JPH0470763B2 - - Google Patents
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- Publication number
- JPH0470763B2 JPH0470763B2 JP63309378A JP30937888A JPH0470763B2 JP H0470763 B2 JPH0470763 B2 JP H0470763B2 JP 63309378 A JP63309378 A JP 63309378A JP 30937888 A JP30937888 A JP 30937888A JP H0470763 B2 JPH0470763 B2 JP H0470763B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- mol
- dielectric constant
- grain boundary
- semiconductor ceramic
- 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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- 239000004065 semiconductor Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 30
- 239000000919 ceramic Substances 0.000 claims description 23
- 229960004643 cupric oxide Drugs 0.000 claims description 15
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- 229910002367 SrTiO Inorganic materials 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative 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
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- -1 0.01 to 1.0 mol% Chemical compound 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017676 MgTiO3 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
Description
［産業上の利用分野］
本発明は粒界絶縁型半導体磁器組成物に係り、
特にチタン酸ストロンチウムとチタン酸マグネシ
ウムとを主成分とする、極めて高い誘電率を有
し、かつ誘電損失、誘電率の温度変化が少ない高
特性粒界絶縁型半導体磁器組成物に関する。
［従来の技術］
粒界絶縁型半導体磁器組成物は、従来よりIC
回路のコンデンサ素子材料として広く利用されて
いる。しかして、従来、粒界絶縁型半導体磁器組
成物としては、例えばチタン酸バリウムを主成分
とし、原子価制御剤等の微量添加物を配合した半
導体磁器の結晶粒界を酸化第二銅（CuO）等を熱
拡散させて絶縁化したものが知られている。この
組成物は、誘電率が50000と大きい反面、誘電損
失も５％と大きく、誘電率の温度変化も−25℃〜
＋85℃の範囲において、±15％を超えるという欠
点を有していた。
近年、上記粒界絶縁型半導体磁器組成物の欠点
を改良した粒界絶縁型半導体磁器組成物として、
チタン酸ストロンチウムを主成分とするものが数
多く報告されている。例えば、特公昭60−46811
号公報には、チタン酸ストロンチウム97.7〜
99.85重量％、二酸化マンガン0.05〜0.8重量％、
及び酸化ランタン0.1〜1.5重量％からなる半導体
磁器の結晶粒界に酸化ビスマス等を拡散させて絶
縁体化した組成物が開示されている。組成物は、
誘電率が50000、誘電損失が0.8％、誘電率の温度
変化率が−30〜＋85℃の範囲で＋８％以下という
特性を有しており、上記組成物に対して誘電損
失、誘電率の温度変化が改善されている。
［発明が解決しようとする課題］
近年、回路のIC化が急速に進み、コンデンサ
の小型大容量化への要望は更に高くなつており、
誘電損失や誘電率の温度変化がより少なく、しか
もよい高い誘電率を有する粒界絶縁型半導体磁器
組成物の開発が強く要求されている。
本発明は上記実情に鑑みてなされたものであつ
て、極めて高い誘電率を有し、かつ誘電損失、誘
電率の温度変化が著しく小さい、高特性粒界絶縁
型半導体磁器組成物を提供することを目的とす
る。
［課題が解決しようとする手段及び作用］
請求項１の粒界絶縁型半導体磁器組成物は、チ
タン酸ストロンチウム92〜80モル％及びチタン酸
マグネシウム８〜20モル％からなる主成分に、該
主成分に対するとモル比で、酸化第二銅0.01〜
0.5モル％と、酸化珪素0.01〜1.0モル％、酸化ニ
オブ、酸化ランタン、酸化イツトリウム、酸化タ
ンタル及び酸化タングステンよりなる群から選ば
れる少なくとも１種を0.05〜0.8モル％とが添加
された組成を有し、半導体磁器の結晶粒界を絶縁
化してなることを特徴とする。
請求項２の粒界絶縁型半導体磁器組成物は請求
項１において、半導体磁器の表面にビスマス及
び／又は銅の酸化物又は硝酸塩を含む絶縁化剤を
塗布して熱拡散することにより、該半導体磁器の
結晶粒界を絶縁化したことを特徴とする。
以下に本発明を詳細に説明する。
本発明の粒界絶縁型半導体磁器組成物は、チタ
ン酸ストロンチウム（SrTiO3）及びチタン酸マ
グネシウム（MgTiO3）を主成分とし、これに諸
特性改善のための各種添加剤を加えたものであ
る。
本発明の粒界絶縁型半導体磁器組成物におい
て、MgTiO3は、結晶粒子成長を適度に抑制し、
磁器に粒子の均一かつ安定な成長をもたらし、誘
電率の温度変化を低減する機能を有するものであ
る。MgTiO3の添加量が８モル％未満でSrTiO3
の添加量が92モル％を超えると、誘電率の温度変
化率が±８％程度と比較的大きくするため、十分
な改善効果が得られない。逆にMgTiO3が20モル
％を超え、SrTiO3が80モル％未満では、結晶粒
子の成長が極度に抑制されて誘電率が低下し、誘
電損失も増大する。従つて、主成分である
SrTiO3及びMgTiO3の配合割合は、SrTiO392〜
80モル％、MgTiO38〜20モル％とする。
SrTiO3及びMgTiO3よりなる主成分に添加す
る添加剤のうち、酸化第二銅（CuO）は、結晶粒
子の成長を制御する機能を有し、上記主成分に対
するCuOの添加量が、0.01モル％未満では、粒子
成長が不均一となり誘電率が低下し、誘電損失が
増加する。逆に0.5モル％を超えると粒子成長が
抑制され誘電率が低下する。従つて、CuOの添加
量は主成分に対して0.01〜0.5モル％とする。
酸化珪素（SiO2）は結晶粒子を成長させる機
能を有し、主成分に対するSiO2の添加量が0.01モ
ル％未満では粒子成長が不十分となり、誘電率の
低下、誘電率の温度変化の増大を招く。逆に1.0
モル％を超えると、粒子成長が抑制されて誘電率
が低下する。従つて、SiO2の添加量は主成分に
対して0.01〜1.0モル％とする。
酸化ニオブ、酸化ランタン、酸化イツトリウ
ム、酸化タンタル、酸化タングステンは、原子価
制御剤として添加されるものであつて、酸化スト
ロンチウムの半導体化を促進する作用を奏する。
これらは１種を単独で用いても良く、２種以上を
併用しても良いが、その添加量（２種以上を併用
する場合は合計の添加量）が、前記主成分に対し
て0.05モル％未満では、半導体の体積抵抗率が高
くなつて誘電率が低下する。逆に、0.8モル％を
超えると、結晶粒子の成長が抑制されて誘電率が
低下するとともに誘電損失も増加する。従つて、
これらの原子制御剤の添加量は主成分に対して
0.05〜0.8モル％とする。
本発明の粒界絶縁型半導体磁器組成物は、上記
主成分及び各種添加剤の所定量を配合して得られ
る半導体磁器の結晶粒界を絶縁化してなるもので
あるが、この絶縁化方法としては、ビスマスの酸
化物、硝酸塩及び銅の酸化物、硝酸塩よりなる群
から選ばれる１種又は２種以上を絶縁化剤として
用い、これを半導体磁器表面に塗布して熱拡散す
る方法が好適である。
本発明の粒界絶縁型半導体磁器組成物は、例え
ば次のようにして製造することができる。
即ち、まず、SrTiO3、MgTiO3、CuO、SiO2
及び原子価制御剤の所定量を湿式ボールミル等で
十分に混合粉砕する。この場合、SrTiO3は、炭
酸ストロンチウム（SrCO3）と二酸化チタン
（TiO2）とを配合することにより、MgTiO3は炭
酸マグネシウム（MgCO3）と二酸化チタン
（TiO2）とを配合することにより調製することが
できる。得られた混合物を乾燥後、大気中で1000
〜1200℃にて２〜３時間程度仮焼し、冷却後粉砕
する。得られた粉末にバインダーを加えて常法に
従つて加圧成形した後、大気中、700〜1000℃に
て２〜３時間程度仮焼してバインダーを除去し、
その後水素１〜10容量％の窒素又はアルゴン気流
中で1400〜1450℃で４〜６時間程度焼成して焼結
する。
得られた焼結体の表面に、前記絶縁化剤をアル
コール等の溶液として塗布し、900〜1250℃で30
分〜２時間熱処理することによりこれを結晶粒界
に熱拡散させて、絶縁化する。
このようにして得られる本発明の粒界絶縁型半
導体磁器組成物は、通常の場合、誘電率が40000
〜50000と高く、誘電損失が0.8％以下、誘電率の
温度変化が−25℃〜＋85℃の範囲で±２％以内と
極めて低いものである。
［実施例］
以下に実施例及び比較例を挙げて、本発明をよ
り具体的に説明するが、本発明はその要旨を超え
ない限り、以下の実施例に限定されるものではな
い。
実施例１〜６、比較例１、２
チタン酸ストロンチウム（SrTiO3）とチタン
酸マグネシウム（MgTiO3）が第１表に示す割合
となるように、炭酸ストロンチウム（SrCO3）、
炭酸マグネシウム（MgCO3）、二酸化チタン
（TiO2）をそれぞれ秤量した。また、チタン酸ス
トロンチウムとチタン酸マグネシウムの合計100
モルに対し、五酸化ニオブ（Nb2O5）、酸化第二
銅（CuO）、酸化珪素（SiO2）を第１表の配合割
合となるように秤量した。
これらを湿式ボールミルで20時間混合粉砕処理
を行なつた後、乾燥した。この混合物を大気中
1100℃で３時間仮焼し、冷却後、微粉砕した。得
られた粉末にバインダーを加え、圧力1ton／cm2で
直径10mmの円盤に成形した。成形品は、大気中
1000℃で２時間仮焼してバインダーを除いた後、
水素１〜10容量％の窒素気流中にて1440℃の温度
で５時間焼結した。
得られた焼結体の表面に、絶縁化剤として酸化
ビスマス（Bi2O3）及び酸化第二銅（CuO）のア
ルコール溶液（Bi2O395重量％、CuO5重量％）
を約0.2mg／mm2塗布した後、1000℃で２時間拡散
処理し、粒界層の絶縁化を行なつた。
このようにして得られた粒界絶縁型半導体磁器
の両面に銀電極を塗布焼付し、これを用いて、諸
特性の測定を行なつた。なお、誘電率と誘電損失
は、1kHz、25℃で測定した。また、絶縁抵抗は、
25℃において直流電圧25Vを印加し、60秒後の抵
抗値で測定した。誘電率の温度特性は、−25℃〜
＋85℃の温度範囲で25℃を基準とし算出した。
結果を第２表に示す。
第２表より、本発明の粒界絶縁型半導体磁器組
成物は、著しく誘電率が高く、誘電損失は非常に
小さく、特に誘電率の温度変化が著しく小さい、
高特性粒界絶縁型半導体磁器組成物であることが
明らかである。
[Industrial Application Field] The present invention relates to a grain boundary insulated semiconductor ceramic composition,
In particular, the present invention relates to a grain boundary insulated semiconductor ceramic composition having extremely high dielectric constant and having low dielectric loss and small temperature change in dielectric constant, which is mainly composed of strontium titanate and magnesium titanate. [Prior art] Grain boundary insulated semiconductor ceramic compositions have traditionally been used for IC
It is widely used as a material for capacitor elements in circuits. Conventionally, grain boundary insulated semiconductor porcelain compositions have been made using cupric oxide (CuO ) etc. are known to be insulated by thermal diffusion. Although this composition has a large dielectric constant of 50,000, it also has a large dielectric loss of 5%, and the temperature change in the dielectric constant is from -25℃ to
It had the disadvantage that it exceeded ±15% in the +85°C range. In recent years, grain boundary insulated semiconductor ceramic compositions have been developed that improve the drawbacks of the above-mentioned grain boundary insulated semiconductor ceramic compositions.
Many products containing strontium titanate as a main component have been reported. For example, Special Public Interest Publication Showa 60-46811
In the publication, strontium titanate 97.7 ~
99.85% by weight, manganese dioxide 0.05-0.8% by weight,
Also disclosed is a composition in which bismuth oxide or the like is diffused into the grain boundaries of a semiconductor ceramic made of 0.1 to 1.5% by weight of lanthanum oxide to make it an insulator. The composition is
It has the characteristics of a dielectric constant of 50,000, a dielectric loss of 0.8%, and a temperature change rate of the dielectric constant of +8% or less in the range of -30 to +85°C. Changes have been improved. [Problem to be solved by the invention] In recent years, the use of IC circuits has progressed rapidly, and the demand for smaller capacitors with larger capacities has become even higher.
There is a strong demand for the development of a grain-boundary insulated semiconductor ceramic composition that has less dielectric loss and temperature change in dielectric constant, and has a high dielectric constant. The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a high-quality grain boundary insulated semiconductor ceramic composition which has an extremely high dielectric constant and exhibits extremely small dielectric loss and temperature change in the dielectric constant. With the goal. [Means and effects to solve the problem] The grain boundary insulated semiconductor ceramic composition of claim 1 is characterized in that the main components are 92 to 80 mol% of strontium titanate and 8 to 20 mol% of magnesium titanate. In molar ratio to the components, cupric oxide 0.01~
0.5 mol% and 0.05 to 0.8 mol% of at least one selected from the group consisting of silicon oxide, 0.01 to 1.0 mol%, niobium oxide, lanthanum oxide, yttrium oxide, tantalum oxide, and tungsten oxide. It is characterized in that it is made by insulating the crystal grain boundaries of semiconductor porcelain. The grain boundary insulated semiconductor ceramic composition according to claim 2 is the semiconductor ceramic composition according to claim 1, which is prepared by applying an insulating agent containing an oxide or nitrate of bismuth and/or copper to the surface of the semiconductor ceramic and thermally diffusing it. It is characterized by insulating the grain boundaries of porcelain. The present invention will be explained in detail below. The grain boundary insulated semiconductor ceramic composition of the present invention contains strontium titanate (SrTiO 3 ) and magnesium titanate (MgTiO 3 ) as main components, to which various additives are added to improve various properties. . In the grain boundary insulated semiconductor ceramic composition of the present invention, MgTiO 3 moderately suppresses crystal grain growth,
It has the function of causing uniform and stable growth of particles in porcelain and reducing temperature changes in dielectric constant. SrTiO 3 when the amount of MgTiO 3 added is less than 8 mol%
If the amount added exceeds 92 mol %, the temperature change rate of the dielectric constant becomes relatively large, about ±8%, and a sufficient improvement effect cannot be obtained. Conversely, if MgTiO 3 exceeds 20 mol % and SrTiO 3 exceeds 80 mol %, the growth of crystal grains is extremely suppressed, the dielectric constant decreases, and the dielectric loss also increases. Therefore, the main component is
The blending ratio of SrTiO 3 and MgTiO 3 is SrTiO 3 92 ~
80 mol%, MgTiO3 8-20 mol%. Among the additives added to the main components consisting of SrTiO 3 and MgTiO 3 , cupric oxide (CuO) has the function of controlling the growth of crystal grains, and the amount of CuO added to the above main components is 0.01 mol. If it is less than %, grain growth becomes non-uniform, the dielectric constant decreases, and dielectric loss increases. On the other hand, if it exceeds 0.5 mol%, grain growth is suppressed and the dielectric constant decreases. Therefore, the amount of CuO added is 0.01 to 0.5 mol% based on the main components. Silicon oxide (SiO 2 ) has the function of growing crystal grains, and if the amount of SiO 2 added to the main component is less than 0.01 mol%, grain growth will be insufficient, resulting in a decrease in dielectric constant and an increase in temperature changes in dielectric constant. invite. 1.0 on the contrary
If it exceeds mol%, grain growth is suppressed and the dielectric constant decreases. Therefore, the amount of SiO 2 added is 0.01 to 1.0 mol % based on the main components. Niobium oxide, lanthanum oxide, yttrium oxide, tantalum oxide, and tungsten oxide are added as valence control agents, and have the effect of promoting the conversion of strontium oxide into a semiconductor.
One type of these may be used alone or two or more types may be used in combination, but the amount added (if two or more types are used together, the total amount added) is 0.05 mol with respect to the main component. If it is less than %, the volume resistivity of the semiconductor increases and the dielectric constant decreases. On the other hand, if it exceeds 0.8 mol%, the growth of crystal grains is suppressed, the dielectric constant decreases, and the dielectric loss also increases. Therefore,
The amount of these atomic control agents added is based on the main component.
The amount should be 0.05 to 0.8 mol%. The grain boundary insulated semiconductor porcelain composition of the present invention is obtained by insulating the grain boundaries of semiconductor porcelain obtained by blending predetermined amounts of the above-mentioned main components and various additives. A suitable method is to use one or more insulating agents selected from the group consisting of bismuth oxides, nitrates, and copper oxides and nitrates, and to apply this to the surface of the semiconductor porcelain and thermally diffuse it. be. The grain boundary insulated semiconductor ceramic composition of the present invention can be produced, for example, as follows. That is, first, SrTiO 3 , MgTiO 3 , CuO, SiO 2
A predetermined amount of the valence control agent and the valence control agent are thoroughly mixed and ground using a wet ball mill or the like. In this case, SrTiO 3 is prepared by blending strontium carbonate (SrCO 3 ) and titanium dioxide (TiO 2 ), and MgTiO 3 is prepared by blending magnesium carbonate (MgCO 3 ) and titanium dioxide (TiO 2 ). can do. After drying the resulting mixture, 1000 min in air
Calcinate at ~1200°C for about 2 to 3 hours, cool, and then crush. After adding a binder to the obtained powder and press-molding it according to a conventional method, it is calcined in the atmosphere at 700 to 1000°C for about 2 to 3 hours to remove the binder.
Thereafter, it is sintered by firing at 1400 to 1450° C. for about 4 to 6 hours in a nitrogen or argon stream containing 1 to 10% hydrogen by volume. The insulating agent was applied as a solution of alcohol etc. to the surface of the obtained sintered body, and heated at 900 to 1250°C for 30 minutes.
By performing heat treatment for minutes to 2 hours, this is thermally diffused into the grain boundaries and insulated. The grain boundary insulated semiconductor ceramic composition of the present invention thus obtained usually has a dielectric constant of 40,000.
-50,000, the dielectric loss is 0.8% or less, and the temperature change in dielectric constant is extremely low, within ±2% in the range of -25°C to +85°C. [Examples] The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Examples 1 to 6, Comparative Examples 1 and 2 Strontium carbonate (SrCO 3 ) ,
Magnesium carbonate (MgCO 3 ) and titanium dioxide (TiO 2 ) were each weighed. In addition, a total of 100% of strontium titanate and magnesium titanate
Niobium pentoxide (Nb 2 O 5 ), cupric oxide (CuO), and silicon oxide (SiO 2 ) were weighed in the proportions shown in Table 1 based on the mole. These were mixed and pulverized in a wet ball mill for 20 hours, and then dried. This mixture in the atmosphere
The mixture was calcined at 1100°C for 3 hours, cooled, and then finely ground. A binder was added to the obtained powder, and the mixture was molded into a disk with a diameter of 10 mm under a pressure of 1 ton/cm 2 . Molded products are exposed to the atmosphere.
After calcining at 1000℃ for 2 hours and removing the binder,
Sintering was carried out at a temperature of 1440° C. for 5 hours in a nitrogen stream containing 1 to 10% hydrogen by volume. An alcoholic solution of bismuth oxide (Bi 2 O 3 ) and cupric oxide (CuO) (Bi 2 O 3 95% by weight, CuO 5% by weight) was applied to the surface of the obtained sintered body as an insulating agent.
After applying approximately 0.2 mg/mm 2 of the material, diffusion treatment was performed at 1000°C for 2 hours to insulate the grain boundary layer. Silver electrodes were coated and baked on both sides of the grain boundary insulated semiconductor porcelain thus obtained, and various properties were measured using the electrodes. Note that the dielectric constant and dielectric loss were measured at 1kHz and 25°C. In addition, the insulation resistance is
A DC voltage of 25V was applied at 25°C, and the resistance value was measured after 60 seconds. The temperature characteristics of dielectric constant are -25℃~
Calculated based on 25°C in a temperature range of +85°C. The results are shown in Table 2. From Table 2, it can be seen that the grain boundary insulated semiconductor ceramic composition of the present invention has a significantly high dielectric constant, a very small dielectric loss, and a particularly small temperature change in the dielectric constant.
It is clear that this is a grain boundary insulated semiconductor ceramic composition with high properties.
【表】【table】
【表】
［発明の効果］
以上詳述した通り、本発明の粒界絶縁型半導体
磁器組成物は、著しく誘電率が高く、誘電損失は
非常に小さく、また誘電率の温度変化は著しく小
さい、高特性粒界絶縁型半導体磁器組成物である
ため、本発明の粒界絶縁型半導体磁器組成物によ
れば、優れた特性を有するコンデンサの提供が可
能となり、IC回路の小型化、高容量化を図り信
頼性の高い製品を提供することができる。
特に、本発明の粒界絶縁型半導体磁器組成物
は、誘電率の温度変化率が著しく小さいため、温
度補償用コンデンサとして、静電容量の高いコン
デンサの提供が可能となり、回路の小型化、高信
頼性の面で工業上極めて有用である。[Table] [Effects of the Invention] As detailed above, the grain boundary insulated semiconductor ceramic composition of the present invention has an extremely high dielectric constant, an extremely small dielectric loss, and an extremely small temperature change in the dielectric constant. Since it is a grain-boundary insulated semiconductor ceramic composition with high characteristics, the grain-boundary insulated semiconductor ceramic composition of the present invention can provide capacitors with excellent characteristics, allowing for miniaturization and high capacity of IC circuits. We are able to provide highly reliable products. In particular, the grain-boundary insulated semiconductor ceramic composition of the present invention has a significantly small rate of change in dielectric constant with temperature, so it is possible to provide a capacitor with a high capacitance as a temperature compensation capacitor, resulting in smaller circuits and higher It is extremely useful industrially in terms of reliability.
Claims (1)
タン酸マグネシウム８〜20モル％からなる主成分
に、該主成分に対するモル比で、酸化第二銅0.01
〜0.5モル％と、酸化珪素0.01〜1.0モル％と、酸
化ニオブ、酸化ランタン、酸化イツトリウム、酸
化タンタル及び酸化タングステンよりなる群から
選ばれる少なくとも１種を0.05〜0.8モル％とが
添加された組成を有し、半導体磁器の結晶粒界を
絶縁化してなることを特徴とする粒界絶縁型半導
体磁器組成物。 ２ 半導体磁器の表面にビスマス及び／又は銅の
酸化物又は硝酸塩を含む絶縁化剤を塗布して熱拡
散することにより、該半導体磁器の結晶粒界を絶
縁化したことを特徴とする特許請求の範囲第１項
に記載の粒界絶縁型半導体磁器組成物。[Scope of Claims] 1 Main components consisting of 92 to 80 mol% of strontium titanate and 8 to 20 mol% of magnesium titanate, and 0.01 cupric oxide in a molar ratio to the main components.
~0.5 mol%, 0.01 to 1.0 mol% of silicon oxide, and 0.05 to 0.8 mol% of at least one selected from the group consisting of niobium oxide, lanthanum oxide, yttrium oxide, tantalum oxide, and tungsten oxide. 1. A grain boundary insulated semiconductor porcelain composition, characterized in that the grain boundary of the semiconductor porcelain is insulated. 2. A patent claim characterized in that the crystal grain boundaries of the semiconductor porcelain are insulated by applying an insulating agent containing bismuth and/or copper oxide or nitrate to the surface of the semiconductor porcelain and thermally diffusing the insulating agent. The grain boundary insulated semiconductor ceramic composition according to scope 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63309378A JPH02155210A (en) | 1988-12-07 | 1988-12-07 | Grain boundary insulation type semiconductor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63309378A JPH02155210A (en) | 1988-12-07 | 1988-12-07 | Grain boundary insulation type semiconductor porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02155210A JPH02155210A (en) | 1990-06-14 |
| JPH0470763B2 true JPH0470763B2 (en) | 1992-11-11 |
Family
ID=17992283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63309378A Granted JPH02155210A (en) | 1988-12-07 | 1988-12-07 | Grain boundary insulation type semiconductor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02155210A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111908914B (en) * | 2020-07-16 | 2021-06-18 | 广州天极电子科技股份有限公司 | Grain boundary layer ceramic material, preparation method and application of grain boundary layer ceramic substrate |
-
1988
- 1988-12-07 JP JP63309378A patent/JPH02155210A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02155210A (en) | 1990-06-14 |
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