼原料を粉砕し、さらにバインダを加
えて造粒し、成形圧力１０００ｋｇ／ｃＩｉで円板状に
成形した。成形された円板を１３２０℃〜１４００℃で
焼成し、直径１７．５ｍ。The obtained mixed raw material was dehydrated and dried, and calcined at 1150° C. for 1 hour. Next, the calcined raw material was pulverized, a binder was added thereto, granulated, and molded into a disk shape at a molding pressure of 1000 kg/cIi. The formed disc was fired at 1320°C to 1400°C and had a diameter of 17.5 m.
厚み０．６ｍの円板状の半導体磁器を得た。A disk-shaped semiconductor porcelain with a thickness of 0.6 m was obtained.
得られた半導体磁器の両生表面にＩｎ−Ｇａ合金からな
る電極材をこすり付け、試料とした。これらの試料につ
いて常温（２５℃）における比抵抗、キュリー点、耐電
圧特性を測定した。測定結果を第２表に示す、上述の各
特性のうち、耐電圧特性は試料に印加する電圧を徐々に
上昇させてゆき、試料の破壊が生じる直前の最高印加電
圧値を示したものである。An electrode material made of an In-Ga alloy was rubbed on the amphiboid surface of the obtained semiconductor porcelain to prepare a sample. The specific resistance, Curie point, and withstand voltage characteristics of these samples at room temperature (25° C.) were measured. The measurement results are shown in Table 2. Among the above-mentioned characteristics, the withstand voltage characteristic shows the maximum applied voltage value immediately before the sample breaks down by gradually increasing the voltage applied to the sample. .
なお、第１表及び第２表において＊を付した試料は本発
明の範囲外の組成の半導体磁器であり、それ以外は、半
導体磁器の組成についてはすべて本発明の範囲内のもの
である。Note that the samples marked with * in Tables 1 and 2 are semiconductor porcelains whose compositions are outside the scope of the present invention, and all other compositions of the semiconductor porcelains are within the scope of the present invention.
第２表より、実施例の試料は、低比抵抗かつ高耐電圧特
性を有することがわかる。From Table 2, it can be seen that the samples of Examples have low resistivity and high withstand voltage characteristics.
（以下、余白）
第
表
（その１）
第
表
（その３）
第
表
（その２）
第
表
（その４）
（以下、
余白）
（その１）
（その３）
第
表
（その２）
第
表
（その４）
次に、試料番号２，３，７．３９及び４４の磁器に無電
解めっき法によりニッケル電極を施し、さらに、この上
に銀ペーストを塗布した後、６００℃の温度で熱処理し
てＮ ｉ Ａ ｇ １ｉ極を形成した素子を得た。(Hereafter, margin) Table (Part 1) Table (Part 3) Table (Part 2) Table (Part 4) (Hereafter, margin) (Part 1) (Part 3) Table (Part 2) Table (Part 4) Next, nickel electrodes were applied to the porcelains of sample numbers 2, 3, 7.39, and 44 by electroless plating, and then silver paste was applied on top of the nickel electrodes, followed by heat treatment at a temperature of 600°C. An element in which a N i A g 1i pole was formed was obtained.
同様に、試料番号２，３，７．３９及び４４の磁器に第
１ｔ８ｉとしてＣｒ、第２電極としてＮｉをスパッタリ
ングにより付与した素子を作製した。Similarly, elements were fabricated in which Cr was applied as the first t8i and Ni was applied as the second electrode to ceramic samples Nos. 2, 3, 7, 39, and 44 by sputtering.
上記のようにして用意した素子試料について、湯中負荷
寿命試験を行った。A hot water load life test was conducted on the element samples prepared as described above.
また、Ｉｎ−ＧａＴｌ極が付与されていた試料との比抵
抗の差（加工変化）を、次式に従って求めた。Further, the difference in resistivity (processing change) with respect to the sample provided with the In-GaTl electrode was determined according to the following formula.
但し、ΔＰ：比抵抗の変化率（％）
ＰＬ ＝計算上束めた比抵抗（Ω・ｃｌｌ）Ｐｔ ：電
極形成後の比抵抗（Ω・ｃｍ）Ｐ、：Ｉｎ−Ｇａ＠極で
の比抵抗（Ω・ｃｍ）湯中負荷寿命試験及び加工変化の
結果を下記の第３表に示す。However, ΔP: Rate of change in specific resistance (%) PL = Calculated specific resistance (Ω・cll) Pt: Specific resistance after electrode formation (Ω・cm) P,: Ratio at In-Ga@pole Resistance (Ω cm) The results of the hot water load life test and processing changes are shown in Table 3 below.
第３表
第３表から明らかなように、Ｎ ｉ −Ａ ｇ電極ヲ形
成した素子試料では、ＮｉとＡｇとの界面に抵抗層が存
在するため、比抵抗を低下させ難いだけでなく、湯中負
荷寿命試験での抵抗値変化率が著しく劣化した。また加
工変化も大きく、実際に使用するのには問題がある。さ
らに、低比抵抗化を図るためには、素子の厚みを薄くす
る必要があるが、このときＡｇのマイグレーション等が
起こる可能性もあり、特性劣化を引き起こす可能性があ
る。Table 3 As is clear from Table 3, in the device sample in which the Ni-Ag electrode was formed, there is a resistance layer at the interface between Ni and Ag, so it is not only difficult to reduce the specific resistance, but also The rate of change in resistance value in the medium load life test deteriorated significantly. Furthermore, the processing changes are large, which poses a problem in actual use. Furthermore, in order to lower the specific resistance, it is necessary to reduce the thickness of the element, but at this time, migration of Ag may occur, which may cause deterioration of characteristics.
これに対して、Ｃｒ−Ｎｉスパッタリングによる電極が
形成された素子試料では、比抵抗値が低く、負荷による
変化も少ない。また、この組成系とのマツチングが良い
ため、加工変化も少ない。On the other hand, an element sample in which electrodes were formed by Cr--Ni sputtering had a low specific resistance value and little change due to load. In addition, since it matches well with this composition system, there are few processing changes.
以上のように、本発明によれば、特定組成の主成分に特
定割合で半導体化剤及び添加物を含有させた組成を有す
るチタン酸バリウム系半導体磁器にＣｒ、Ｔｉもしくは
Ａｆまたはこれらの合金によりなる第１電極、並びに熱
膨張係数が第１電極材料より大きく、はんだより小さい
材料よりなる第２電極がスパッタリングにより形成され
ているので、従来に比べて比抵抗が低く、耐電圧特性に
優れ、さらに負荷寿命試験にも優れ、加工変化が小さい
電子部品を提供することが可能となる。As described above, according to the present invention, barium titanate-based semiconductor porcelain having a composition in which a main component of a specific composition contains a semiconducting agent and an additive in a specific proportion is coated with Cr, Ti, Af, or an alloy thereof. The first electrode is formed by sputtering, and the second electrode is made of a material whose coefficient of thermal expansion is larger than that of the first electrode material and smaller than that of the solder. Furthermore, it is possible to provide electronic components that are excellent in load life tests and have small processing changes.
Claims (1)
ＣａＴｉＯ＿３を３〜２５モル％、ＳｒＴｉＯ＿３が１
〜３０モル％及びＰｂＴｉＯ＿３を１〜５０モル％含む
組成であり、 半導体化剤として、希土類元素またはＮｂ、Ｔａ、Ｖ、
Ｓｂ、Ｂｉ、Ｗ、Ｔｈ、ＭｏもしくはＣｒのうち少なく
とも１種を０．００１〜０．４モル％含み、 Ｍｎを０．００１〜０．１００モル％並びにＳｉＯ＿２
を０．０１〜５モル％含む組成からなるチタン酸バリウ
ム系半導体磁器と、 前記半導体磁器の表面にスパッタリングにより形成され
ており、かつＣｒ、ＴｉもしくはＡｌまたはこれらの合
金からなる第１電極と、 前記第１電極上にスパッタリングにより形成されており
、かつ熱膨張係数が第１電極を構成する材料よりも大き
く、はんだよりも小さい金属または合金からなる第２電
極とを備えるチタン酸バリウム系半導体磁器を用いた電
子部品。(1) The main component is 30 to 95 mol% BaTiO_3,
3 to 25 mol% of CaTiO_3, 1 of SrTiO_3
~30 mol% and 1~50 mol% of PbTiO_3, and as a semiconductor agent, rare earth elements or Nb, Ta, V,
Contains 0.001 to 0.4 mol% of at least one of Sb, Bi, W, Th, Mo, or Cr, 0.001 to 0.100 mol% of Mn, and SiO_2
a barium titanate-based semiconductor ceramic having a composition containing 0.01 to 5 mol% of the semiconductor ceramic; a first electrode formed on the surface of the semiconductor ceramic by sputtering and made of Cr, Ti, Al, or an alloy thereof; a barium titanate-based semiconductor porcelain comprising a second electrode formed on the first electrode by sputtering and made of a metal or alloy whose coefficient of thermal expansion is larger than that of the material constituting the first electrode and smaller than that of the solder; Electronic components using
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2150517A JP2541344B2 (en) | 1990-06-08 | 1990-06-08 | Electronic parts using barium titanate based semiconductor porcelain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2150517A JP2541344B2 (en) | 1990-06-08 | 1990-06-08 | Electronic parts using barium titanate based semiconductor porcelain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0442501A true JPH0442501A (en) | 1992-02-13 |
| JP2541344B2 JP2541344B2 (en) | 1996-10-09 |
Family
ID=15498591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2150517A Expired - Lifetime JP2541344B2 (en) | 1990-06-08 | 1990-06-08 | Electronic parts using barium titanate based semiconductor porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2541344B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| KR20030092720A (en) * | 2002-05-31 | 2003-12-06 | 현대자동차주식회사 | PTC ceramic compound having low electric resistivity |
| JP2008193042A (en) * | 2006-07-28 | 2008-08-21 | Tdk Corp | Laminated thermistor and its manufacturing method |
| JP2014205585A (en) * | 2013-04-11 | 2014-10-30 | ニチコン株式会社 | Semiconductor ceramic composition and method of producing the same |
| JPWO2013065441A1 (en) * | 2011-11-01 | 2015-04-02 | 株式会社村田製作所 | PTC thermistor and method for manufacturing PTC thermistor |
| US9321689B2 (en) | 2008-08-07 | 2016-04-26 | Epcos Ag | Molded object, heating device and method for producing a molded object |
| US9363851B2 (en) | 2008-08-07 | 2016-06-07 | Epcos Ag | Heating device and method for manufacturing the heating device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5410996A (en) * | 1977-06-27 | 1979-01-26 | Mitsubishi Electric Corp | Manufacture of titanium oxide electrode |
| JPS57157502A (en) * | 1981-03-24 | 1982-09-29 | Murata Manufacturing Co | Barium titanate series porcelain composition |
-
1990
- 1990-06-08 JP JP2150517A patent/JP2541344B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5410996A (en) * | 1977-06-27 | 1979-01-26 | Mitsubishi Electric Corp | Manufacture of titanium oxide electrode |
| JPS57157502A (en) * | 1981-03-24 | 1982-09-29 | Murata Manufacturing Co | Barium titanate series porcelain composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| US6187707B1 (en) | 1996-11-20 | 2001-02-13 | Murata Manufacturing Co., Ltd. | Barium titanate-based semiconductive ceramic composition |
| KR20030092720A (en) * | 2002-05-31 | 2003-12-06 | 현대자동차주식회사 | PTC ceramic compound having low electric resistivity |
| JP2008193042A (en) * | 2006-07-28 | 2008-08-21 | Tdk Corp | Laminated thermistor and its manufacturing method |
| US9321689B2 (en) | 2008-08-07 | 2016-04-26 | Epcos Ag | Molded object, heating device and method for producing a molded object |
| US9363851B2 (en) | 2008-08-07 | 2016-06-07 | Epcos Ag | Heating device and method for manufacturing the heating device |
| JPWO2013065441A1 (en) * | 2011-11-01 | 2015-04-02 | 株式会社村田製作所 | PTC thermistor and method for manufacturing PTC thermistor |
| JP2014205585A (en) * | 2013-04-11 | 2014-10-30 | ニチコン株式会社 | Semiconductor ceramic composition and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2541344B2 (en) | 1996-10-09 |
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