JPS58201201A - Conductive composition and electrode forming method for semiconductor porcelain - Google Patents
Conductive composition and electrode forming method for semiconductor porcelainInfo
- Publication number
- JPS58201201A JPS58201201A JP57085305A JP8530582A JPS58201201A JP S58201201 A JPS58201201 A JP S58201201A JP 57085305 A JP57085305 A JP 57085305A JP 8530582 A JP8530582 A JP 8530582A JP S58201201 A JPS58201201 A JP S58201201A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- conductive composition
- semiconductor porcelain
- weight
- semiconductor
- 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 description 30
- 229910052573 porcelain Inorganic materials 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 229910000807 Ga alloy Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000007772 electroless plating Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005036 potential barrier Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 241000531897 Loma Species 0.000 description 1
- 241000220225 Malus Species 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
Landscapes
- Details Of Resistors (AREA)
- Non-Adjustable Resistors (AREA)
- Thermistors And Varistors (AREA)
- Conductive Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は、主として、ｎ型半導体磁器の電極形成に使用
される導電性組成物及びその電極形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to a conductive composition used for forming an electrode of n-type semiconductor ceramics and a method for forming the electrode.
ｎ型半導体磁器は、正の抵抗温度係数を有する正特性半
導体磁器、負の抵抗温度係数を有する負特性半導体磁器
または印加電圧により抵抗値の変化する電圧非直線性半
導体磁器等、電子部品としての有用性が非常に高いもの
である。このようなｎ型半導体磁器を電子部品として用
いるには、磁において、電極を形成する場合、銀Ａｇの
焼付けまたはニッケル１等の無電解メッキ等が一般的で
あった。しかしながら、ｎ型半導体磁器においては、Ａ
ｇの焼付は処理によって電極を形成すると、電極と半導
体界面との間に電位障壁層が形成され、半導体磁器自体
の持つ電気的特性が、電極形成により半減してしまう欠
点がある。しかもこのような電位障壁は、電気的或は熱
的に弱い場合が多く、特に半田付は時等によって特性が
劣化し、信頼性が悪くなる等の欠点を生じる。N-type semiconductor porcelain is used as an electronic component, such as positive characteristic semiconductor porcelain with a positive temperature coefficient of resistance, negative characteristic semiconductor porcelain with a negative temperature coefficient of resistance, or voltage nonlinear semiconductor porcelain whose resistance value changes depending on the applied voltage. It is extremely useful. In order to use such n-type semiconductor ceramics as electronic components, in order to form electrodes in the magnets, baking with silver Ag or electroless plating with nickel 1 or the like has been common. However, in n-type semiconductor porcelain, A
Baking has the disadvantage that when an electrode is formed by processing, a potential barrier layer is formed between the electrode and the semiconductor interface, and the electrical characteristics of the semiconductor ceramic itself are halved by the electrode formation. Moreover, such a potential barrier is often electrically or thermally weak, and the characteristics of soldering in particular deteriorate over time, resulting in drawbacks such as poor reliability.
この電位゛障壁層の形成による欠点を除去する手段とし
て、半導体磁器に対してオーミック性電極を形成する方
法が試みられている。オーミック性電極の形成方法とし
ては、半導体磁器の表面にＩｎ−Ｇａ合金を塗り付ける
方法、Ｉｎ−Ｇａ合金を超音波ろう付けする方法、半導
体磁器に対してＮｉ無電解メッキ処理を行なった後に、
３００〜５００℃の温度条件で熱処理を行なう方法、ま
たはＡｇペースト中にＩｎ−Ｇａ合金を分散させたペー
ストを半導体磁器に塗布し、４００〜５５０℃の低温で
焼付は処理を行なう方法等が知られている。As a means of eliminating the drawbacks caused by the formation of this potential barrier layer, attempts have been made to form ohmic electrodes on semiconductor ceramics. The ohmic electrode can be formed by applying an In-Ga alloy to the surface of the semiconductor porcelain, by ultrasonic brazing the In-Ga alloy, or after performing Ni electroless plating on the semiconductor porcelain.
There are known methods such as heat treatment at a temperature of 300 to 500°C, or applying a paste in which In-Ga alloy is dispersed in Ag paste to semiconductor porcelain and baking at a low temperature of 400 to 550°C. It is being
しかしながら、Ｉｎ−Ｇａ合金を塗布し或は超音波ろう
付けする方法では、高価なガリウムＧａを使用するため
コスト高になること、Ｉｎ −Ｇａ合金が低融点である
ため電極に対して半田付けができないこと、半導体磁器
に対する接着強度が極めて弱いこと等の欠点がある。However, in the method of applying In-Ga alloy or ultrasonic brazing, the cost is high due to the use of expensive gallium Ga, and the low melting point of In-Ga alloy makes it difficult to solder the electrode. There are drawbacks such as the fact that the adhesive strength to semiconductor porcelain is extremely weak.
次に、Ａｇペースト中にＩｎ−Ｇａ合金を分散させたペ
ーストを塗布焼付けする方法は、焼付は時にＩｎ−Ｇａ
合金が酸化されるため半田付けができないこと、低温焼
付けのため半導体磁器に対する接着強度が弱いこと、ガ
リウムＧａを使用するためコスト高になること等の欠点
がある。Next, in the method of applying and baking a paste in which In-Ga alloy is dispersed in Ag paste, baking is sometimes performed using In-Ga alloy.
There are disadvantages such as the inability to solder because the alloy is oxidized, the adhesive strength to semiconductor ceramics being weak due to low temperature baking, and the high cost due to the use of gallium Ga.
更にＮｉ無電解メッキ方法は、無電解メッキ後の熱処理
によって電極表面が酸化され、半田付は性が悪くなるこ
と、形成される電極の厚みが薄くかつＮ１の固有抵抗値
が比較的大きいため電極面の抵抗が大きくなること、メ
ッキ液への浸漬によって半導体磁器素体が悪影響を受け
ること等の欠点がある。Furthermore, in the Ni electroless plating method, the electrode surface is oxidized by the heat treatment after electroless plating, resulting in poor solderability, and the formed electrode is thin and the specific resistance value of N1 is relatively large. There are disadvantages such as increased surface resistance and the semiconductor ceramic body being adversely affected by immersion in the plating solution.
本発明は上述する従来の欠点を除去し、半導体磁器に対
して、半田付は性、接着強度及び電気的特性が良好で、
しかも安価なオーミック性または準オーミック性電極を
形成し得る導電性組成物及び電極形成方法を提供するこ
とを目的とする。The present invention eliminates the above-mentioned conventional drawbacks, and provides good solderability, adhesive strength, and electrical properties for semiconductor porcelain.
Moreover, it is an object of the present invention to provide a conductive composition and a method for forming an electrode that can form an inexpensive ohmic or quasi-ohmic electrode.
上記目的を達成するため、本発明に係る導電性組成物は
、銀、アルミニュム及びガラスフリットを含有すること
を特徴とする。In order to achieve the above object, the conductive composition according to the present invention is characterized by containing silver, aluminum, and glass frit.
前記銀及びアルミニュウムの相対的な含イ１量は、銀を
４０乃至９０重量％、前記アルミニュウムを１０乃至６
０重量％の割合とすることが望ましい。The relative content of silver and aluminum is 40 to 90% by weight for silver and 10 to 6% for aluminum.
It is desirable that the proportion be 0% by weight.
この導電性組成物を使用して、半導体磁器に電極を形成
するには、前記組成に成るＡｇ及び旧の混合粉または合
金粉を、ガラスフリットと共に有機質ビヒクル中に分散
せしめてペーストを調製し、このペーストをスクリーン
印刷等の周知の手段によって半導体磁器に塗布した後、
焼付は処理を行なう。焼付は処理は３００乃至７５０°
Ｃの温度条件で行なう。In order to form an electrode on semiconductor porcelain using this conductive composition, a paste is prepared by dispersing Ag and the old mixed powder or alloy powder having the above composition in an organic vehicle together with glass frit, After applying this paste to semiconductor porcelain by well-known means such as screen printing,
Burning is processed. Baking treatment is 300 to 750°
The test was carried out under temperature conditions of C.
このようにして形成された電極は、半田付は性か良好で
、半導体磁器に対する接着強度が大きく、かつ半導体磁
器に対して電位障壁を持たないオーミック性電極となり
、半導体磁器自体の持つ電気的特性がそのまま取出され
る。しかも、高価なＧａを使用せずに、安価なＡＩを使
用しているので、従来のＩｎ−Ｇａ合金を用いる方法に
比べて著しく安価になる。また、本発明によって得られ
た電極は、焼付は温度が３００〜７５０℃であるから、
例えば正特性サーミスタのように、２００°Ｃ程度の温
度条件で使用される半導体磁器においても、従来と異な
って、特性が変化することがない。更に、Ｎｉ無電解メ
ッキの場合と異なって、メッキ液中へ半導体磁器を浸漬
することもないので、電極形成工程において半導体磁器
が悪影響を受けることがない。また、ペースト化してス
クリーン印刷等の手段によって電極を形成することかで
きるので、複雑な形状の電極構造のものであっても容易
に形成することができる。The electrode formed in this way has good solderability, has high adhesion strength to the semiconductor porcelain, and is an ohmic electrode that does not have a potential barrier to the semiconductor porcelain, and has the electrical properties of the semiconductor porcelain itself. is taken out as is. Moreover, since inexpensive AI is used instead of expensive Ga, the cost is significantly lower than the conventional method using an In-Ga alloy. Furthermore, since the electrode obtained according to the present invention is baked at a temperature of 300 to 750°C,
For example, even in semiconductor porcelain, such as a positive temperature coefficient thermistor, which is used under a temperature condition of about 200° C., the characteristics do not change, unlike in the past. Furthermore, unlike the case of Ni electroless plating, the semiconductor ceramic is not immersed in the plating solution, so the semiconductor ceramic is not adversely affected in the electrode forming process. Further, since the electrodes can be formed into a paste and formed by means such as screen printing, even electrode structures having complicated shapes can be easily formed.
次に実施例を上げて本発明の内容を更に具体的に説明す
る。Next, the content of the present invention will be explained in more detail with reference to Examples.
Ａｇと８１の４属成分の相対的な配合比を種々に変えた
混合粉１００部と、ガラスフリット粉３部とを、有機質
ビヒクル５０部に分散させて各ペーストを調製した。こ
れらのペーストをｎ型半導体磁器であるＴ ｉ０２を主
成分とする半導体磁器の表面に塗布し、空気中で６５０
°Ｃの温度条件で焼付け、電圧非直線性抵抗素子を得た
。こう°して得られた電圧非直線性抵抗素子の特性評価
を、Ｉｎ−Ｇａ合金電極を形成した電圧非直線性抵抗素
子のそれと比較して、表１に示しである。また、Ａｇ蔽
を８０重量％、Ａｌ量を２０重鼠％としたものについて
、焼付は温度を変えた時の特性評価を表２に示しである
。Each paste was prepared by dispersing 100 parts of mixed powder in which the relative blending ratios of Ag and 4th group component 81 were varied and 3 parts of glass frit powder in 50 parts of an organic vehicle. These pastes were applied to the surface of semiconductor porcelain whose main component is T i02, which is n-type semiconductor porcelain, and heated for 650 min in air.
A voltage nonlinear resistance element was obtained by baking at a temperature of °C. Table 1 shows the evaluation of the characteristics of the voltage nonlinear resistance element thus obtained, in comparison with that of a voltage nonlinear resistance element formed with an In-Ga alloy electrode. Furthermore, Table 2 shows the evaluation of the characteristics of the baking at different temperatures when the Ag coverage was 80% by weight and the Al content was 20% by weight.
表１及び２において、ＥｌＯは電圧非直線性抵抗素子に
ｌｏｍＡの電流が流れた時、素子の両端に現われる電圧
である。αは電圧非直線性係数であり、次の式から算出
される。In Tables 1 and 2, ElO is the voltage that appears across the voltage nonlinear resistance element when a current of lomA flows through the element. α is a voltage nonlinearity coefficient and is calculated from the following formula.
α＝ １ ／ （ｌｏｇ Ｅ １０／ Ｅ １ ）但し
Ｅｌは＊流１ｍＡの時の電圧
電極強度は粘着テープによるビーリングテストによって
測定した。また耐パルス性はＯ→５０Ｖ（ピーク値）の
パルスを１０サイクル印加した場合のＥｌＯ値の変化と
して示しである。α=1/(log E10/E1) where El is *The voltage electrode strength at a current of 1 mA was measured by a beading test using an adhesive tape. Further, pulse resistance is shown as a change in ElO value when a pulse of O→50V (peak value) is applied for 10 cycles.
凡例 ×；弱い Δ；やや弱い ・；強い表１から
明らかなように、本発明に係る導電性組成物で電極を形
成した試料Ｎｏ１〜７は、従来のＩｎ−Ｇａ合金電極と
した試料ＮＯ８と比較して、電極強度が非常に高くなる
。特にＡｇ１ｔを４０乃至９０重醗％、Ａｌ量を１０乃
至６０重都％の割合で含イ１する導電性ペーストを使用
して電極を形成した試料ＮＯ３〜６は、ＥＩＯ１α及び
耐パルス性において、従来のＩｎ−Ｇａ合金電極とした
試料ＮＯ８と比較して、勝るとも劣らない優れた特性を
示す。９０重量％を超過するＡｇ敬、１０重量％未猫の
Ａ１値を含有させた試料Ｎｏｔ、２及び４０東駿％未満
のＡｇ量、６０重量％を超過するＡｌ量を含有させた試
料ＮＯ７は、従来のＩｎ−Ｇａ合金電極とした試ネ１Ｎ
０８と比較して、電極強度は高くなるものの、ＥｌＯ値
が高くなり、耐パルス性も１０％以［の変化をしてしま
うので実用」−は不Ｅｌである。Legend ×: Weak Δ: Slightly weak ・: Strong As is clear from Table 1, samples Nos. 1 to 7 in which electrodes were formed using the conductive composition according to the present invention are different from sample No. 8 in which conventional In-Ga alloy electrodes were formed. In comparison, the electrode strength is much higher. In particular, samples Nos. 3 to 6 in which electrodes were formed using a conductive paste containing 40 to 90% Ag1t and 10 to 60% Al in terms of EIO1α and pulse resistance. Compared with sample No. 8, which is a conventional In--Ga alloy electrode, it exhibits excellent characteristics that are comparable to those of sample No. 8. Sample No. 7 contained an Ag amount exceeding 90% by weight, an Ag amount of less than 2 and 40% by weight, and an Al amount of more than 60% by weight. , a sample 1N using a conventional In-Ga alloy electrode.
Compared to 08, although the electrode strength is higher, the ElO value is higher and the pulse resistance changes by more than 10%, so it is not practical.
次に表２を参照すると、Ａｇ量を８０重重量、 Ａｌ量
を２０重量％の割合で含有させた本発明に係る試ネ：Ｊ
ＮＯ４においても、焼付は温度が３００ ’Ｏ未満であ
ると電極強度が低くなり、また焼付は温度が７５０℃を
超過すると、ＥｌＯ値が高くなり、耐／マルス性も１０
％以りの変化を示し、実用性力く失われる。つまり、本
発明に係る導電性組成物を含有する導電性ペーストを使
用して電極を形成する場合、Ａｇ量を４０乃至６０重量
％、Ａ１値を１０乃至６０重量％の範囲とし、３００〜
７５０ ’Ｃの焼イ１け温ｌで焼付は処理を行なうこと
番こより、実用−１−良好な特性が得られることが解る
。Next, referring to Table 2, the test sample according to the present invention containing 80% by weight of Ag and 20% by weight of Al: J
Even in NO4, if the temperature is less than 300°C, the electrode strength will be low, and if the temperature exceeds 750°C, the ElO value will be high and the resistance/malus resistance will be 10%.
% or more, and the practicality is seriously lost. That is, when forming an electrode using a conductive paste containing the conductive composition according to the present invention, the amount of Ag is 40 to 60% by weight, the A1 value is in the range of 10 to 60% by weight, and the
It can be seen that by performing the baking process at a baking temperature of 750'C, good properties can be obtained in practical use.
以１−述べたように、本発明に係る導電性組成物は、銀
、アルミニュム及びガラスフ１）・ントを含イ１するこ
とを特徴とするから、これらの組成比及び焼付は温度等
を通出に選定すること番こより、）￥導体磁器に対して
、半田付は性、接着強度及び電気的特性か良好で、しか
も安価なオーミ・ンク性または準オーミンク性電極を形
成し得る導電性組成物、及び電極形成方法を提供するこ
とができる。As described above, the conductive composition according to the present invention is characterized by containing silver, aluminum, and glass powder, so the composition ratio and baking of these components are determined by temperature and other factors. For conductive porcelain, select a conductive composition that has good solderability, adhesive strength, and electrical properties, and can form inexpensive ohmic or quasi-ohmic electrodes. and a method for forming an electrode.
Claims (3)
ることを特徴とする導電性組成物。(1) A conductive composition characterized by containing silver, aluminum and glass frit.
ウムをｌＯ乃至６０重量％の割合で含有することを特徴
とする特許請求の範囲第１項に記載の導電性組成物。(2) The conductive composition according to claim 1, characterized in that the silver is contained in a proportion of 40 to 90% by weight, and the aluminum is contained in a proportion of 1O to 60% by weight.
Ｏ乃至６０重量％の範囲の銀及びアルミニュウムの混合
粉または合金粉と、ガラスフリントとを有機質ビヒクル
中に分散せしめたペーストを半導体磁器に塗布し、３０
０乃至７５０℃の温度条件で焼付は処理を行なうことを
特徴とする半導体磁器の電極形成方法。(3) Silver is 40 to 60% by weight, aluminum is 1
A paste prepared by dispersing silver and aluminum mixed powder or alloy powder in the range of O to 60% by weight and glass flint in an organic vehicle is applied to semiconductor porcelain, and
A method for forming electrodes of semiconductor ceramics, characterized in that baking is performed at a temperature of 0 to 750°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57085305A JPS58201201A (en) | 1982-05-20 | 1982-05-20 | Conductive composition and electrode forming method for semiconductor porcelain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57085305A JPS58201201A (en) | 1982-05-20 | 1982-05-20 | Conductive composition and electrode forming method for semiconductor porcelain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58201201A true JPS58201201A (en) | 1983-11-24 |
| JPH0370361B2 JPH0370361B2 (en) | 1991-11-07 |
Family
ID=13854882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57085305A Granted JPS58201201A (en) | 1982-05-20 | 1982-05-20 | Conductive composition and electrode forming method for semiconductor porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58201201A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6166303A (en) * | 1984-09-06 | 1986-04-05 | 太陽誘電株式会社 | Conductive paste for thick film |
| JPH02306606A (en) * | 1989-05-22 | 1990-12-20 | Tdk Corp | Semiconductor porcelain electronic parts and conductive composition |
| JP2008147033A (en) * | 2006-12-11 | 2008-06-26 | Kyoto Elex Kk | Conductive paste |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5156997A (en) * | 1974-09-18 | 1976-05-19 | Siemens Ag |
-
1982
- 1982-05-20 JP JP57085305A patent/JPS58201201A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5156997A (en) * | 1974-09-18 | 1976-05-19 | Siemens Ag |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6166303A (en) * | 1984-09-06 | 1986-04-05 | 太陽誘電株式会社 | Conductive paste for thick film |
| JPH02306606A (en) * | 1989-05-22 | 1990-12-20 | Tdk Corp | Semiconductor porcelain electronic parts and conductive composition |
| JP2008147033A (en) * | 2006-12-11 | 2008-06-26 | Kyoto Elex Kk | Conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0370361B2 (en) | 1991-11-07 |
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