JPH0828306B2 - Method for manufacturing grain boundary insulated semiconductor porcelain - Google Patents
Method for manufacturing grain boundary insulated semiconductor porcelainInfo
- Publication number
- JPH0828306B2 JPH0828306B2 JP3314092A JP31409291A JPH0828306B2 JP H0828306 B2 JPH0828306 B2 JP H0828306B2 JP 3314092 A JP3314092 A JP 3314092A JP 31409291 A JP31409291 A JP 31409291A JP H0828306 B2 JPH0828306 B2 JP H0828306B2
- Authority
- JP
- Japan
- Prior art keywords
- grain boundary
- semiconductor
- porcelain
- sample
- insulating 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 - Lifetime
Links
- 239000004065 semiconductor Substances 0.000 title claims description 50
- 229910052573 porcelain Inorganic materials 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 5
- 238000009413 insulation Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000011810 insulating material Substances 0.000 description 22
- 239000003990 capacitor Substances 0.000 description 19
- 238000003303 reheating Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- -1 (S r Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、磁器コンデンサ等のた
めの粒界絶縁型半導体磁器の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a grain boundary insulation type semiconductor ceramic for a ceramic capacitor or the like.
【０００２】[0002]
【従来の技術】チタン酸ストロンチウム系半導体磁器コ
ンデンサを製造するために、半導体磁器原料の成形体を
還元性雰囲気中で焼成して半導体磁器焼結体を得、次に
酸化ビスマス、酸化鉛、酸化ホウ素等の金属酸化物から
成る粒界絶縁化物質を焼結体の表面にスクリーン印刷等
によって塗布し、これを大気中で熱処理を施して粒界絶
縁化物質を粒界に拡散させ、しかる後銀ペーストを塗布
して焼き付けることによって一対の電極を形成すること
は公知である。2. Description of the Related Art In order to manufacture a strontium titanate based semiconductor porcelain capacitor, a molded body of a semiconductor porcelain raw material is fired in a reducing atmosphere to obtain a semiconductor porcelain sintered body, and then bismuth oxide, lead oxide, and oxidization. A grain boundary insulating substance composed of a metal oxide such as boron is applied to the surface of the sintered body by screen printing or the like, and this is subjected to heat treatment in the air to diffuse the grain boundary insulating substance to the grain boundaries. It is known to form a pair of electrodes by applying and baking a silver paste.
【０００３】[0003]
【発明が解決しようとする課題】ところで、半導体磁器
の表面から必要量のみの粒界絶縁化物質を半導体粒子の
境界に均一に拡散させ、十分な絶縁抵抗を得ることは困
難であった。このため、粒界絶縁化物質を半導体磁器の
表面から過剰に供給する必要があった。このように粒界
絶縁化物質を過剰に供給すると、確かに絶縁抵抗は高く
なる。しかし、磁器の表面に一対の電極を形成してコン
デンサを完成させた後に、これを高温、高湿環境に置
き、且つ電極間に電圧を印加した状態を長時間保つと、
電極を形成している金属がイオン化することにより生成
される電子が絶縁化物質に取り込まれる。この結果、粒
界絶縁層に電気的及び構造的欠陥が生じ、粒界絶縁層の
抵抗値の低下や磁器の強度の低下が生じる。By the way, it has been difficult to obtain a sufficient insulation resistance by uniformly diffusing only a necessary amount of the grain boundary insulating material from the surface of the semiconductor porcelain to the boundaries of the semiconductor particles. Therefore, it is necessary to excessively supply the grain boundary insulating material from the surface of the semiconductor ceramic. If the grain boundary insulating material is excessively supplied in this manner, the insulation resistance is certainly increased. However, when a pair of electrodes are formed on the surface of the porcelain to complete the capacitor, and then the capacitor is placed in a high temperature and high humidity environment and a voltage is applied between the electrodes for a long time,
Electrons generated by ionization of the metal forming the electrodes are taken into the insulating substance. As a result, electrical and structural defects occur in the grain boundary insulating layer, and the resistance value of the grain boundary insulating layer and the strength of the porcelain decrease.
【０００４】そこで、本発明の目的は、粒界絶縁型半導
体磁器の安定性を向上させることにある。Therefore, an object of the present invention is to improve the stability of a grain boundary insulating semiconductor ceramic.
【０００５】上記目的を達成するための本発明は、半導
体磁器原料の成形体を焼成して半導体粒子の集まりから
なる半導体磁器を得る工程と、前記半導体磁器の表面に
粒界絶縁化物質を付着させ、前記半導体磁器を大気中で
加熱することによって前記粒界絶縁化物質を前記半導体
粒子の境界領域に拡散させて粒界絶縁層を形成する工程
と、前記粒界絶縁層を形成した半導体磁器に対して、酸
素の割合が大気以上の酸化性雰囲気中で前記粒界絶縁層
を形成した時の加熱温度よりも低い温度によって加熱処
理を施す工程とを有することを特徴とする粒界絶縁型半
導体磁器の製造方法に係わるものである。The present invention for achieving the above object comprises the steps of firing a molded body of a semiconductor porcelain raw material to obtain a semiconductor porcelain composed of a collection of semiconductor particles, and attaching a grain boundary insulating material to the surface of the semiconductor porcelain. And heating the semiconductor porcelain in the atmosphere to diffuse the grain boundary insulating material into the boundary region of the semiconductor particles to form a grain boundary insulating layer, and the grain boundary insulating layer. the formed for the semiconductor porcelain, acid
The grain boundary insulating layer in an oxidizing atmosphere in which the proportion of the element is atmospheric or higher.
And a step of performing heat treatment at a temperature lower than the heating temperature at the time of forming the grain boundary insulating semiconductor porcelain.
【０００６】なお、絶縁抵抗の低下を抑えるためには、
粒界絶縁層形成後の加熱処理の温度を拡散工程における
加熱処理温度よりも低く設定することが望ましい。ま
た、加熱処理を酸化性雰囲気（好ましくは大気よりも酸
素濃度の高い雰囲気）中で行うことが望ましい。In order to prevent the insulation resistance from decreasing,
It is desirable to set the temperature of the heat treatment after forming the grain boundary insulating layer lower than the heat treatment temperature in the diffusion step. In addition, it is desirable that the heat treatment be performed in an oxidizing atmosphere (preferably an atmosphere having a higher oxygen concentration than the atmosphere).
【０００７】[0007]
【作用】半導体磁器の表面に粒界絶縁化物質を付着させ
て大気中で加熱すると、粒界絶縁化物質が粒界に拡散さ
れると共に酸化作用が生じて粒界絶縁層が形成される。
この工程後に再び酸化性雰囲気中で加熱処理を施すと、
過剰な粒界絶縁化物質が排出され、均一な粒界絶縁層が
得られる。また、再加熱処理を酸化性雰囲気で行うと、
前の工程で形成された粒界絶縁層の不安定な絶縁化物質
を安定化させて絶縁抵抗を高めることができる。[Function] Attaching a grain boundary insulating material to the surface of the semiconductor porcelain
When heated in air at room temperature, the grain boundary insulating material diffuses to the grain boundaries.
At the same time, an oxidation action occurs and a grain boundary insulating layer is formed.
After this step , if heat treatment is applied again in an oxidizing atmosphere ,
Excessive grain boundary insulating material is discharged, and a uniform grain boundary insulating layer is obtained. Further, when re-heat treatment in an oxidizing atmosphere,
The unstable insulating material of the grain boundary insulating layer formed in the previous step can be stabilized to increase the insulation resistance.
【０００８】[0008]
【実施例】次に、図１〜図４を参照して本発明の実施例
に係わる粒界絶縁型半導体磁器コンデンサの製造方法を
説明する。EXAMPLES Next, a method of manufacturing a grain boundary insulation type semiconductor ceramic capacitor according to an example of the present invention will be described with reference to FIGS.
【０００９】表１に示すように種々の条件を変えて２４
種類の磁器コンデンサを作製し、その電気的特性を調べ
た。なお、表１には半導体磁器の組成と絶縁化物質の組
成と再加熱温度とが示されている。As shown in Table 1, various conditions are changed to 24
Various types of porcelain capacitors were produced and their electrical characteristics were investigated. Table 1 shows the composition of the semiconductor porcelain, the composition of the insulating material, and the reheating temperature.
【００１０】[0010]
【表１】 [Table 1]
【００１１】表１の試料Ｎｏ．１に従う磁器コンデンサ
を作製するために、 ＳｒＴｉＯ3 （チタン酸ストロンチウム）１００．００
重量部 Ｎｂ2 Ｏ5 （酸化ニオブ）０．２５重量部 の混合物に水を加えてボールミルで１５時間撹拌し、こ
れを乾燥して原料粉末を得た。Sample No. 1 in Table 1 SrTiO 3 (strontium titanate) 100.00 to make a porcelain capacitor according to 1.
Water was added to a mixture of 0.25 parts by weight of Nb 2 O 5 (niobium oxide), and the mixture was stirred with a ball mill for 15 hours and dried to obtain a raw material powder.
【００１２】次に、この原料粉末に対して１０〜１５重
量％のポリビニルアルコールを有機結合剤として混入
し、造粒したものを型にいれて約１トン／ｃｍ2 の圧力
で成形し、直径８．０ｍｍ、厚さ０．５ｍｍの円板状成
形体を得た。Next, 10 to 15% by weight of polyvinyl alcohol was mixed as an organic binder with respect to the raw material powder, and the granulated product was put into a mold and molded at a pressure of about 1 ton / cm 2 to obtain a diameter. A disk-shaped molded body having a thickness of 8.0 mm and a thickness of 0.5 mm was obtained.
【００１３】次に、この成形体を炉にいれて、Ｎ2 （９
６容積％）＋Ｈ2 （４容積％）の還元性雰囲気で１４０
０℃、３時間焼成し、図１に原理的に示す焼結体から成
る円板状半導体磁器１を得た。この半導体磁器１は半導
体粒子２の集合体である。Next, this molded body is put into a furnace and N 2 (9
140% in a reducing atmosphere of 6% by volume + H 2 (4% by volume)
Firing was performed at 0 ° C. for 3 hours to obtain a disk-shaped semiconductor ceramic 1 composed of a sintered body shown in principle in FIG. The semiconductor porcelain 1 is an aggregate of semiconductor particles 2.
【００１４】次に、図２に示すように半導体磁器１の表
面にＢｉ2 Ｏ3 （酸化ビスマス）と有機結合剤とから成
る絶縁化物質ペーストをスクリーン印刷で塗布して絶縁
化物質層３を形成した。絶縁化物質層３に含まれる絶縁
化物質（Ｂｉ2 Ｏ3 ）の量は１００重量部の半導体磁器
１に対して３．０重量部となるように決定されており、
粒界絶縁層を形成するために要求される量よりも多い。Next, as shown in FIG. 2, an insulating material paste composed of Bi 2 O 3 (bismuth oxide) and an organic binder is applied to the surface of the semiconductor porcelain 1 by screen printing to form an insulating material layer 3. Formed. The amount of the insulating substance (Bi 2 O 3 ) contained in the insulating substance layer 3 is determined to be 3.0 parts by weight with respect to 100 parts by weight of the semiconductor ceramic 1.
Greater than the amount required to form the grain boundary insulating layer.
【００１５】次に、図２に示すものを大気（酸化性雰囲
気）中で１１５０℃、２時間熱処理し、絶縁化物質（Ｂ
ｉ2 Ｏ3 ）を粒界層に拡散させた。これにより、図３に
示すように半導体粒子２の間に粒界絶縁層４が生じる。Next, the material shown in FIG. 2 is heat-treated at 1150 ° C. for 2 hours in the air (oxidizing atmosphere) to obtain an insulating material (B
i 2 O 3 ) was diffused into the grain boundary layer. As a result, the grain boundary insulating layer 4 is generated between the semiconductor particles 2 as shown in FIG.
【００１６】次に、半導体磁器１の温度を室温（約２０
℃）まで下げた後に、再び大気中で、１１００℃、２時
間の加熱処理を施した。この再加熱処理によって粒界絶
縁層４中の余分な絶縁物質が半導体磁器１から排出さ
れ、且つ粒界絶縁層４の安定化が達成される。Next, the temperature of the semiconductor porcelain 1 is set to room temperature (about 20
C.), and then heat-treated again at 1100.degree. C. for 2 hours in the atmosphere. By this reheating treatment, the excess insulating material in the grain boundary insulating layer 4 is discharged from the semiconductor ceramic 1 and the grain boundary insulating layer 4 is stabilized.
【００１７】次に、半導体磁器１の両主面に銀ペースト
を塗布して大気中８００℃で焼付けして図４に示す電極
５、６を形成した。Next, silver paste was applied to both main surfaces of the semiconductor porcelain 1 and baked at 800 ° C. in the atmosphere to form the electrodes 5 and 6 shown in FIG.
【００１８】得られた磁器コンデンサの静電容量Ｃ1 、
誘電体損失ｔａｎδ1 、及び絶縁抵抗Ｒ1 を測定したと
ころ、表２の試料Ｎｏ．１に示す結果が得られた。即
ち、静電容量Ｃ1 は３９．６０ｎＦであり、誘電体損失
ｔａｎδ1 は０．９０％であり、絶縁抵抗Ｒ1 は３２０
０ＭΩであった。なお、静電容量Ｃ1 及び誘電体損失ｔ
ａｎδ1 は１ｋＨｚ、１Ｖ（実効値）の条件で測定し
た。絶縁抵抗Ｒ1 はＤＣ（直流）５０Ｖで測定した。The capacitance C1 of the obtained ceramic capacitor,
The dielectric loss tan δ1 and the insulation resistance R1 were measured. The results shown in 1 were obtained. That is, the capacitance C1 is 39.60 nF, the dielectric loss tan .delta.1 is 0.90%, and the insulation resistance R1 is 320.
It was 0 MΩ. Note that the capacitance C1 and the dielectric loss t
An δ1 was measured under the conditions of 1 kHz and 1 V (effective value). The insulation resistance R1 was measured at DC (direct current) 50V.
【００１９】次に、上記の初期測定が終了した磁器コン
デンサを、温度６０℃、湿度９５％の恒温恒湿槽中に配
置し、且つ一対の電極５，６間に直流５０Ｖを印加し、
この状態を１０００時間維持する耐湿負荷試験後にコン
デンサを常温（２０℃）常湿（６０％）に２時間放置
し、しかる後再び静電容量Ｃ2 、誘電体損失ｔａｎδ
2、及び絶縁抵抗Ｒ2 を測定したところ、表２に示す結
果が得られた。即ち、試料Ｎｏ．１においては耐湿負荷
試験後の静電容量Ｃ2 は３８．４０ｎＦ、誘電体損失ｔ
ａｎδ2 は０．９２％、絶縁抵抗Ｒ2 は３０００ＭΩで
あった。なお、表２は静電容量Ｃ2 のＣ1に対する変化
率△Ｃ、誘電体損失ｔａｎδ2 のｔａｎδ1に対する変
化率△ｔａｎδ、絶縁抵抗Ｒ2 のＲ1 に対する変化率△
Ｒが夫々示されている。Next, the porcelain capacitor whose initial measurement has been completed is placed in a thermo-hygrostat having a temperature of 60 ° C. and a humidity of 95%, and a direct current of 50 V is applied between the pair of electrodes 5 and 6.
After the humidity resistance load test for maintaining this state for 1000 hours, the capacitor is left at room temperature (20 ° C.) and normal humidity (60%) for 2 hours, and then the capacitance C2 and the dielectric loss tanδ are again measured.
When 2 and the insulation resistance R2 were measured, the results shown in Table 2 were obtained. That is, the sample No. In No. 1, the electrostatic capacity C2 after the humidity resistance test is 38.40 nF and the dielectric loss t.
An δ2 was 0.92%, and insulation resistance R2 was 3000 MΩ. Table 2 shows the rate of change ΔC of capacitance C2 with respect to C1, the rate of change of dielectric loss tan δ2 with respect to tan δ1, Δtan δ, and the rate of change of insulation resistance R2 with respect to R1.
Each R is shown.
【００２０】試料Ｎｏ．２〜１８においては半導体磁器
の組成又は絶縁化物質の組成又は再加熱温度を変えた他
は試料Ｎｏ．１と同一の方法で磁器コンデンサを作り、
同様に特性を測定した。なお、試料Ｎｏ．４〜６、１０
〜１２、１６〜１８、２２〜２４では半導体磁器がＳｒ
ＴｉＯ3 とＣａＴｉＯ3 とＮｂ2 Ｏ5 とから成る。ま
た、試料Ｎｏ．２、５、８、１１、１４、１７、２０、
２３では、絶縁化物質がＢｉ2 Ｏ3 とＰｂＯの組み合せ
から成り、試料Ｎｏ．３、６、９、１２、１８、２１、
２４では、Ｂｉ2 Ｏ3 とＰｂＯとＢ2 Ｏ3の組み合せか
ら成る。Sample No. 2 to 18, except that the composition of the semiconductor porcelain or the composition of the insulating material or the reheating temperature was changed. Make a porcelain capacitor in the same way as 1.
The characteristics were measured in the same manner. Sample No. 4-6, 10
~ 12, 16-18, 22-24, the semiconductor porcelain is Sr.
It consists of TiO 3 , CaTiO 3 and Nb 2 O 5 . In addition, the sample No. 2, 5, 8, 11, 14, 17, 20,
In No. 23, the insulating substance is a combination of Bi 2 O 3 and PbO, and the sample No. 3, 6, 9, 12, 18, 21,
24 consists of a combination of Bi 2 O 3 , PbO and B 2 O 3 .
【００２１】試料Ｎｏ．１９〜２４においては、再加熱
処理を施さない従来方法で磁器コンデンサを作り、その
特性を試料Ｎｏ．１と同様に測定した。なお、試料Ｎ
ｏ．１９〜２４の磁器コンデンサは、試料Ｎｏ．１〜９
と同一の半導体磁器組成及び絶縁化物質組成を有するよ
うに形成され、且つ拡散工程後の再加熱処理工程を省い
た以外は試料Ｎｏ．１と同一の処理が施されている。Sample No. In Nos. 19 to 24, a porcelain capacitor was manufactured by a conventional method which was not subjected to a reheating treatment, and its characteristics were measured with respect to Sample No. The measurement was performed in the same manner as 1. Sample N
o. The porcelain capacitors Nos. 19 to 24 are sample Nos. 1-9
Sample No. 1 except that it was formed so as to have the same semiconductor porcelain composition and insulating material composition as in Example 1 and the reheating treatment step after the diffusion step was omitted. The same processing as 1 is performed.
【００２２】[0022]
【表２】 [Table 2]
【００２３】表１及び表２から明らかなように、本発明
に従う試料Ｎｏ．１〜１８に示す磁器コンデンサの初期
特性と耐湿負荷試験後の特性との差は、試料Ｎｏ．１９
〜２４に示す比較例の磁器コンデンサの初期特性と耐湿
負荷試験後の特性との差よりも大幅に小さい。例えば、
試料Ｎｏ．１においては静電容量が−３．０３％変化す
るのみであるのに対し、試料Ｎｏ．１９の比較例では−
１４．７０％変化する。また、絶縁抵抗は試料Ｎｏ．１
において耐湿負荷試験の前後で−６．６６％変化する
が、試料Ｎｏ．１９の比較例では−９７．４％変化す
る。As is clear from Tables 1 and 2, the sample No. The difference between the initial characteristics of the porcelain capacitors shown in Nos. 1 to 18 and the characteristics after the moisture resistance load test is as follows. 19
It is significantly smaller than the difference between the initial characteristics and the characteristics after the humidity resistance load test of the porcelain capacitors of the comparative examples shown in FIGS. For example,
Sample No. In the case of Sample No. 1, the capacitance changes only by −3.03%. In the comparative example of 19, −
14.70% change. Further, the insulation resistance is the same as Sample No. 1
In the sample No. 1, although it changes by −6.66% before and after the moisture resistance load test. In the comparative example of 19, the change is -97.4%.
【００２４】試料Ｎｏ．１〜１２では、再加熱処理の温
度が拡散工程の加熱温度（１１５０℃）と同一又はこれ
以下の温度１１００℃に設定されている。この場合に
は、絶縁化物質の不要な排出が制限されるために、絶縁
抵抗の低下を防ぐことができる。試料Ｎｏ．１３〜１８
では再加熱温度が拡散工程の温度（１１５０℃）よりも
高い１２００℃に設定されている。この高い再加熱温度
の場合には、特性の安定化効果が試料Ｎｏ．１〜１２よ
りも強く得られる。半面、絶縁抵抗は試料Ｎｏ．１〜１
２よりも低下しているが、実用的範囲には収まってい
る。Sample No. In 1 to 12, the temperature of the reheating treatment is set to 1100 ° C. which is the same as or lower than the heating temperature (1150 ° C.) of the diffusion step. In this case, since unnecessary discharge of the insulating material is limited, it is possible to prevent the insulation resistance from decreasing. Sample No. 13-18
In the above, the reheating temperature is set to 1200 ° C. which is higher than the temperature of the diffusion process (1150 ° C.). In the case of this high reheating temperature, the effect of stabilizing the characteristics is that of sample No. Stronger than 1-12. On the other hand, the insulation resistance of the sample No. 1-1
Although it is lower than 2, it is within the practical range.
【００２５】再加熱処理時の酸化性雰囲気の酸素濃度と
特性の関係を調べるために、半導体磁器の組成、絶縁化
物質の組成及び再加熱処理の温度を試料Ｎｏ．７〜１２
と同一にし、再加熱処理の雰囲気をＮ2 ９０容積％＋Ｏ
2１０容積％とした他は試料Ｎｏ．１と同一の方法で試
料Ｎｏ．２５〜３０の磁器コンデンサを作り、同一の方
法で特性を測定したところ、次の表３に示す結果が得ら
れた。In order to investigate the relationship between the oxygen concentration and the characteristics of the oxidizing atmosphere during the reheating treatment, the composition of the semiconductor porcelain, the composition of the insulating material and the temperature of the reheating treatment were set to Sample No. 7-12
The same as above, and the reheating atmosphere is N 2 90% by volume + O
Sample No. 2 except that 10% by volume was used. Sample No. When 25 to 30 porcelain capacitors were made and the characteristics were measured by the same method, the results shown in the following Table 3 were obtained.
【００２６】[0026]
【表３】 [Table 3]
【００２７】耐湿負荷試験後の絶縁抵抗Ｒ2 について、
表３の試料Ｎｏ．２５〜３０と表２の試料Ｎｏ．１９〜
２４とを比較すると、試料Ｎｏ．２５〜３０の方が優れ
ていることは明らかである。Regarding the insulation resistance R2 after the moisture resistance load test,
Sample No. of Table 3 25-30 and the sample No. of Table 2. 19-
When compared with Sample No. 24, Sample No. Obviously, 25 to 30 is superior.
【００２８】絶縁化物質の拡散後における再加熱処理の
雰囲気を大気よりも酸素濃度が高い雰囲気にすることが
好ましいことを確かめるために、半導体磁器の組成、絶
縁化物質の組成及び再加熱処理の温度を試料Ｎｏ．７〜
１２と同一にし、再加熱処理の雰囲気をＮ2 ７０容積％
＋Ｏ2 ３０容積％とした他は試料Ｎｏ．１と同一の方法
で試料Ｎｏ．３１〜３６の磁器コンデンサを作り、同一
の方法で特性を測定したところ、次の表４に示す結果が
得られた。In order to confirm that it is preferable that the atmosphere for the reheating treatment after the diffusion of the insulating material is an atmosphere having an oxygen concentration higher than that of the atmosphere, the composition of the semiconductor porcelain, the composition of the insulating material and the reheating treatment are performed. Sample No. 7-
12 and the reheating atmosphere is N 2 70% by volume
+ O 2 30% by volume, except for sample No. Sample No. When the porcelain capacitors Nos. 31 to 36 were made and the characteristics were measured by the same method, the results shown in Table 4 below were obtained.
【００２９】[0029]
【表４】 [Table 4]
【００３０】表４の試料Ｎｏ．３１〜３６の絶縁抵抗Ｒ
1 、Ｒ2 と表２の試料Ｎｏ．７〜１２の絶縁抵抗Ｒ1 、
Ｒ2 との比較から明らかなように、酸素の濃度を大気よ
りも高くすると、絶縁抵抗が高くなり、且つ安定性もよ
くなる。従って、再加熱処理は大気よりも酸素濃度の大
きい雰囲気で行うことが望ましい。Sample No. of Table 4 Insulation resistance R of 31 to 36
1, R2 and the sample No. of Table 2. Insulation resistance R1 of 7 to 12,
As is clear from the comparison with R2, when the oxygen concentration is higher than that in the atmosphere, the insulation resistance becomes higher and the stability becomes better. Therefore, it is desirable that the reheating treatment be performed in an atmosphere having a higher oxygen concentration than the air.
【００３１】[0031]
【変形例】本発明は上述の実施例に限定されるものでな
く、例えば次の変形が可能なものである。 （１） 実施例にはＳｒＴｉＯ3 磁器コンデンサ、（Ｓ
ｒ、Ｃａ）ＴｉＯ3 磁器コンデンサが示されているが、
ＢａＴｉＯ3 又はこのＢａサイト（Ａサイト）をＢａ、
Ｓｒ、Ｃａ、Ｍｇ、Ｚｎの２価の物質の組み合せとし、
Ｔｉサイト（Ｂサイト）の一部をＴｉ以外の４価の物質
（Ｚｒ等）に置き換えることができる。要するに、あら
ゆる粒界絶縁型磁器コンデンサに本発明を適用すること
ができる 。 （２） Ｎｂ2 Ｏ5 の他に、Ｙ2 Ｏ3 、Ｌａ
2 Ｏ3 、ＣｅＯ2 、ＷＯ3 等の物質を単独又は組み合せ
で使用することができる。 （３） 絶縁化物質としてＢｉ2 Ｏ3 、ＰｂＯ、Ｂ2Ｏ
3 、の他に、ＭｎＯ、ＣｕＯ、ＳｉＯ2 、Ａｌ2 Ｏ3 、
Ｔｌ2 Ｏ3 、Ｓｂ2 Ｏ3 、Ｆｅ2 Ｏ3 等の種々の金属酸
化物を単独で又は組み合せで使用することができる。 （４） 絶縁化物質のペーストをスクリーン印刷する代
りに、絶縁化物質を蒸着等で半導体磁器の表面に付着さ
せることができる。 （５） 半導体磁器の出発原料として炭酸ストロンチウ
ム、炭酸カルシウム、酸化チタン等を使用し、大気雰囲
気中での仮焼工程を設けてもよい。 （６） 半導体磁器を得る工程と、絶縁化物質を拡散す
る工程と、再加熱処理の工程とを連続的に設けることが
できる。 （７） 再加熱処理の雰囲気中に、ＣｕＯ（酸化銅）、
Ｃｒ2 Ｏ3 （酸化クロム）、Ｃｏ3 Ｏ4 （酸化コバル
ト）、ＮｉＯ（酸化ニッケル）、ＡｇＯ（酸化銀）、Ｚ
ｎＯ（酸化亜鉛）、Ｍｎ3 Ｏ4 （酸化マンガン）、Ｆｅ
2 Ｏ3 （酸化鉄）を含めることができる。[Modifications] The present invention is not limited to the above-described embodiment, and for example, the following modifications are possible. (1) An SrTiO 3 porcelain capacitor, (S
r, Ca) TiO3 porcelain capacitors are shown,
BaTiO 3 or this Ba site (A site) is Ba,
A combination of divalent substances of Sr, Ca, Mg and Zn,
A part of the Ti site (B site) can be replaced with a tetravalent substance (Zr or the like) other than Ti. In short, the present invention can be applied to any grain boundary insulating porcelain capacitor. (2) In addition to Nb 2 O 5 , Y 2 O 3 and La
Substances such as 2 O 3 , CeO 2 and WO 3 can be used alone or in combination. (3) Bi 2 O 3 , PbO, B 2 O as insulating materials
3 , MnO, CuO, SiO 2 , Al 2 O 3 ,
Various metal oxides such as Tl 2 O 3 , Sb 2 O 3 and Fe 2 O 3 can be used alone or in combination. (4) Instead of screen-printing the insulating substance paste, the insulating substance can be deposited on the surface of the semiconductor porcelain by vapor deposition or the like. (5) Strontium carbonate, calcium carbonate, titanium oxide or the like may be used as a starting material for the semiconductor porcelain, and a calcination step in the atmosphere may be provided. (6) The step of obtaining the semiconductor porcelain, the step of diffusing the insulating substance, and the step of reheating treatment can be continuously provided. (7) CuO (copper oxide) in the atmosphere of the reheating treatment,
Cr 2 O 3 (chromium oxide), Co 3 O 4 (cobalt oxide), NiO (nickel oxide), AgO (silver oxide), Z
nO (zinc oxide), Mn 3 O 4 (manganese oxide), Fe
2 O 3 (iron oxide) can be included.
【００３２】[0032]
【発明の効果】上述から明らかなように、本発明によれ
ば絶縁抵抗が高く且つ安定性が高い磁器コンデンサを提
供することができる。As is apparent from the above, according to the present invention, it is possible to provide a porcelain capacitor having high insulation resistance and high stability.
【図１】本発明の実施例に従う磁器コンデンサを製造す
るための半導体磁器を原理的に示す断面図である。1 is a sectional view showing in principle a semiconductor porcelain for manufacturing a porcelain capacitor according to an embodiment of the present invention.
【図２】半導体磁器の表面に粒界絶縁化物質層を形成し
た状態を示す断面図である。FIG. 2 is a cross-sectional view showing a state in which a grain boundary insulating material layer is formed on the surface of a semiconductor ceramic.
【図３】粒界絶縁層を形成した半導体磁器を原理的に示
す断面図である。FIG. 3 is a sectional view showing in principle a semiconductor porcelain having a grain boundary insulating layer formed thereon.
【図４】粒界絶縁型半導体磁器コンデンサを原理的に示
す断面図である。FIG. 4 is a sectional view showing in principle a grain boundary insulation type semiconductor ceramic capacitor.
１ 半導体磁器 ２ 粒子 ４ 粒界絶縁層 1 semiconductor porcelain 2 particles 4 grain boundary insulating layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井口 喜章 東京都台東区上野６丁目16番20号 太陽誘 電株式会社内 (56)参考文献 特開 昭53−142650（ＪＰ，Ａ) 実開 平２−194510（ＪＰ，Ｕ) 特公 昭49−25999（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiaki Iguchi 6-16-20 Ueno, Taito-ku, Tokyo Within Taiyo Denki Co., Ltd. (56) Reference JP-A-53-142650 (JP, A) 2-194510 (JP, U) JP-B-49-25999 (JP, B1)
Claims (1)
体粒子の集まりからなる半導体磁器を得る工程と、 前記半導体磁器の表面に粒界絶縁化物質を付着させ、前
記半導体磁器を大気中で加熱することによって前記粒界
絶縁化物質を前記半導体粒子の境界領域に拡散させて粒
界絶縁層を形成する工程と、 前記粒界絶縁層を形成した半導体磁器に対して、酸素の
割合が大気以上の酸化性雰囲気中で前記粒界絶縁層を形
成した時の加熱温度よりも低い温度によって加熱処理を
施す工程とを有することを特徴とする粒界絶縁型半導体
磁器の製造方法。1. A obtaining a semiconductor ceramic made of a collection of semiconductor particles by firing a compact of a semiconductor ceramic material, to adhere the grain boundary insulated material on the surface of the semiconductor ceramic, the semiconductor ceramic in air said grain boundary insulated material is diffused into the boundary region of the semiconductor particles by heating and forming a grain boundary insulating layer, for the semiconductor ceramic forming the grain boundary insulating layer, oxygen
Forming the grain boundary insulating layer in an oxidizing atmosphere with a proportion higher than air
Heat treatment at a temperature lower than the heating temperature when
A method for manufacturing a grain boundary insulation type semiconductor porcelain, comprising:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-86217 | 1991-03-26 | ||
| JP8621791 | 1991-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0536560A JPH0536560A (en) | 1993-02-12 |
| JPH0828306B2 true JPH0828306B2 (en) | 1996-03-21 |
Family
ID=13880615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3314092A Expired - Lifetime JPH0828306B2 (en) | 1991-03-26 | 1991-10-31 | Method for manufacturing grain boundary insulated semiconductor porcelain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0828306B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4925999A (en) * | 1972-04-20 | 1974-03-07 | ||
| JPS6057213B2 (en) * | 1977-05-18 | 1985-12-13 | 株式会社村田製作所 | Manufacturing method of grain boundary insulated semiconductor ceramic capacitor |
| JPH02194510A (en) * | 1989-01-23 | 1990-08-01 | Sumitomo Metal Ind Ltd | Manufacturing method of semiconductor ceramic capacitor |
-
1991
- 1991-10-31 JP JP3314092A patent/JPH0828306B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536560A (en) | 1993-02-12 |
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