JPH039601B2 - - Google Patents
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- Publication number
- JPH039601B2 JPH039601B2 JP56104690A JP10469081A JPH039601B2 JP H039601 B2 JPH039601 B2 JP H039601B2 JP 56104690 A JP56104690 A JP 56104690A JP 10469081 A JP10469081 A JP 10469081A JP H039601 B2 JPH039601 B2 JP H039601B2
- Authority
- JP
- Japan
- Prior art keywords
- atomic
- thermistor
- resistance
- present
- samples
- 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.)
- Expired - Lifetime
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- Magnetic Ceramics (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Description
本発明は、酸化マンガンを主成分とし、特に酸
化ジルコニウムを含有することを特徴とした負の
抵抗温度係数を有するサーミスタ用酸化物半導体
に関するものである。
従来、酸化ジルコニウムを含有し、酸化マンガ
ンを主成分とするサーミスタ用酸化物半導体の組
成としては、Mn−Zr系、Co−Zr系、Ni−Zr系、
Cu−Zr系の２成分系がよく知られている。また、
Mn−Ni−Cu−Zr系の４成分系については、本
発明者らによつて既に提案済み（特願昭54−
145840号＝特公昭60−13285号公報）である。
本発明のサーミスタ組成は、上記先出願特許を
さらに検討した結果、上記先出願特許に匹敵する
組成領域を見いだしたもので、酸化ジルコニウム
微量含有効果として高温直流電圧負荷特性に優れ
る高安定性の材料である。
本発明のサーミスタ組成は、金属元素として
Mn94.6〜60原子％、Ni5〜30原子％、Cu0.1〜10
原子％、Zr0.05〜0.3原子％（但し、0.3原子％は
含まない。）の４種を含有し、これらの合計が100
原子％である。ここで、銅が10原子％を超えると
比抵抗およびＢ定数の低下が著しく、実用上要求
される特性値範囲外となる可能性が高く好ましく
ない。また、Zrの含有量が0.05原子％未満では全
く効果を示さないが、0.05〜0.3原子％の微量で
も効果を示す。この原因については現在検討中で
ある。
以下、実施例を挙げて本発明の内容を説明す
る。まず、市販の原料MnCo3、NiO、ZrO2を後
述する表に示すように配合した。これらの配合組
成物をジルコニアボールを玉石とするボールミル
で湿式混合し、これらのスラリーを乾燥後、800
℃で仮焼し、この仮焼物を乾式粉砕後バインダを
添加混合し、所要量採つて円板状に加圧成形し、
成形品を多数作成した。この成形体を空気中1000
〜1200℃で焼成し、これらの円板状焼結体（（直
径約6.5mm、厚み1.2mm）の両面にAgを主成分とす
る電極を焼付けてオーミツク接触を得た。これら
の試料について、25℃および50℃での抵抗値（そ
れぞれＲ
25℃およびR50℃）を測定し、25℃での
抵抗率ρ
25℃を下記(1)式より、またＢ定数を(2)式
より算出した。
ρ
25℃＝R25×Ｓ／ｄ ……(1)
（Ｓ：電極面積、ｄ：電極間距離）
Ｂ＝8.868×103logＲ〓／Ｒ〓 ……(2)
さらに各試料の抵抗安定性を検討するために、
150℃の恒温槽中で直流10V／mmの電場を印加し、
抵抗値の経時変化を3000時間まで測定した。
これらの結果を次表にまとめて示す。
The present invention relates to an oxide semiconductor for a thermistor that has a negative temperature coefficient of resistance and is characterized by containing manganese oxide as a main component and, in particular, containing zirconium oxide. Conventionally, the compositions of oxide semiconductors for thermistors containing zirconium oxide and manganese oxide as a main component include Mn-Zr, Co-Zr, Ni-Zr,
The Cu-Zr two-component system is well known. Also,
The four-component Mn-Ni-Cu-Zr system has already been proposed by the present inventors (Japanese Patent Application No. 1983-
No. 145840 = Special Publication No. 13285 (Sho 60-13285). The composition of the thermistor of the present invention was obtained by further examining the earlier-filed patent and found a composition range comparable to that of the earlier-filed patent.The thermistor composition of the present invention is a highly stable material with excellent high-temperature DC voltage load characteristics due to the effect of containing a small amount of zirconium oxide. It is. The thermistor composition of the present invention has a metal element as
Mn94.6~60 at%, Ni5~30 at%, Cu0.1~10
atomic%, Zr0.05 to 0.3 atomic% (however, 0.3 atomic% is not included), and the total of these is 100
It is atomic percent. Here, if the content of copper exceeds 10 atomic %, the specific resistance and the B constant are significantly lowered, and the characteristic values are likely to be out of the range required for practical use, which is not preferable. Further, if the content of Zr is less than 0.05 atomic %, no effect is shown at all, but even a trace amount of 0.05 to 0.3 atomic % shows an effect. The cause of this is currently under investigation. Hereinafter, the content of the present invention will be explained with reference to Examples. First, commercially available raw materials MnCo 3 , NiO, and ZrO 2 were blended as shown in the table below. These compounded compositions were wet mixed in a ball mill using zirconia balls as cobblestones, and after drying these slurries,
Calcinate at ℃, dry crush the calcined product, add and mix a binder, take the required amount and press-form it into a disk shape.
Many molded products were created. This molded body is placed in the air for 1000 min.
The samples were fired at ~1200°C, and electrodes containing Ag as the main component were baked on both sides of these disc-shaped sintered bodies (diameter approximately 6.5 mm, thickness 1.2 mm) to obtain ohmic contact. Regarding these samples, Measure the resistance values at 25℃ and 50℃ (R 25℃ and R 50 ℃, respectively), calculate the resistivity ρ at 25℃ from the following formula (1), and calculate the B constant from the formula (2) below. ρ 25℃=R 25 ×S/d ……(1) (S: electrode area, d: distance between electrodes) B=8.868×10 3 logR〓/R〓 ……(2) Furthermore, the resistance of each sample To consider stability,
Apply a DC 10V/mm electric field in a constant temperature bath at 150℃,
Changes in resistance over time were measured for up to 3000 hours. These results are summarized in the table below.
【表】
試料100、101、1003、2001、2002は比較用であ
り、抵抗値経時変化率が大きく実用上安定性に欠
ける。混合工程によるジルコニア玉石からのZr
混入量は0.05原子％であり、2002番と同組成でジ
ルコニア玉石を用いると、ρ
25℃＝1810Ω・cm、
Ｂ定数3830°K、抵抗直経時変化率は−2.0％であ
つた。
また、この中で試料2003、2005、2007は抵抗値
経時変化率が3000時間経過後で±2.0％以内でき
わめて小さく、しかも実用特性値範囲内で充分実
用に供しうるものである。なお、Zr添加による
この効果についてのメカニズムを現在検討中であ
る。
以上のように、本発明は優れた特性を示すサー
ミスタ用酸化物半導体を提案するものであり、そ
の産業性は大なるものがある。[Table] Samples 100, 101, 1003, 2001, and 2002 are for comparison, and have a large rate of change in resistance value over time and lack practical stability. Zr from zirconia cobbles by mixing process
The mixed amount is 0.05 at%, and if zirconia cobblestone is used with the same composition as No. 2002, ρ 25℃ = 1810Ω・cm,
The B constant was 3830°K, and the direct resistance change rate over time was -2.0%. Moreover, among these samples, samples 2003, 2005, and 2007 have extremely small resistance value change rates over time of within ±2.0% after 3000 hours, and are within the practical characteristic value range and can be used for practical use. The mechanism behind this effect of Zr addition is currently under investigation. As described above, the present invention proposes an oxide semiconductor for a thermistor that exhibits excellent characteristics, and has great industrial potential.
Claims (1)
元素がマンガン94.6〜60原子％、ニツケル５〜30
原子％、銅0.1〜10原子％及びジルコニウム0.05
原子％以上0.3原子％未満の４種を合計100原子％
含有することを特徴とするサーミスタ用酸化物半
導体。1 Consists of a sintered mixture of metal oxides, the metal elements of which are 94.6 to 60 atomic percent manganese and 5 to 30 atomic percent nickel.
atomic%, copper 0.1-10 atomic% and zirconium 0.05
A total of 100 atomic% of 4 types of atomic% or more and less than 0.3 atomic%
An oxide semiconductor for a thermistor comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56104690A JPS586102A (en) | 1981-07-03 | 1981-07-03 | Oxide semiconductor for thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56104690A JPS586102A (en) | 1981-07-03 | 1981-07-03 | Oxide semiconductor for thermistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS586102A JPS586102A (en) | 1983-01-13 |
| JPH039601B2 true JPH039601B2 (en) | 1991-02-08 |
Family
ID=14387461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56104690A Granted JPS586102A (en) | 1981-07-03 | 1981-07-03 | Oxide semiconductor for thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS586102A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013285A (en) * | 1983-07-04 | 1985-01-23 | 株式会社東芝 | Method of operating boiling water reactor |
-
1981
- 1981-07-03 JP JP56104690A patent/JPS586102A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS586102A (en) | 1983-01-13 |
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