JPH01236607A - Porcelain composition for reduction-reoxidation type semiconductor capacitor - Google Patents
Porcelain composition for reduction-reoxidation type semiconductor capacitorInfo
- Publication number
- JPH01236607A JPH01236607A JP63063955A JP6395588A JPH01236607A JP H01236607 A JPH01236607 A JP H01236607A JP 63063955 A JP63063955 A JP 63063955A JP 6395588 A JP6395588 A JP 6395588A JP H01236607 A JPH01236607 A JP H01236607A
- Authority
- JP
- Japan
- Prior art keywords
- reduction
- type semiconductor
- dielectric constant
- composition
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 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 claims description 11
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 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
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical group [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 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
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000015556 catabolic process 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
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium 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
- 239000003153 chemical reaction reagent Substances 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement 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, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
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底物に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a barium titanate based ceramic assembly 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
熱処理全行って表面に薄い誘電体層全形成して、これに
電極全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Ｍ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６
１−４４７３８号公報や特開昭５８−４８９０８号公報
に開示されているようにＢａＴｉ０ 、金主成分として
Ｌａ 、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７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。−万、誘電率の温度特性を改善
するためには、特公昭５θ−３７６９１号公報や特公昭
６６−４０９６５号公報に開示されているようにＢ１ｆ
ｔ添加したものが提案されている。Conventional technology In general, reduction-reoxidation type semiconductor capacitors are made by heat-treating dielectric ceramic in a reducing atmosphere to make it a semiconductor, then heat-treating it in air to form a thin dielectric layer on the surface, and then attaching all electrodes to this. obtained by doing. In this reduction-reoxidation type semiconductor capacitor, the dielectric M can be made thinner, so that the capacitor has a large apparent upper dielectric constant and is small in size and has a large 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, there are known BaTi0, gold-based materials to which oxides of rare earth elements such as La, Ce, Nd, etc. are added. These rare earth element oxides not only serve as semiconductor elements but also serve as 7-layers above the Curie point, so that 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. - In order to improve the temperature characteristics of the dielectric constant, B1f
It has been proposed to add t.
発明が解決しようとする課題
しかし、このようなりｉｔ添加した組成物では、焼成時
にＢｉ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１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
が一気特性のバラツキに与える影響が大きく問題となる
０
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
ンサ用磁器組成物ヲ提供することを目的とするものであ
る。Problems to be Solved by the Invention However, in such compositions in which it is added, Bi evaporates during firing, causing variations in electrical properties. In particular, since reduction and reoxidation type semiconductor capacitors use a dielectric layer with a thin surface and an electric layer, the non-uniformity near the surface due to the evaporation of B1 has a large effect on the variation in characteristics, which poses a problem. The object of the present invention is to provide a ceramic composition for reduction and reoxidation type semiconductor capacitors that is excellent in mass production and has good dielectric constant temperature characteristics.
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、ＢａＴ１０３８７
．４〜９７．３モルチ、Ｙｂ２０３ｏ、ｙ〜２．６モル
チ、ＴｉＯ２またはＺｒＯ２の少なくとも１つを２．０
〜１０．０モルチからなる組成物に対して、さらにＭｎ
０２ｔ−０〜ム、０重量％および８１０□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 BaT10387
．． 4 to 97.3 molti, Yb203o, y to 2.6 molti, at least one of TiO2 or ZrO2 to 2.0
For a composition consisting of ~10.0 molt.
02t-0~mu, 0% by weight and 810□0~1.0
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、半導体化元累兼キエ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 、Ｃｏ
、Ｐｒ 、Ｈｄ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、
これらよシイオン半径の小さな５１１Ｉ。Function: As a result of a detailed investigation of rare earth elements, which were previously considered to be shifters of the Chierly point at the origin of semiconductors, we found that La, Co,
, Pr, Hd, and other elements with relatively large ionic radii serve as semiconductor elements and Curie point shifters,
These 511I have a small ion radius.
Ｅｕ 、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Ｙｂ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、
ｙｂ２ｏ、の添加によ多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 the amount of shift of the Curie point is small for Eu and Gd. Furthermore, Yb, 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 multi-temperature characteristics can be obtained by adding yb2o.
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０ＢａＴｉ０５．Ｙｂ２０Ｂ 、 ＴｉＯ２、Ｚｒ
Ｏ２と試薬特級のＭｎＯ２、５ｉ０２ （純度はいずれ
も９９．９−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直径ｅ閣、厚さ
０．３６簡の円板に約１０００ｋｇ／ｄ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、直径約７．６調、厚み０．３ｍ
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８５０’Ｃ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１ＫＨｚ １Ｖ ｒｍｓで容量、ｔａｎδを測定
し誘電率を求めた。EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples. High purity 0BaTi05. Yb20B, TiO2, Zr
O2 and special reagent grade MnO2 and 5i02 (purities of 99.9 or higher) were blended to give the composition ratios shown in Table 1, mixed in a ball mill using agate stones, and dried. Next, the granules were granulated using an aqueous polyvinyl alcohol solution as a binder, sized to 32 mesh passes, and molded into a disc with a diameter of E and a thickness of 0.36 at a pressure of about 1000 kg/d. These molded bodies were fired in air at a temperature of 1300 to 1340°C for 2 hours to obtain a diameter of approximately 7.6 cm and a thickness of 0.3 m.
A disc-shaped dielectric porcelain was obtained. Next, silver paste was printed on both sides of this porcelain and baked at 850'C to form electrodes. Regarding the thus produced ceramic capacitor, the capacitance and tan δ were measured at 1 KHz and 1 V rms at 20° C., and the dielectric constant was determined.
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９５０〜１１６０℃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
８５０〜１０６０℃で４時間酸・化処理し、両面に銀ペ
ーストを印刷し８５０’Ｃ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。このようにして作成
した半導体コンデンサにライて、２０℃においてＩ Ｋ
Ｈｚ ｏ、１ｖｒｍｇで単位面積当りの容量（ｎＦ／ｄ
）、直流２５Ｖ印加で絶縁抵抗ＩＲ（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（ＴＯ）（−２５℃〜＋８５℃で２０℃基準
の変化率）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) for 4 hours at 950 to 1160°C to obtain semiconductor porcelain, which was then oxidized and oxidized in air at 850 to 1060°C for 4 hours to print silver paste on both sides. Then, baking was carried out at 850'C to form electrodes, and a reduction and reoxidation type semiconductor capacitor was obtained. Lying on the semiconductor capacitor made in this way, the I K
Capacity per unit area (nF/d
), insulation resistance IR (Ω) when DC 25V is applied, breakdown voltage BDV (V) and capacitance (permittivity) using DC boost breakdown method.
The temperature characteristics (TO) (rate of change from -25°C to +85°C with respect to 20°C) were measured. The results of these measurements are shown in Table 2.
（以下余白）
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ｓｂ、それ以外は本発明の範囲内のものであ
る。(The following is a margin) Those marked with * in Tables 1 and 2 are outside the scope of the present invention sb, and the others are within the scope of the present invention.
Ｙｂ２０．が０．７モル係より少ない場合、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
。Yb20. If it is less than 0.7 molar coefficient, the temperature characteristics of the dielectric constant deteriorate, and the insulation resistance and breakdown voltage decrease.
また、２．６モル％をこえる場合は誘電率の温度特性が
悪くなる。ＴｉＯ２またはｚｒｏ２の少なくとも１つｉ
２．０〜１０．Ｏモ／Ｌ／％としたのは、２．０モル係
よυ少ない場合、焼結体表面に針状結晶の析出が多くな
り、面積当シの容量および破壊電圧が低下し、１０．０
モル係よシ多くなると絶縁抵抗および破壊電圧が低下す
る。ＭｎＯ２の添加はｔａｎδの向上および絶縁抵抗の
向上に効果があるが、２．０Ｍ！％をこえると誘電率の
低下が大きくなる。５１０２の添加はＭｎＯ２と同様な
効果の池に焼成温度依存性を少なくする効果があるが、
１．０重重チをこえると誘電率の低下が大きくなる。Moreover, when it exceeds 2.6 mol%, the temperature characteristics of the dielectric constant deteriorate. at least one of TiO2 or zro2
2.0-10. The reason for setting Omo/L/% is that if the ratio is less than 2.0 mol, more acicular crystals will precipitate on the surface of the sintered body, and the capacity per area and breakdown voltage will decrease.
As the molar ratio increases, insulation resistance and breakdown voltage decrease. Addition of MnO2 is effective in improving tanδ and insulation resistance, but 2.0M! %, the decrease in dielectric constant becomes large. Although the addition of 5102 has the same effect as MnO2, it has the effect of reducing the dependence on firing temperature.
When the weight exceeds 1.0 weight, the decrease in dielectric constant becomes large.
なお、本実施例では出発原料としてＭｎ０２ｉ用いたが
、ＭｎＣ０Ｂ全ノ杓いてもＭｎとして１司量であれは同
様な結果が得られる。In this example, Mn02i was used as the starting material, but similar results can be obtained if all the MnC0B is used or if only one 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アリ、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. 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)
＿３０．７〜２．６モル％、ＴｉＯ＿２またはＺｒＯ＿
２の少なくとも１つを２．０〜１０．０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_387.4-97.3 mol%, Yb_2O
_30.7-2.6 mol%, TiO_2 or ZrO_
Furthermore, 0 to 2.0% by weight of MnO_2 is added to the composition containing 2.0 to 10.0 mol% of at least one of 2.
and a ceramic composition for a reduction and reoxidation type semiconductor capacitor containing 0 to 1.0% by weight of SiO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063955A JP2681981B2 (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 |
|---|---|---|---|
| JP63063955A JP2681981B2 (en) | 1988-03-17 | 1988-03-17 | Porcelain composition for reduction-reoxidation type semiconductor capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01236607A true JPH01236607A (en) | 1989-09-21 |
| JP2681981B2 JP2681981B2 (en) | 1997-11-26 |
Family
ID=13244252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63063955A Expired - Fee Related JP2681981B2 (en) | 1988-03-17 | 1988-03-17 | Porcelain composition for reduction-reoxidation type semiconductor capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2681981B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100415561B1 (en) * | 2001-04-02 | 2004-01-24 | 삼성전기주식회사 | A Dielectic Composition and a Method of Manufacturing Dielectric Body for Multilayer Ceramic Capacitor Using it |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940263A (en) * | 2018-06-07 | 2018-12-07 | 太仓萃励新能源科技有限公司 | A kind of MnO2Load TiO2The preparation method of monodimension nanometer material |
-
1988
- 1988-03-17 JP JP63063955A patent/JP2681981B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100415561B1 (en) * | 2001-04-02 | 2004-01-24 | 삼성전기주식회사 | A Dielectic Composition and a Method of Manufacturing Dielectric Body for Multilayer Ceramic Capacitor Using it |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2681981B2 (en) | 1997-11-26 |
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