JPH0426102A - Positive characteristic semiconductor magnetic device - Google Patents
Positive characteristic semiconductor magnetic deviceInfo
- Publication number
- JPH0426102A JPH0426102A JP2131531A JP13153190A JPH0426102A JP H0426102 A JPH0426102 A JP H0426102A JP 2131531 A JP2131531 A JP 2131531A JP 13153190 A JP13153190 A JP 13153190A JP H0426102 A JPH0426102 A JP H0426102A
- Authority
- JP
- Japan
- Prior art keywords
- molded
- resistivity
- positive characteristic
- characteristic semiconductor
- voltage
- 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.)
- Pending
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 24
- 238000002156 mixing Methods 0.000 abstract description 10
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 9
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 229940093474 manganese carbonate Drugs 0.000 abstract description 2
- 235000006748 manganese carbonate Nutrition 0.000 abstract description 2
- 239000011656 manganese carbonate Substances 0.000 abstract description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000008188 pellet Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011572 manganese Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical group [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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、ある温度範囲で抵抗が正の温度係数を示す正
特性半導体磁器に関するものであって、詳しくは、Ｂａ
ＴｉＯ３とＳｒＴｉＯ３とを基本組成とするものにおい
て、室温抵抗率、抵抗変化幅、抵抗率の電圧依存性及び
耐電圧などを向上させた正特性半導体磁器に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to positive characteristic semiconductor porcelain whose resistance exhibits a positive temperature coefficient in a certain temperature range.
The present invention relates to a positive characteristic semiconductor porcelain whose basic composition is TiO3 and SrTiO3 and which has improved room temperature resistivity, resistance change width, voltage dependence of resistivity, withstand voltage, etc.
チタン酸バリウム（ＢａＴｉＯコ）を主成分とする磁器
は、希土類元素の微量添加により半導体化すると共に、
ある温度範囲で抵抗温度係数が正となって温度上昇に従
い電気抵抗率が大幅に増大するという ＰＴＣ現象を示
すことが知られている。Porcelain whose main component is barium titanate (BaTiO) can be made into a semiconductor by adding trace amounts of rare earth elements, and
It is known that the PTC phenomenon occurs, in which the temperature coefficient of resistance becomes positive within a certain temperature range and the electrical resistivity increases significantly as the temperature rises.
このような特異な性質を有する正特性半導体磁器は、様
々な方面への利用が可能と考えられており、実用化を図
るべく、緒特性の改善が従来より試みられている。It is believed that positive characteristic semiconductor ceramics having such unique properties can be used in a variety of fields, and attempts have been made to improve their properties in order to put them into practical use.
正特性半導体磁器を実用に供し得るだめの条件はいろい
ろあるが、
■室温抵抗率が小さいこと
■抵抗変化幅が大きいこと
■抵抗率の電圧依存性が少ないこと
■耐電圧が大きいこと
の４つの特性に優れていることが条件として挙げられる
。There are various conditions for putting positive characteristic semiconductor porcelain into practical use, but there are four: - Low room temperature resistivity - Large range of resistance change - Little dependence of resistivity on voltage - High withstand voltage One of the conditions is that it has excellent characteristics.
正特性半導体磁器の室温抵抗率を小さくする手段として
は、特公昭４４−２７４１８号公報に記載の技術がある
。これは、ＢａＴｉＯ３に適当量のＡ１２０コ、 Ｔｉ
Ｃｈ及び５ｉＯｚを組み合わせて配合することにより、
室温抵抗率を低い値に制御するというものである。As a means for reducing the room temperature resistivity of positive characteristic semiconductor ceramics, there is a technique described in Japanese Patent Publication No. 44-27418. This is an appropriate amount of A120 and Ti for BaTiO3.
By combining Ch and 5iOz,
The purpose is to control the room temperature resistivity to a low value.
また特開昭４９−８９１９８号公報には、ＢａＴｉＯ３
とＳｒＴｉＯ３とを基本組成とし、これにＭｎを含有さ
せた半導体磁器に、Ｂｉ （ビスマス）又はＬａ （ラ
ンタン）の−方とＷｂ （ニオブ）又はＴａ （タンタ
ル）の一方とをそれぞれ等モル量配合することにより、
室温抵抗率を低下させることが記載されている。さらに
特開昭５１−３６５９５号公報には、ＢａＴｉＯ３にＳ
ｒ、 Ｔａ、 Ｍｎ。Moreover, in Japanese Patent Application Laid-open No. 49-89198, BaTiO3
SrTiO3 and SrTiO3 are the basic composition, and Mn is added to the semiconducting porcelain, and one of Bi (bismuth) or La (lanthanum) and one of Wb (niobium) or Ta (tantalum) are blended in equimolar amounts, respectively. By doing so,
It is described that it reduces room temperature resistivity. Furthermore, in Japanese Patent Application Laid-Open No. 51-36595, S
r, Ta, Mn.
Ｓｔを含有させることにより、室温における抵抗率の低
い正特性半導体磁器を提供できると述べられている。It is stated that by containing St, it is possible to provide a positive characteristic semiconductor ceramic having low resistivity at room temperature.
抵抗変化幅の増大化を図るための技術として、特公昭４
１−１２１４６号公報に、１ｌａＴｉｏｓにＮｄ （ネ
オジウム）とＭｎとを配合することが開示されている。As a technology for increasing the resistance change width,
1-12146 discloses that 1laTios is blended with Nd (neodymium) and Mn.
また特公昭５１−．１１４４０号公報には、ＢａＴｉＯ
３を基本組成とする半導体磁器にＮｂ及びＭｎを配合す
ることが、特開昭４７−４３９９６号公報には、基本組
成がｒｌａＴｉｏａの半導体磁器に？ｌｉ、量のＤｙ
（ディスプロシウム）及びＭｎを配合することがそれぞ
れ記載されている。Also, special public service 51-. No. 11440 discloses BaTiO
JP-A-47-43996 discloses that Nb and Mn are blended into semiconductor porcelain whose basic composition is rlaTioa. li, quantity Dy
(Dysprosium) and Mn are respectively described.
抵抗率の電圧依存性、つまり印加電圧の増加に伴って抵
抗率が低下するというバリスタ効果を小さくすると共に
耐電圧を高めるための手段とじては、特公昭５５−４２
４４２号公報に、ＢａＴｉαを基本組成とする半導体磁
器にＮｂ＋ Ｍｎ及びＳｉを配合することが開示されて
いる。A means to reduce the voltage dependence of resistivity, that is, the varistor effect in which resistivity decreases as the applied voltage increases, and to increase withstand voltage is disclosed in Japanese Patent Publication No. 55-42.
No. 442 discloses blending Nb+Mn and Si into semiconductor porcelain whose basic composition is BaTiα.
上述したように、正特性半導体磁器の特性改善のため、
従来、様々な試みがなされてきたが、実用に供するには
、さらに緒特性の向上を図ることが望まれている。具体
的な数値を挙げれば、室温抵抗率が１００Ω・口未満、
抵抗変化幅が６桁以上で例えば５０Ｖ／ｍ領の直流電圧
印加時における抵抗変化幅が少なくとも４桁以上を維持
すると共に、耐電圧は１５０Ｖ／ｍ−以上という特性値
を同時に満足することである。室温抵抗率が高いと、室
温下における低電圧での使用が困難になる。抵抗変化幅
、特に電圧印加時の抵抗変化幅が小さいと、高い印加電
圧下で使用した場合に電流値を低下させるスイッチング
機能が充分に発揮されない、のみならず、自己発熱によ
り、抵抗温度係数が負に変化する温度ｍ域へ容易に達し
、過電流が流れて熱破壊を招く。さらに、耐電圧が低い
と、使用態様が限定され、利用範囲が狭くなる。As mentioned above, in order to improve the characteristics of positive characteristic semiconductor porcelain,
Various attempts have been made in the past, but in order to put them into practical use, it is desired to further improve the strength characteristics. To give specific numbers, the room temperature resistivity is less than 100 Ω.
The resistance change width is 6 digits or more, for example, when a DC voltage in the 50 V/m range is applied, the resistance change width is at least 4 digits or more, and the withstand voltage is 150 V/m or more. . High room temperature resistivity makes it difficult to use at low voltages at room temperature. If the width of resistance change, especially the width of resistance change when voltage is applied, is small, not only will the switching function to reduce the current value not be fully demonstrated when used under high applied voltage, but also the temperature coefficient of resistance will decrease due to self-heating. It easily reaches the temperature range m where it changes negatively, causing overcurrent to flow and causing thermal breakdown. Furthermore, if the withstand voltage is low, the manner of use is limited and the range of use is narrowed.
このような観点から従来技術をみた場合、いずれも前記
条件の全てを同時に満足するものではなかった。前掲の
先願公報のうちのい（つかには、室温抵抗率が１００Ω
・ｃｍ未満であって、且つ抵抗変化幅（電圧非印加時）
が６桁以上の値を示すものが記載されている。しかし、
そのような先願公報において、抵抗率の電圧依存性やバ
リスタ効果及び耐電圧について検討が全くなされていな
い。When looking at the prior art from this point of view, none of the prior art satisfies all of the above conditions at the same time. One of the above-mentioned earlier publications (one of them has a room temperature resistivity of 100Ω).
・Less than cm and resistance change width (when no voltage is applied)
is described as having a value of 6 digits or more. but,
In such prior publications, there is no study at all about voltage dependence of resistivity, varistor effect, and withstand voltage.
他方、特公昭５５−４２４４２号公報に記載された技術
は、電圧依存性を考」Ｆしているものの、電圧印加時の
Ｉｆ、抗変化幅の値が余り大きくないので、実用性に乏
しい。On the other hand, although the technique described in Japanese Patent Publication No. 55-42442 takes voltage dependence into consideration, it is not very practical because the values of If and resistance variation width when voltage is applied are not very large.
いずれにしても、従来の技術は、正特性半導体磁器を実
用化するための前記条件を到底満たすものではなかった
。In any case, the conventional techniques have not completely satisfied the above-mentioned conditions for putting positive characteristic semiconductor porcelain into practical use.
本発明は、小さい室温抵抗率１大きい抵抗変化幅、少な
い電圧依存性及び高い耐電圧を同時に発揮する正特性半
導体磁器の提供を目的とするものであって、その特徴と
するところは、基本組成がＢａＴｉＯ３と５ｒＴｉＯａ
とからなり、これにＴ ｉ ０２ ＋ Ｓ ｉ Ｏｚ＾
１２０３及びＭｎＯ２を含有させた半導体磁器において
、Ｙ（イツトリウム）及びＳｂが配合されていることで
ある。The present invention aims to provide a positive characteristic semiconductor porcelain that simultaneously exhibits a small room temperature resistivity, a large resistance change width, a small voltage dependence, and a high withstand voltage. is BaTiO3 and 5rTiOa
This consists of T i 02 + S i Oz^
In the semiconductor porcelain containing 1203 and MnO2, Y (yttrium) and Sb are blended.
ＢａＴｉＯ３及び５ｒＴｉＯａを基本組成とする正特性
半導体磁器において、Ｔ ｉ Ｏｆ ＋ Ｓ ｔ ０２
＋＾１２０３及びＭｎＯ２を含をさせる量を適当に調
節することにより、室温抵抗率を１００Ω・ｃｍ未隅に
小さくできると共に、抵抗変化幅をある程度まで大きく
することが可能である。In positive characteristic semiconductor porcelain whose basic composition is BaTiO3 and 5rTiOa, T i Of + S t 02
By appropriately adjusting the amounts of +^1203 and MnO2, it is possible to reduce the room temperature resistivity to less than 100 Ω·cm and to increase the range of resistance change to a certain extent.
上記組成の半導体磁器に微量のＹ及びＳｂを配合するこ
とにより、室温抵抗率の値を小さく維持したまま、抵抗
変化幅をより増大させ、その上、抵抗率の電圧依存性を
小さくでき且つ高い耐電圧を達成することが可能である
。Ｙ又はＳｂの何れか一方を配合することにより、室温
抵抗率を小さくしたり抵抗変化幅を増大させたりできる
ことは知られている。しかしながら、ＹとＳｂとを組み
合わせて配合したことにより、抵抗率の電圧依存性すな
わちバリスタ効果を小さくできると共に耐電圧を高くで
きるという予想外の作用が営まれる。その理由の詳細は
不明であるが、Ｙ及びＳｂを適量配合した正特性半導体
＆ＰＬ器の微細構造を観察したところ、結晶粒子の粒径
の分布範囲が狭く、しかも平均粒径が小さいという事実
が判明した。一般に、正特性半導体磁器において、粒径
が小さく均一であるほど、耐電圧が高く、抵抗率の電圧
依存性の小さいことが知られている。従って、Ｙ及びＳ
ｂの組合せは、正特性半導体磁器における結晶生成メカ
ニズムに何らかの影響を及ぼして、結晶構造を好ましい
状態にするものと推測される。By blending a small amount of Y and Sb into the semiconductor porcelain having the above composition, the range of resistance change can be increased while keeping the value of room temperature resistivity small, and in addition, the voltage dependence of resistivity can be made small and high. It is possible to achieve withstand voltage. It is known that by incorporating either Y or Sb, the room temperature resistivity can be lowered or the resistance change range can be increased. However, the combination of Y and Sb has the unexpected effect of reducing the voltage dependence of resistivity, that is, the varistor effect, and increasing the withstand voltage. The details of the reason are unknown, but when we observed the microstructure of a positive temperature semiconductor and PL device containing appropriate amounts of Y and Sb, we found that the distribution range of crystal grain sizes was narrow and the average grain size was small. found. It is generally known that in positive characteristic semiconductor ceramics, the smaller and more uniform the grain size, the higher the withstand voltage and the smaller the voltage dependence of resistivity. Therefore, Y and S
It is presumed that the combination b exerts some influence on the crystal formation mechanism in positive characteristic semiconductor ceramics to bring the crystal structure into a favorable state.
以下、本発明の詳細を実施例に基づいて説明する。 Hereinafter, details of the present invention will be explained based on examples.
始めに、本発明に係る正特性半導体磁器の！Ｉｉ！Ｉ造
手順を述べる。本発明に係る正特性半導体磁器の製造原
料として、高純度のＢａＣ０ａ、 Ｔｉ０ｚ、 ＳｒＣ
Ｏ３゜Ａ１２０ａ、 ５ｉＯｚ、 硝酸マンガン（又は
炭酸マンガン）Ｓｂ２０ｓ、 Ｙ２０３を用いる。上
記原料を、所定分量ずつ計量したのち、樹脂ボットミル
で湿式混合を２０時間行う。これを乾燥したのち、加圧
成形し又は成形せずに、大気中にて焼成温度１１５０℃
で仮焼する。この仮焼物を粗砕後、上記ボットミルで２
０時時間式粉砕する。得られた粉砕物にバインダーとし
てＰＶＡを添加したのち、スプレードライヤーで造粒し
た顆粒を、１００１００Ｏ／−の圧力で直径２０ｍｍ厚
さ２１■のベレットに成形する。Firstly, the positive characteristic semiconductor porcelain according to the present invention! Ii! The I-building procedure will be described. High purity BaC0a, Ti0z, SrC are used as raw materials for producing the positive characteristic semiconductor porcelain according to the present invention.
O3°A120a, 5iOz, manganese nitrate (or manganese carbonate) Sb20s, and Y203 are used. After measuring the above raw materials in predetermined amounts, wet mixing is performed in a resin bot mill for 20 hours. After drying this, it is baked at a temperature of 1150℃ in the atmosphere with or without pressure molding.
Calculate it. After coarsely crushing this calcined material, use the above bot mill for 2
0 o'clock time type crushing. After adding PVA as a binder to the obtained pulverized product, the granules were granulated using a spray dryer and formed into pellets with a diameter of 20 mm and a thickness of 21 cm under a pressure of 100,100 O/-.
次に、成形された成形物を、１３５０℃まで昇温しで１
時間保持し、しかる後、６０℃／時の速度で降温する。Next, the molded product was heated to 1350°C and
The temperature is maintained at a rate of 60° C./hour.
このようにして得られた焼成体の両面にオーミック性銀
電極を焼き付け、諸特性の測定及び内部の微細構造の観
察を行った。Ohmic silver electrodes were baked on both sides of the fired body thus obtained, and various properties were measured and the internal microstructure was observed.
測定した特性は、室温抵抗率、電圧非印加時における室
温と２００°Ｃとの抵抗変化幅、電場強度５０Ｖ／ｍｕ
の直流電圧を印加した時の室温と２００℃との抵抗変化
幅、及び耐電圧である。上記抵抗変化幅は、室温の抵抗
率と２００℃の抵抗率との比率の対数で表したものであ
って、すなわち、抵抗変化幅を甲、室温抵抗率をＰ。、
２００℃における抵抗率をＰ、とすると、甲−１ａｇ
（Ｐ＋ ／ ｐａ ）で表される。また、耐電圧は、交
流電圧を印加して、破壊に至ったときの電場強度を測定
したものである。なお測定時の室温は約２５℃であった
。The measured characteristics were room temperature resistivity, resistance change width between room temperature and 200°C when no voltage was applied, and electric field strength of 50 V/mu.
These are the resistance change range between room temperature and 200° C. when a DC voltage of 200° C. is applied, and the withstand voltage. The above resistance change width is expressed as the logarithm of the ratio between the resistivity at room temperature and the resistivity at 200°C, that is, the resistance change width is A and the room temperature resistivity is P. ,
If the resistivity at 200°C is P, then A-1ag
It is expressed as (P+/pa). Furthermore, the withstand voltage is measured by applying an alternating current voltage and measuring the electric field strength when breakdown occurs. Note that the room temperature at the time of measurement was about 25°C.
本実施例において特性測定に供した正特性半導体磁器の
組成は、ＢａＴｉＯ３，ＳｒＴｉＯ３，Ｔｉ０ｚ、 ５
ｉＯｚＡ１２０ｓ、 ＭｎＯをそれぞれモル比で、８０
： ２０ ： ０．３：＋、５：ｏ、５：ｏ、ｏｓの
割合で含有するものであって、これに５ｂ２０３及びＹ
２Ｏ３を比率を変えて配合したものである。The composition of the positive characteristic semiconductor porcelain used for characteristic measurement in this example was BaTiO3, SrTiO3, Ti0z, 5
The molar ratio of iOzA120s and MnO was 80
: 20 : Contains in the ratio of 0.3: +, 5: o, 5: o, os, and 5b203 and Y
It is a mixture of 2O3 in different ratios.
始メニ、Ｙ ２０３ヲ０．１５．５ｂ２０３を０．０５
（７）比率で配合して製造した複数個の正特性半導体磁
器のうちから、任意に選んだ一個の製品について測定し
た抵抗温度特性（電圧非印加時）のグラフを、第１図に
示す、この正特性半導体磁器は、室温（約２５℃）にお
ける抵抗率が約３８Ω・ｃｍ、２００ ’Ｃにおける抵
抗率が約６．４ Ｘ １０８Ω・ｃｒａであり、抵抗変
化幅は７桁を超えている。なお、キュリー点は約４２℃
、最小抵抗率の１０倍と１００倍の２点間の抵抗温度係
数は約１３．４％／℃であり、室温で使用した場合、ス
イッチング素子として所要の機能を発揮するものである
。First menu, Y 203 wo 0.15.5b203 0.05
(7) Figure 1 shows a graph of the resistance-temperature characteristics (when no voltage is applied) measured for one product arbitrarily selected from a plurality of positive characteristic semiconductor porcelains manufactured by mixing the ratios. This positive characteristic semiconductor porcelain has a resistivity of approximately 38 Ω・cm at room temperature (approximately 25 degrees Celsius), a resistivity of approximately 6.4 x 108 Ω・cra at 200'C, and a resistance change range of over 7 digits. . In addition, the Curie point is approximately 42℃
The temperature coefficient of resistance between two points, 10 times and 100 times the minimum resistivity, is about 13.4%/°C, and when used at room temperature, it exhibits the required function as a switching element.
次に、５ｂ２０３及びＹ２Ｏ３の配合比率をいろいろ変
えて製造した正特性半導体磁器において諸特性を測定し
た結果を、第１表及び第２表に示す。表中の数値は、同
一組成の製品５個について得られた測定値を平均したも
のである。なお、同表における５ｂ２０３とＹ２Ｏ３の
配合量の値は、ＢａＴｉＯ３及び５ｒＴｉＯａからなる
基本組成を１００とした場合の、これに対するモル比で
表した数値である。また、キュリー点は約４０℃で、製
品間で数値の大きな変ＩＪ＋は無かった。Next, Tables 1 and 2 show the results of measuring various properties of positive characteristic semiconductor porcelains manufactured with various blending ratios of 5b203 and Y2O3. The numerical values in the table are the average of the measured values obtained for five products of the same composition. Note that the values of the blending amounts of 5b203 and Y2O3 in the same table are numerical values expressed as molar ratios with respect to the basic composition consisting of BaTiO3 and 5rTiOa, which is set to 100. In addition, the Curie point was approximately 40°C, and there was no large change in IJ+ between the products.
（以下余白）
第
表
第
表
第１表かられかるように、Ｓｂ及びＹを共Ｇこ配合した
正特性半導体磁器のうち、試番２〜８しこ掲”たものは
、１００Ω・ｃｍ未満の低い室’ｔ＝ ｔｆｆｉ抗率を
有し、抵抗変化幅は電圧非印加時において６桁以」二、
電圧印加時においても４乃至５桁以上の大きい値を示す
と共に、耐電圧は１５０Ｖ／■Ｉ以上の優れた値を示し
ている。これに対し、第２表から明らかなように、Ｓｂ
又はＹの一方のみを配合した場合には、室温抵抗率が１
００Ω・値よりも高かに大きかったり（賦香１２参照）
、室温抵抗率の値が小さくても耐電圧に劣っていたり
（賦香１３〜１５参照）、抵抗変化幅が小さかったり（
試番１７参照）しており、前述した実用化するための条
件を満足するものではない、なお、賦香１１及び１６は
、製品が半導体化しなかったため、各特性の測定が不可
能であったものである。(Left below) As shown in Table 1, among the positive characteristic semiconductor porcelains containing both Sb and Y, sample numbers 2 to 8 had a resistance of less than 100 Ω・cm. It has a low resistivity of t = tffi, and the resistance change width is more than 6 orders of magnitude when no voltage is applied.
Even when voltage is applied, it shows a large value of 4 to 5 orders of magnitude or more, and the withstand voltage shows an excellent value of 150 V/I or more. On the other hand, as is clear from Table 2, Sb
Or, if only one of Y is blended, the room temperature resistivity is 1
00Ω・It is higher than the value (see Fuka 12)
, even if the room temperature resistivity value is small, the withstand voltage is poor.
(Refer to 13 to 15), the resistance change range is small (
(Refer to Trial No. 17), which does not satisfy the conditions for practical use as described above.In addition, it was impossible to measure each characteristic of Fuka 11 and 16 because the products were not made into semiconductors. It is something.
ところで、Ｓｂ及びＹの配合量は、多ずぎても少なすぎ
ても所要の特性を備えた正特性半導体磁器を得ることは
できない。このことは、第１表の試番１及び９．１０よ
り理解される。すなわち、Ｓｂ２αとＹ２Ｏ３の配合量
合計が０．１０ ｍｏｌ以下では半導体化が難しくなり
、５ｂ２０３が０．１５ ｍｏ１以上で且つ配合量合計
が０．２５ ｍｏ１以上では、室温抵抗率が高くなる。By the way, if the blending amounts of Sb and Y are too large or too small, it is not possible to obtain a positive characteristic semiconductor ceramic having the required characteristics. This can be understood from trial numbers 1 and 9.10 in Table 1. That is, if the total amount of Sb2α and Y2O3 is less than 0.10 mol, it becomes difficult to make it into a semiconductor, and if the total amount of 5b203 is 0.15 mol or more and the total amount of 5b203 is 0.25 mol or more, the room temperature resistivity becomes high.
従って、本実施例における好ましい５ｂ２０３及びＹ２
Ｏ３の配合量の範囲は、両者の合計が０．１０ｍｏｌを
超え０．２５ ｍｏｌ以下であって、両者の合計が０．
２５１１０１の場合にはＳｔ＋＋Ｏａが０．１５ ｍｏ
１未満であることと言える。但し、この配合量は、その
他の組成、つまり基本組成を構成するＢａＴｉＯ３とＳ
ｒＴ、ｉ０３との比率や、これに含有されるＴ ｉ ０
２ 、 Ｓ ｉ Ｏｚ 、八１２０３Ｍｎ０の割合など
に応じて、最適な範囲が選択される。Therefore, preferred 5b203 and Y2 in this example
The range of the blended amount of O3 is such that the total of both exceeds 0.10 mol and is 0.25 mol or less, and the total of both exceeds 0.10 mol and is 0.25 mol or less.
In the case of 251101, St++Oa is 0.15 mo
It can be said that it is less than 1. However, this blending amount is based on the other compositions, that is, BaTiO3 and S, which constitute the basic composition.
The ratio of rT and i03 and the T i 0 contained therein
The optimum range is selected depending on the ratio of 2, S i Oz, 81203Mn0, etc.
ところで、抵抗率の電圧依存性や耐電圧などの特性は、
正特性半導体磁器を構成する結晶粒子の粒径や粒度分布
と密接な関係を持っていることが知られている。そこで
、本発明に係る正特性半導体磁器と従来製品とについて
、微細構造を観察し、粒径の分布範囲と平均粒径とにつ
いて調査したところ、次のような事実が判明した。すな
わち、従来製品は、平均粒径が約１５〜４０珈であった
のに対し、本発明品は平均粒径が６〜１５Ｊ４と極めて
小さく、粒径の分布範囲が狭く均一であった。一般に、
粒径が小さく均一である方が、バリスタ効果が小さく耐
電圧が高いことは知られている。従って、微細構造の観
察からも、本発明の優れた特性が裏付けられる。By the way, characteristics such as voltage dependence of resistivity and withstand voltage are
It is known that there is a close relationship with the grain size and grain size distribution of the crystal grains that make up positive characteristic semiconductor porcelain. Therefore, the microstructures of the positive characteristic semiconductor porcelain according to the present invention and conventional products were observed, and the grain size distribution range and average grain size were investigated, and the following facts were found. That is, while the conventional product had an average particle size of about 15 to 40 ka, the product of the present invention had an extremely small average particle size of 6 to 15 J4, and the particle size distribution range was narrow and uniform. in general,
It is known that the smaller and more uniform the particle size, the smaller the varistor effect and the higher the withstand voltage. Therefore, observation of the microstructure also supports the excellent characteristics of the present invention.
なお本発明の実施例は、前述したちの以外に、基本組成
を構成するＢａとＳｒとの比率を変えることによりキュ
リー点を移動させたり、Ｔｉ、 Ｓｉ、 ＡｌＭｎの含
有率を変えることにより、例えば抵抗温度係数の値を加
減する等の、実施の態様に応じた変更を妨げるものでは
ない。In addition to the above-mentioned methods, the embodiments of the present invention can move the Curie point by changing the ratio of Ba and Sr that constitute the basic composition, and by changing the content of Ti, Si, and AlMn. This does not preclude changes depending on the embodiment, such as adjusting the value of the temperature coefficient of resistance.
本発明は、１ｌａＴｉｏａ及びＳｒＴｉＯ３を基本組成
とし、これにＴ ｉ ０２ 、 Ｓ ｉ Ｏｚ 、八１
２０３及びＭｎＯを含有させた半導体磁器に、さらにＹ
及びＳｂを配合したことにより、室温抵抗率が１００Ω
・０未満の小さい値であって、抵抗変化幅が電圧非印加
時においては６桁以上の値を示すと共に、抵抗率の電圧
依存性が小さく、その上、少なくとも１５０Ｖ／＊■以
上の面１電圧を備えた正特性半導体磁器を製造すること
ができる。従って、本発明によれば、従来に増して実用
性に優れた正特性半導体磁器を提供することが可能であ
り、利用可能範囲の拡大を図ることができる。The present invention has a basic composition of 1laTioa and SrTiO3, in which T i 02 , S i Oz , 81
In addition to the semiconductor porcelain containing 203 and MnO, Y
By incorporating Sb and Sb, the room temperature resistivity is 100Ω.
・A surface 1 with a small value less than 0, a resistance change width of 6 digits or more when no voltage is applied, a small voltage dependence of resistivity, and at least 150 V/*■ Positive characteristic semiconductor porcelain with voltage can be produced. Therefore, according to the present invention, it is possible to provide positive characteristic semiconductor porcelain that is more practical than ever before, and it is possible to expand the usable range.
第１図は、本発明の一実施例に係る正特性半導体磁器の
抵抗温度特性を示すグラフである。
特許出願人 株式会社 イ す ソ り ス出願代理人
弁理士 内 田敏彦FIG. 1 is a graph showing the resistance temperature characteristics of a positive characteristic semiconductor ceramic according to an embodiment of the present invention. Patent Applicant Isu Risu Co., Ltd. Application Agent Patent Attorney Toshihiko Uchida
Claims (1)
なり、これにＴｉＯ＿２，ＳｉＯ＿２，Ａｌ＿２Ｏ＿３
及びＭｎＯ＿２を含有させた半導体磁器において、Ｙ及
びＳｂが配合されていることを特徴とする正特性半導体
磁器。1. The basic composition consists of BaTiO_3 and SrTiO_3, in addition to which TiO_2, SiO_2, Al_2O_3
A positive characteristic semiconductor porcelain characterized by containing Y and Sb in the semiconductor porcelain containing MnO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131531A JPH0426102A (en) | 1990-05-21 | 1990-05-21 | Positive characteristic semiconductor magnetic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131531A JPH0426102A (en) | 1990-05-21 | 1990-05-21 | Positive characteristic semiconductor magnetic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0426102A true JPH0426102A (en) | 1992-01-29 |
Family
ID=15060253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131531A Pending JPH0426102A (en) | 1990-05-21 | 1990-05-21 | Positive characteristic semiconductor magnetic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0426102A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312790A (en) * | 1993-06-09 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | Ceramic ferroelectric material |
-
1990
- 1990-05-21 JP JP2131531A patent/JPH0426102A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312790A (en) * | 1993-06-09 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | Ceramic ferroelectric material |
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