JPH01236608A - Porcelain composition for reduction-reoxidation type semiconductor capacitor - Google Patents
Porcelain composition for reduction-reoxidation type semiconductor capacitorInfo
- Publication number
- JPH01236608A JPH01236608A JP63063957A JP6395788A JPH01236608A JP H01236608 A JPH01236608 A JP H01236608A JP 63063957 A JP63063957 A JP 63063957A JP 6395788 A JP6395788 A JP 6395788A JP H01236608 A JPH01236608 A JP H01236608A
- Authority
- JP
- Japan
- Prior art keywords
- reduction
- type semiconductor
- composition
- dielectric constant
- porcelain composition
- 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.)
- Pending
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 8
- 239000004065 semiconductor Substances 0.000 title claims description 20
- 239000003990 capacitor Substances 0.000 title claims description 16
- 238000010405 reoxidation reaction Methods 0.000 title description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- 230000015556 catabolic process Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1272—Semiconductive ceramic capacitors
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は各種電子機器に利用されるチタン酸バリウム系
の還元再酸化型半導体コンデンサ用磁器組成物に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a barium titanate-based ceramic composition for reduction and reoxidation type semiconductor capacitors used in various electronic devices.
従来の技術
一般に還元再酸化型半導体コンデンサは、誘電体磁器を
還元雰囲気中で熱処理して半導体化し、さらに空気中で
熱処理を行って表面に薄い誘電体層を形成して、これに
電極を付与することによって得られる。この還元再酸化
型半導体コンデンサは誘電体層を薄くできるため、見掛
は上誘電率が大きく小形で大容量で得られる。還元再酸
化型半導体コンデンサが得られる磁器組成は、特公昭５
１−４４７３８号公報や特開昭５８−４８９０８号公報
に開示嘔れているようにＢａＴｉ０ 、を主成分として
Ｌ＆、 Ｃｅ 、 Ｎｄ等の希土類元素酸化物を添加し
たものが知られている。これらの希土類元素酸化物は、
半導体化元素となるのみならずキュリー点のシフターと
なるため、室温付近で高誘電率が得られ、反面誘電率の
温度変化率が大きい。一方、誘電率の温度特性を改善す
るためには、特公昭６６−３７６９１号公報や特公昭５
６−４０９６５号公報に開示されているように８１を添
加したものが提案されている。Conventional technology In general, reduction-reoxidation semiconductor capacitors are made by heat-treating dielectric porcelain in a reducing atmosphere to turn it into a semiconductor, then heat-treating it in air to form a thin dielectric layer on the surface, and then attaching electrodes to this. obtained by doing. Since the dielectric layer of this reduction/reoxidation type semiconductor capacitor can be made thin, the capacitor has a large apparent upper dielectric constant and can be made compact and large in capacity. The ceramic composition from which reduction-reoxidation type semiconductor capacitors can be obtained is
As disclosed in JP-A No. 1-44738 and JP-A-58-48908, it is known that the main component is BaTi0 and rare earth element oxides such as L&, Ce, and Nd are added thereto. These rare earth element oxides are
Since it not only serves as a semiconductor element but also as a shifter of the Curie point, a high dielectric constant can be obtained near room temperature, and on the other hand, the temperature change rate of the dielectric constant is large. On the other hand, in order to improve the temperature characteristics of the dielectric constant,
As disclosed in Japanese Patent No. 6-40965, a compound containing 81 has been proposed.
発明が解決しようとする課題
しかし、このようなり１ を添加した組成物では、焼成
時にＢ１が蒸発し電気特性のバラツキの原因となる。特
に、還元再酸化型半導体コンデンサは表面の薄い誘電体
層を用いるため、Ｂ１の蒸発による表面付近の不均質が
電気特性のバラツキに与える影響が大きく問題となる。Problems to be Solved by the Invention However, in such a composition to which B1 is added, B1 evaporates during firing, causing variations in electrical properties. In particular, since a reduction-reoxidation type semiconductor capacitor uses a thin dielectric layer on the surface, non-uniformity near the surface due to evaporation of B1 has a large effect on variations in electrical characteristics, which poses a significant problem.
本発明はかかる点に鑑みてなされたもので、量産性に優
れ誘電率の温度特性が良好な還元再酸化型半導体コンデ
ンサ用磁器組成物を提供することを目的とするものであ
る。The present invention has been made in view of these points, and an object of the present invention is to provide a ceramic composition for reduction and reoxidation type semiconductor capacitors that is excellent in mass productivity and has good temperature characteristics of dielectric constant.
課題を解決するための手段
上記課題を解決するために本発明は、ＢａＴｉＯ３８４
，３〜９６，５モ／ｌ／％、Ｙ２Ｏ３１，ｏ〜３．７モ
ル係、ＴｉＯ２またけＺｒＯ２の少なくとも１つを２．
５〜１４．０モル係からなる組成物に対して、さらにＭ
ｎＯ２を０〜２．０重量％計よびＳｉＯ□を０〜１．０
重量％含有してなる還元再酸化型半導体コンデンサ用磁
器組成物を提供するものである。Means for Solving the Problems In order to solve the above problems, the present invention provides BaTiO384
, 3 to 96.5 mo/l/%, Y2O3 1,o to 3.7 mole, and at least one of TiO2 and ZrO2.
For a composition consisting of 5 to 14.0 molar ratio, M
nO2 from 0 to 2.0 wt% and SiO□ from 0 to 1.0
The object of the present invention is to provide a ceramic composition for a reduced and reoxidized semiconductor capacitor containing % by weight.
作用
従来、半導体化元素兼キュリー点のシフターと考えられ
ていた希土類元素を詳細に調べた結果、Ｌａ 、 ０６
、 Ｐｒ 、 Ｈａ 等比較的イオン半径の大きな
元素は、半導体化元素兼キュリー点のシフターの役目を
し、これらよりイオン半径の小さなＳｍ。Function: As a result of detailed investigation of rare earth elements, which were conventionally thought to be semiconducting elements and Curie point shifters, La, 06
, Pr, Ha, and other elements with relatively large ionic radii serve as semiconductor elements and Curie point shifters, and Sm, which has a smaller ionic radius than these, acts as a semiconductor element and a shifter of the Curie point.
ｌｃｕ 、 Ｇｄはキュリー点のシフト量が小さいこと
がわかった。さらにイオン半径の小さなＹは半導体化元
素の役目だけで、キュリー点のシフトはほとんどなく、
Ｙ２Ｏ，の添加により温度特性が良好な還元再酸化型半
導体コンデンサが得られることを見い出した。It was found that lcu and Gd have a small shift amount of the Curie point. Furthermore, Y, which has a small ionic radius, only serves as a semiconductor element, and there is almost no shift in the Curie point.
It has been found that a reduction and reoxidation type semiconductor capacitor with good temperature characteristics can be obtained by adding Y2O.
実施例
以下、実施例をあげて本発明につき詳細に説明する。高
純度のＢａＴｉ０． 、 Ｙ２Ｏ，、Ｔｉｅ□、 Ｚｒ
Ｏ２と試薬特級のＭｎＯ２，５ｉｎ２（純度はいずれ４
９９．９チ以上）を用い、第１表の組成比になるように
配、合し、メノウ玉石を用いたボールミルで混合し乾燥
した。次にポリビニルアルコール水溶液をバインダーと
して造粒し、３２メツシユパスに整粒し。EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples. High purity BaTi0. , Y2O,, Tie□, Zr
O2 and reagent grade MnO2, 5in2 (purity is 4
99.9 cm or more) were blended and combined so as to have the composition ratio shown in Table 1, mixed in a ball mill using agate boulders, and dried. Next, the particles were granulated using an aqueous polyvinyl alcohol solution as a binder, and the particles were sized to 32 mesh passes.
直径９ｍｍ、厚さ０．３５ｍｍの円゛板に約１ ｏ Ｏ
ＯＫｑ／＃の圧力で成形した。これらの成形体を空気中
で１３００〜１３４０℃の温度で２時間焼成して。Approximately 1 o O on a circular plate with a diameter of 9 mm and a thickness of 0.35 mm.
It was molded at a pressure of OKq/#. These molded bodies were fired in air at a temperature of 1300 to 1340°C for 2 hours.
直径約７．５ｍｍ、厚み０．３１１Ｉｍの円板形誘電体
磁器を得た。次にこの磁器の両面に銀ペーストを印刷し
８６０℃で焼付は電極とした。このようにして作成した
磁器コンデンサについて、２０℃において１Ｋｌ−１ｚ
Ｉ Ｖｒｍｓで容量、 ｔａｎδを測定し誘電率を求
めた。A disc-shaped dielectric ceramic having a diameter of about 7.5 mm and a thickness of 0.311 Im was obtained. Next, silver paste was printed on both sides of this porcelain and baked at 860°C to form electrodes. Regarding the ceramic capacitor made in this way, 1Kl-1z at 20℃
The capacitance and tan δ were measured at I Vrms to determine the dielectric constant.
また、空気中で焼成した誘電体磁器を還元雰囲気（Ｎ２
：Ｈ２＝９５：５）中で９６０〜１１６０℃で４時間還
元処理し半導体磁器を得、この半導体磁器を空気中で８
５０〜１０６０℃で４時間酸化゛処理し、両面に銀ペー
ストを印刷し８６０℃で焼付は電極を形成し、還元再酸
化型半導体コンデンサを得た。このよ：）Ｉ／’：して
作成した半導体コンデンサについて、２０″ＣｊＣおい
てＩ ＪＣＨ２ＯｏＩ Ｖｒｍｓで単位面積当りの容量
（ｎＦ／ａｔ）、直流２５Ｖ印加で絶縁抵抗ＸＲ（Ω）
、直流昇圧破壊方式で破壊電圧ＢＤＶ（Ｖ）および容量
（誘電率）の温度特性（Ｔ（５）、（２０’Ｃ基準）を
測定した。これらの測定結果を第２表に示す。In addition, dielectric porcelain fired in air was heated in a reducing atmosphere (N2
:H2=95:5) at 960 to 1160°C for 4 hours to obtain semiconductor porcelain.
Oxidation treatment was carried out at 50 to 1060°C for 4 hours, silver paste was printed on both sides, and electrodes were formed by baking at 860°C to obtain a reduction and reoxidation type semiconductor capacitor. For the semiconductor capacitor made like this :) I/': Capacitance per unit area (nF/at) at 20"CjC at I JCH2OoI Vrms, and insulation resistance XR (Ω) when DC 25V is applied.
The temperature characteristics (T(5), (20'C standard) of breakdown voltage BDV (V) and capacitance (permittivity) were measured using a DC boost breakdown method.The results of these measurements are shown in Table 2.
（以下余白）
〈第１表〉
く 第 ２ 表 〉
第１表および第２表で＊印を付したものは本発明の範囲
外のものであり、それ以外は本発明の範囲内のものであ
る。(Left below) Table 1 Table 2 Tables 1 and 2 marked with an asterisk are outside the scope of the present invention, and the rest are within the scope of the present invention. be.
Ｙ２Ｏ，が１，０モルチより少ない場合、誘電率の温度
特性が悪くなり、絶縁抵抗および破壊電圧が低下する。When Y2O, is less than 1.0 molti, the temperature characteristics of the dielectric constant deteriorate, and the insulation resistance and breakdown voltage decrease.
また、３．７モルチをこえる場合は誘電率の温度特性が
悪くなる。ＴｌＯ２またはＺｒＯ，、の少なくとも１つ
を２．５〜１４．０モルチとしたのは、２．５モルチよ
ジ少ない場合、焼結体表面に針状結晶の析出が多くなり
、面積当りの容量および破壊電圧が低下し、１４．○モ
ルチより多くなると絶縁抵抗および破壊電圧が低下する
。ＭｎＯ２の添力口はｔａｎδの向上および絶縁抵抗の
向上に効果があるが、２．０重量％をこえると誘電率の
低下が大きくなる。５１０２の添加１ｄＭｎｏ２と同様
な効果の他に焼成温度依存性を少なくする効果があるが
、１．０重量％をこえると誘電率の低下が大きくなる。Further, if the value exceeds 3.7 molti, the temperature characteristics of the dielectric constant deteriorate. The reason why at least one of TlO2 or ZrO is set to 2.5 to 14.0 molar is because if the amount is less than 2.5 molar, more acicular crystals will precipitate on the surface of the sintered body, and the capacity per area and the breakdown voltage decreases, 14. ○If the amount is more than 100%, insulation resistance and breakdown voltage will decrease. The addition of MnO2 is effective in improving tan δ and insulation resistance, but if it exceeds 2.0% by weight, the dielectric constant decreases significantly. Addition of 5102 has the same effect as 1 dMno2 and also has the effect of reducing firing temperature dependence, but if it exceeds 1.0% by weight, the dielectric constant will decrease significantly.
なお、本実施例では出発原料としてＭｎＯ，、を用いた
がｌＭｎＣＯ３を用いてもＭｎとして同量であれば同様
な結果が得られる。In this example, MnO was used as the starting material, but similar results can be obtained using lMnCO3 if the same amount of Mn is used.
また、第２表に半導体コンデンサとしての容量（誘電率
）の温度特性を示したが、還元処理する前の磁器コンデ
ンサの誘電率の温度特性もほぼこれと同様であり、本発
明の組成物は磁器コンデンサとしても使えることは言う
までもない。In addition, Table 2 shows the temperature characteristics of the capacitance (permittivity) as a semiconductor capacitor, and the temperature characteristics of the dielectric constant of a ceramic capacitor before reduction treatment are almost the same, and the composition of the present invention Needless to say, it can also be used as a magnetic capacitor.
発明の効果
以上のように本発明の組成物によれば、８１などの不安
定な元素を含まず量産性に優れ、誘電率の温度特性の良
好な還元再酸化型半導体コンデンサが得られ、実用的に
極めて有用である。Effects of the Invention As described above, according to the composition of the present invention, a reduction-reoxidation semiconductor capacitor that does not contain unstable elements such as 81, is excellent in mass production, and has good temperature characteristics of dielectric constant can be obtained, and is suitable for practical use. It is extremely useful.
Claims (1)
３１．０〜３．７モル％、ＴｉＯ＿２またはＺｒＯ＿２
の少なくとも１つを２．５〜１４．０モル％からなる組
成物に対して、さらにＭｎＯ＿２を０〜２．０重量％お
よびＳｉＯ＿２を０〜１．０重量％含有してなる還元再
酸化型半導体コンデンサ用磁器組成物。BaTiO_384.3-96.5 mol%, Y_2O_
31.0-3.7 mol%, TiO_2 or ZrO_2
A reduced and reoxidized type further containing 0 to 2.0% by weight of MnO_2 and 0 to 1.0% by weight of SiO_2 with respect to a composition consisting of 2.5 to 14.0 mol% of at least one of Porcelain composition for semiconductor capacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063957A JPH01236608A (en) | 1988-03-17 | 1988-03-17 | Porcelain composition for reduction-reoxidation type semiconductor capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063957A JPH01236608A (en) | 1988-03-17 | 1988-03-17 | Porcelain composition for reduction-reoxidation type semiconductor capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01236608A true JPH01236608A (en) | 1989-09-21 |
Family
ID=13244304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63063957A Pending JPH01236608A (en) | 1988-03-17 | 1988-03-17 | Porcelain composition for reduction-reoxidation type semiconductor capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01236608A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319517A (en) * | 1992-03-27 | 1994-06-07 | Tdk Corporation | Multilayer ceramic chip capacitor |
| CN102509601A (en) * | 2011-10-12 | 2012-06-20 | 华中科技大学 | Preparation method of barium titanate PTC (positive temperature coefficient) ceramic |
-
1988
- 1988-03-17 JP JP63063957A patent/JPH01236608A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319517A (en) * | 1992-03-27 | 1994-06-07 | Tdk Corporation | Multilayer ceramic chip capacitor |
| CN102509601A (en) * | 2011-10-12 | 2012-06-20 | 华中科技大学 | Preparation method of barium titanate PTC (positive temperature coefficient) ceramic |
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