JPH0115128B2 - - Google Patents
Info
- Publication number
- JPH0115128B2 JPH0115128B2 JP12694682A JP12694682A JPH0115128B2 JP H0115128 B2 JPH0115128 B2 JP H0115128B2 JP 12694682 A JP12694682 A JP 12694682A JP 12694682 A JP12694682 A JP 12694682A JP H0115128 B2 JPH0115128 B2 JP H0115128B2
- Authority
- JP
- Japan
- Prior art keywords
- diffusing agent
- semiconductor ceramic
- grain boundary
- diffusion
- layer
- 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
Links
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000004065 semiconductor Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 17
- 238000009792 diffusion process Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 239000003985 ceramic capacitor Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000008149 soap solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009489 vacuum treatment Methods 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 239000007787 solid Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
Description
本発明は半導体磁器の粒界に拡散剤を熱拡散さ
せて、その粒界領域に誘電体層を設けることによ
り得られる粒界層型半導体セラミツクコンデンサ
の拡散剤塗布方法に関する。
コンデンサとしての粒界誘電体層型半導体は、
半導体化結晶間の粒界領域を高抵抗化し、結晶粒
界に誘電体層を設ける必要があるため、粒界拡散
剤の塗布方法によりコンデンサとしての諸特性が
大きく左右される。
従来における粒界層型半導体セラミツクコンデ
ンサの拡散剤塗布方法は拡散剤として酸化物、金
属等の固体粉末を用いるため、粒子状態という性
格上理論拡散量の約100〜10000倍もの拡散剤が必
要であるばかりでなく、半導体セラミツク表面に
拡散剤層を均一成分、均一膜でつけることが非常
に困難であつた。また、蒸着法により上記の欠点
を解決したものもあるが、量産性がなく非常にコ
スト高となる。これらの解決には、拡散剤成分を
均一に安価に半導体セラミツク表面に形成させる
製造方法を開発することである。
すなわち、本発明に係る粒界層型半導体セラミ
ツクコンデンサの拡散剤塗布方法は、半導体セラ
ミツクコンデンサ基板を、拡散剤の金属成分を含
有する有機系金属石ケンまたはその金属石ケンと
有機系バインダーよりなる混合液につけ、その後
に熱処理等の乾燥処理により、セラミツク表面に
金属成分層を形成させ、拡散処理をすることを特
徴とする。
尚、上記有機系金属石ケン液により第１図に示
すように、半導体セラミツク基板１の表面に有機
系金属石ケン層２を形成させ、熱処理の温度、処
理雰囲気、真空度等により、セラミツク基板１の
表面に、金属層、金属酸化物層等を形成させる。
これにより、半導体セラミツク基板１の表面に、
拡散剤成分よりなる金属層、金属酸化物層６を均
一に形成させ、その後拡散処理を施し、第２図
ａ，ｂに示すように、半導体セラミツク基板１の
半導体化結晶３間の結晶粒界４に誘電体層５を形
成させる。また、熱処理等の乾燥処理を行わない
場合、半導体セラミツク基板１表面上の拡散剤層
の皮膜ムラが発生する。
以下、本発明を実施例を挙げ具体的に説明す
る。試料の調整工程としては工業用原料（純度99
％以上）のSrCO3，TiO2，Nb2O5粉末等を用い、
この粉末を、湿式混合、乾燥、1200℃の温度で仮
焼し、SrO―TiO2―Nb2O5系仮焼原料粉末を得
た。ついで、この仮焼原料粉末を、平均2.5μmの
粉末に粉砕した後、ポリビニルアルコール水溶液
をバインダーとして添加混合し、32メツシユパス
に整粒し、その整粒粉を直径15mm、厚さ0.5mmの
円板形に1ton／cm2の加圧力で成形し、これらの成
形体を空気中1000℃で加熱処理した後に、90％
N2―10％H2の混合ガス気流中において1400℃の
温度で３時間焼成して直径約22.5mm、厚さ約0.4
mmの円板形の半導体磁器を得た。
拡散剤としては、組成として公知のBi：65mol
％、Cu：35mol％よりなり、本発明例としてオク
チル酸Bi―Cu（Bi：65mol％、Cu：35mol％）、
ナフテン酸Bi―Cu（Bi：65mol％、Cu：35mol
％）を、従来例としてBi2O：65mol％、Cu2O：
35mol％よりなる酸化物粉末をペースト状にした
ものを準備した。尚、本発明の拡散剤は、下記の
第１表に示す溶液を用いた。
The present invention relates to a method for applying a diffusing agent to a grain boundary layer type semiconductor ceramic capacitor obtained by thermally diffusing a diffusing agent to the grain boundaries of semiconductor ceramic and providing a dielectric layer in the grain boundary region. Grain boundary dielectric layer semiconductors as capacitors are
Since it is necessary to increase the resistance of the grain boundary region between semiconductor crystals and provide a dielectric layer at the grain boundaries, various characteristics of the capacitor are greatly influenced by the method of applying the grain boundary diffusing agent. Conventional methods of applying a diffusing agent to grain boundary layer type semiconductor ceramic capacitors use solid powders of oxides, metals, etc. as the diffusing agent, and due to the nature of the particles, approximately 100 to 10,000 times the theoretical amount of diffusing agent is required. Not only that, but it was also extremely difficult to apply a diffusion agent layer with a uniform composition and a uniform film on the surface of a semiconductor ceramic. There are also vapor deposition methods that have solved the above drawbacks, but they are not mass-producible and are extremely costly. To solve these problems, it is necessary to develop a manufacturing method that allows the diffusion agent component to be uniformly and inexpensively formed on the semiconductor ceramic surface. That is, in the method for applying a diffusing agent for a grain boundary layer type semiconductor ceramic capacitor according to the present invention, a semiconductor ceramic capacitor substrate is coated with an organic metal soap containing a metal component of a diffusing agent, or an organic metal soap containing the metal component and an organic binder. It is characterized in that it is immersed in a mixed solution and then subjected to drying treatment such as heat treatment to form a metal component layer on the ceramic surface, followed by diffusion treatment. As shown in FIG. 1, an organic metal soap layer 2 is formed on the surface of the semiconductor ceramic substrate 1 using the above organic metal soap solution, and the ceramic substrate is formed by adjusting the heat treatment temperature, treatment atmosphere, degree of vacuum, etc. A metal layer, a metal oxide layer, etc. are formed on the surface of 1.
As a result, on the surface of the semiconductor ceramic substrate 1,
A metal layer and a metal oxide layer 6 made of a diffusing agent component are uniformly formed, and then a diffusion treatment is performed to form grain boundaries between the semiconductor crystals 3 of the semiconductor ceramic substrate 1, as shown in FIGS. 2a and 2b. 4 to form a dielectric layer 5. Further, if drying treatment such as heat treatment is not performed, film unevenness of the diffusing agent layer on the surface of the semiconductor ceramic substrate 1 will occur. Hereinafter, the present invention will be specifically explained with reference to Examples. In the sample preparation process, industrial raw materials (purity 99
% or more) of SrCO 3 , TiO 2 , Nb 2 O 5 powder, etc.
This powder was wet mixed, dried, and calcined at a temperature of 1200° C. to obtain a SrO—TiO 2 —Nb 2 O 5 based calcined raw material powder. Next, this calcined raw material powder was pulverized into a powder with an average size of 2.5 μm, and an aqueous polyvinyl alcohol solution was added and mixed as a binder, and the sized powder was sized into 32 mesh passes, and the sized powder was shaped into a circle with a diameter of 15 mm and a thickness of 0.5 mm. After molding into a plate shape with a pressure of 1 ton/cm 2 and heat-treating these molded bodies in air at 1000°C, 90%
Baked for 3 hours at a temperature of 1400℃ in a mixed gas flow of N 2 - 10% H 2 to create a shape with a diameter of approximately 22.5 mm and a thickness of approximately 0.4 mm.
mm disk-shaped semiconductor porcelain was obtained. As a diffusing agent, the composition is known as Bi: 65mol
%, Cu: 35 mol%, as an example of the present invention Bi-Cu octylate (Bi: 65 mol%, Cu: 35 mol%),
Naphthenic acid Bi-Cu (Bi: 65mol%, Cu: 35mol
%), Bi 2 O: 65 mol%, Cu 2 O: as a conventional example.
A paste of 35 mol% oxide powder was prepared. As the diffusing agent of the present invention, solutions shown in Table 1 below were used.
【表】
上記拡散剤を用い、本発明例では半導体磁器素
子を弗素樹脂系ネツトに入れ、金属石ケン液につ
けた後、半導体磁器素子を50〜100℃で大気中に
おいて乾燥させた。ここで真空処理においても同
等の拡散剤皮膜が得られた。また、これら処理を
しないものについては、第３図に示すように半導
体セラミツク基板１に拡散剤層の皮膜ムラ部７が
発生し、衝撃等においてこの皮膜ムラ部７が剥離
しやすい状態となつた。また、従来例としては、
松やに、テレピン油等を適量加えて混合し、ペー
スト状拡散剤とし、半導体磁器素子表面にむらな
く塗布した。
以上のように拡散剤を塗布した半導体磁器素子
を大気下1100〜1200℃の温度にて拡散処理を行つ
た。この熱拡散処理にあたつては塗布した拡散成
分が蒸発、溶融流失、試料外への拡散などにより
試料外に失なわれないように留意した。また、拡
散剤量、拡散温度、拡散時間については下記第２
表に示す。このようにして得られた粒界誘電体層
型半導体磁器の円板形素子の両面にAg電極を焼
付けてコンデンサ素子とし、下記の第３表に示す
各諸特性を調べた。[Table] Using the above-mentioned diffusing agent, in the example of the present invention, a semiconductor ceramic element was placed in a fluororesin net, immersed in a metal soap solution, and then dried in the atmosphere at 50 to 100°C. Here, an equivalent diffusing agent film was obtained even in the vacuum treatment. Furthermore, as shown in FIG. 3, in the case where these treatments are not applied, uneven coating portions 7 of the diffusing agent layer occur on the semiconductor ceramic substrate 1, and the uneven coating portions 7 are likely to peel off due to impact, etc. . In addition, as a conventional example,
A suitable amount of turpentine oil or the like was added to pine resin and mixed to form a paste-like diffusing agent, which was evenly applied to the surface of a semiconductor ceramic element. The semiconductor ceramic element coated with the diffusing agent as described above was subjected to a diffusion treatment at a temperature of 1100 to 1200° C. in the atmosphere. In this thermal diffusion treatment, care was taken to ensure that the applied diffusion component was not lost to the outside of the sample due to evaporation, melting, or diffusion to the outside of the sample. In addition, regarding the amount of diffusion agent, diffusion temperature, and diffusion time, please refer to the following 2.
Shown in the table. Ag electrodes were baked on both sides of the disk-shaped element of the grain boundary dielectric layer type semiconductor porcelain thus obtained to make a capacitor element, and various properties shown in Table 3 below were investigated.
【表】
(注) 拡散剤量は酸化物粉末に換算して素子１
枚(約250mg)当りの量である。
[Table] (Note) The amount of diffusing agent is converted to oxide powder for element 1.
This is the amount per piece (approximately 250 mg).
【表】
第２表、第３表において本発明範囲内の実施例
は試料No.１〜No.７迄であり、他は範囲外の比較で
ある。上記実施例から明らかなように、εa，
tanδ、昇圧破壊電圧、容量温度変化率、拡散剤使
用量ともに優れている。これらの好結果は、半導
体セラミツク基板表面に拡散剤成分が微粒子状に
均一に付着しているため、その成分の粒界拡散時
のセラミツク基板表面における結晶粒界単位面積
当りの拡散剤成分量が従来例にくらべて多いこと
による。従つて、拡散剤量、拡散温度、拡散時間
についての特性変化も従来例にくらべて優れてい
る。
尚、本実施例では有機系金属石ケンとして、オ
クチル酸系、ナフテン酸系を用いたが、他の有機
系でもよく、また拡散剤としてBi―Cu系を用い
たが、他の成分系でもよく、従来工法よりも優れ
た結果が得られる。
以上のように、本発明は拡散剤の塗布方法とし
て非常に優れた製造方法であり、工業的量産化に
おいても著しく安定なものであり、産業的価値の
大なるものである。[Table] In Tables 2 and 3, Examples within the scope of the present invention are Samples No. 1 to No. 7, and the others are comparisons outside the scope. As is clear from the above example, εa,
Excellent tan δ, boost breakdown voltage, capacitance temperature change rate, and amount of diffusion agent used. These good results are due to the fact that the diffusing agent component is uniformly adhered to the surface of the semiconductor ceramic substrate in the form of fine particles. This is because there are more cases than in the conventional example. Therefore, the changes in characteristics regarding the amount of diffusing agent, diffusion temperature, and diffusion time are also superior to those of the conventional example. In this example, octyl acid type and naphthenic acid type were used as the organic metal soaps, but other organic types may be used, and Bi-Cu type was used as the diffusing agent, but other component types may also be used. Often results are better than conventional methods. As described above, the present invention is an extremely excellent manufacturing method for applying a diffusing agent, is extremely stable even in industrial mass production, and has great industrial value.
第１図は本発明方法を説明するための半導体セ
ラミツク基板への有機系金属石ケンの付着状態を
示す図、第２図ａ，ｂは同じく粒界誘電体層の形
成過程（拡散処理前、拡散処理後）を示す図、第
３図は本発明方法において、熱処理、真空処理等
をしない場合の拡散剤皮膜ムラを示す図である。
１……半導体セラミツク基板、２……有機系金
属石ケン層、３……半導体化結晶、４……結晶粒
界、５……粒界誘電体層、６……熱真空処理後の
拡散成分層、７……皮膜ムラ部。
FIG. 1 is a diagram showing the state of attachment of organic metal soap to a semiconductor ceramic substrate for explaining the method of the present invention, and FIGS. FIG. 3 is a diagram showing the unevenness of the diffusing agent film when heat treatment, vacuum treatment, etc. are not performed in the method of the present invention. DESCRIPTION OF SYMBOLS 1... Semiconductor ceramic substrate, 2... Organic metal soap layer, 3... Semiconductor crystal, 4... Grain boundary, 5... Grain boundary dielectric layer, 6... Diffusion component after thermal vacuum treatment Layer 7... Film unevenness portion.
Claims (1)
を、拡散剤の金属成分を含有する有機系金属石ケ
ン液またはその有機系金属石ケンと有機バインダ
ーよりなる混合溶液につけ、その後に乾燥処理
し、セラミツク表面に金属成分層を形成させ、拡
散処理をすることを特徴とする粒界層型半導体セ
ラミツクコンデンサの拡散剤塗布方法。1. A grain boundary layer type semiconductor ceramic capacitor substrate is immersed in an organic metal soap solution containing a metal component as a diffusing agent or a mixed solution of the organic metal soap and an organic binder, and then dried to coat the ceramic surface. A method for applying a diffusing agent to a grain boundary layer type semiconductor ceramic capacitor, which comprises forming a metal component layer and performing a diffusion treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12694682A JPS5917228A (en) | 1982-07-20 | 1982-07-20 | Method of coating dispersant of grain boundary layer type semiconductor ceramic condenser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12694682A JPS5917228A (en) | 1982-07-20 | 1982-07-20 | Method of coating dispersant of grain boundary layer type semiconductor ceramic condenser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5917228A JPS5917228A (en) | 1984-01-28 |
| JPH0115128B2 true JPH0115128B2 (en) | 1989-03-15 |
Family
ID=14947802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12694682A Granted JPS5917228A (en) | 1982-07-20 | 1982-07-20 | Method of coating dispersant of grain boundary layer type semiconductor ceramic condenser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5917228A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049619A (en) * | 1983-08-27 | 1985-03-18 | 松下電器産業株式会社 | Method of producing grain goundary type semiconductor ceramic capacitor |
-
1982
- 1982-07-20 JP JP12694682A patent/JPS5917228A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5917228A (en) | 1984-01-28 |
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