JPH04318902A - Manufacture of voltage nonlinear element - Google Patents
Manufacture of voltage nonlinear elementInfo
- Publication number
- JPH04318902A JPH04318902A JP3112514A JP11251491A JPH04318902A JP H04318902 A JPH04318902 A JP H04318902A JP 3112514 A JP3112514 A JP 3112514A JP 11251491 A JP11251491 A JP 11251491A JP H04318902 A JPH04318902 A JP H04318902A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- zno
- voltage
- nonlinear element
- sintered body
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 172
- 239000011787 zinc oxide Substances 0.000 claims abstract description 86
- 239000000843 powder Substances 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 61
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 36
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims abstract description 26
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 25
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 19
- 239000011592 zinc chloride Substances 0.000 claims abstract description 19
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 abstract description 3
- 239000011565 manganese chloride Substances 0.000 abstract description 3
- 235000002867 manganese chloride Nutrition 0.000 abstract description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 2
- 235000011150 stannous chloride Nutrition 0.000 abstract description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 38
- 239000011521 glass Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 238000010304 firing Methods 0.000 description 11
- 229940102001 zinc bromide Drugs 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229910016264 Bi2 O3 Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 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
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020967 Co2 O3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- SHZGCJCMOBCMKK-KGJVWPDLSA-N beta-L-fucose Chemical compound C[C@@H]1O[C@H](O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-KGJVWPDLSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- KAGOZRSGIYZEKW-UHFFFAOYSA-N cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Co+3].[Co+3] KAGOZRSGIYZEKW-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は印加電圧によって抵抗値
が変化する電圧非直線性素子に関するもので，電圧安定
化，異常電圧制御，さらにはマトリクス駆動の液晶，Ｅ
Ｌなどの表示デバイスのスイッチング素子などに利用さ
れるものである。[Industrial Application Field] The present invention relates to a voltage nonlinear element whose resistance value changes depending on an applied voltage.
It is used for switching elements of display devices such as L.
【０００２】0002
【従来技術】従来の電圧非直線性素子は，酸化亜鉛（Ｚ
ｎＯ）に酸化ビスマス（Ｂｉ２ Ｏ３ ），酸化コバル
ト（Ｃｏ２ Ｏ３），酸化マンガン（ＭｎＯ２ ），酸
化アンチモン（Ｓｂ２ Ｏ３ ）などの酸化物を添加し
て，１０００〜１３５０℃で焼結したバリスタなど，種
々のものがある。その中で，ＺｎＯバリスタは電圧非直
線指数α，サージ耐量が大きいことから，最も一般的に
使われている（特公昭４６−１９４７２号公報参照）。
このような従来の電圧非直線性素子は，ＺｎＯバリスタ
を始めとして，素子の厚みを薄く（数十μｍ以下）する
ことに限界があるため，バリスタ電圧（バリスタに電流
１ｍＡを流した時の電圧Ｖ１ｍＡで表される）を低くす
ることに限界があり，低電圧用ＩＣの保護素子や低電圧
における電圧安定化素子としては使えなかった。[Prior Art] Conventional voltage nonlinear elements are made of zinc oxide (Z
Various types of varistors are made by adding oxides such as bismuth oxide (Bi2 O3), cobalt oxide (Co2 O3), manganese oxide (MnO2), and antimony oxide (Sb2 O3) to sintered at 1000 to 1350°C. There is something like that. Among them, ZnO varistors are the most commonly used because of their large voltage nonlinearity index α and surge resistance (see Japanese Patent Publication No. 46-19472). Conventional voltage nonlinear elements such as ZnO varistors have a limit in reducing the thickness of the element (several tens of micrometers or less), so the varistor voltage (the voltage when 1 mA of current is passed through the varistor) There is a limit to how low the current (expressed as V1mA) can be made to be, so it cannot be used as a protection element for low-voltage ICs or as a voltage stabilizing element at low voltages.
【０００３】また，上述したように，焼結時に，１００
０℃以上の高温プロセスを必要とするため，ガラス基板
上あるいは回路基板上に電圧非直線性素子を直接形成で
きないという問題があった。さらに，従来のものは並列
静電容量が大きく，たとえば液晶などのスイッチ素子と
しては不適当であるなどの問題点を有していた。この問
題点を解決し，たとえば液晶のスイッチング素子として
使えるようにするために，半導体化したＺｎＯ焼結体粒
子を主体とし，この粒子の表面に薄い絶縁性被膜を形成
させたものの集合体からなる電圧非直線性素子が開発さ
れた（たとえば特開昭６２−１９０８０１号公報参照）
。この方法は特に低電圧で電圧非直線性の優れたものが
比較的容易に得られること，並列静電容量が小さいもの
ができるという特徴がある。[0003] Furthermore, as mentioned above, during sintering, 100
Since a high temperature process of 0° C. or higher is required, there is a problem in that a voltage nonlinear element cannot be directly formed on a glass substrate or a circuit board. Furthermore, conventional devices have a large parallel capacitance, making them unsuitable as switching elements for liquid crystals, for example. In order to solve this problem and make it usable, for example, as a switching element for liquid crystals, we developed an aggregation system that consists mainly of semiconducting ZnO sintered particles with a thin insulating film formed on the surface of these particles. A voltage nonlinear element was developed (for example, see Japanese Patent Application Laid-open No. 190801/1983).
. This method is particularly characterized in that it is relatively easy to obtain a product with excellent voltage nonlinearity at low voltage, and that it can produce a product with a small parallel capacitance.
【０００４】この方法を更に詳しく説明すると，先ずＺ
ｎＯ，或いはこれに微量の添加物を加えたものを７００
℃以上の高温で焼成する。このようにして得られる焼結
体を０．５〜５０μｍの粒子径（平均粒子径１〜１０μ
ｍ）に粉砕する。この粉末に，高抵抗層化合物として，
たとえばＢｉ，Ｃｏ，Ｍｎ，Ｓｂなどの酸化物を添加し
て７００℃以上の温度で焼成する。これによってＺｎＯ
粉末の個々の粒子の表面がこれらの添加物成分を含む高
抵抗層で覆われた状態になる。To explain this method in more detail, first, Z
nO, or this with a small amount of additives added to 700
Fire at high temperatures above ℃. The sintered body thus obtained has a particle size of 0.5 to 50 μm (average particle size of 1 to 10 μm).
m). This powder is added as a high resistance layer compound.
For example, oxides such as Bi, Co, Mn, and Sb are added and fired at a temperature of 700° C. or higher. This allows ZnO
The surfaces of the individual particles of powder become coated with a high resistance layer containing these additive components.
【０００５】ところで，前記ＺｎＯバリスタの場合は，
焼結体を構成するＺｎＯ微結晶粒子自体の境界に高抵抗
の境界層を形成させて，この高抵抗層でバリスタ特性を
出していた。これに対して，上記電圧非直線性素子は，
高抵抗層がＺｎＯ微結晶粉末の表面に形成されたもので
ある。また，基本的には，この場合の表面高抵抗層は，
ＺｎＯバリスタの焼結体の微結晶粒子境界層と同質のも
のである。そして，上記ＺｎＯ微結晶粉末を，無機質あ
るいは有機質の結合材で固めて電極を付けて，電圧非直
線性素子としたものである。By the way, in the case of the ZnO varistor,
A high-resistance boundary layer is formed at the boundaries of the ZnO microcrystal particles that make up the sintered body, and this high-resistance layer provides varistor characteristics. On the other hand, the above voltage nonlinear element is
A high resistance layer is formed on the surface of ZnO microcrystalline powder. Also, basically, the surface high resistance layer in this case is
It is of the same quality as the microcrystal grain boundary layer of the sintered body of the ZnO varistor. Then, the ZnO microcrystalline powder is solidified with an inorganic or organic binder and electrodes are attached to form a voltage nonlinear element.
【０００６】こうして得られる電圧非直線性素子は，高
抵抗層で覆われたＺｎＯ微結晶粒子集合体の粒子接触を
，無機質あるいは有機質結合材で固着させた構造になっ
ている（後述の図１参照）。また，その電圧電流特性は
，非常に急峻な非直線性を示す。その微構造をＺｎＯバ
リスタとの比較で見れば，ＺｎＯバリスタは，微結晶粒
子は高抵抗層を通じて面接触しているのに対して，この
方法の素子は，微結晶粒子は高抵抗層を介して点接触し
ている。したがって，上記素子の持つ並列静電容量は，
従来のＺｎＯバリスタと比較して桁違いに小さい。
このことは，本素子を液晶のマトリックス駆動における
アクティブ素子として用いる場合，静電容量によるロス
がなくなり，高デューティー駆動に好適である。この方
法は，結合材を適当に選ぶことにより，液晶のＩＴＯ基
板上にバリスタ素子を形成することを可能にする。The voltage nonlinear element obtained in this way has a structure in which the particle contacts of the ZnO microcrystalline particle aggregate covered with the high resistance layer are fixed with an inorganic or organic binder (see Fig. 1 described later). reference). In addition, its voltage-current characteristics exhibit extremely steep nonlinearity. Comparing the microstructure with a ZnO varistor, we find that in the ZnO varistor, the microcrystalline particles are in surface contact through the high-resistance layer, whereas in devices using this method, the microcrystalline particles are in surface contact through the high-resistance layer. There is point contact. Therefore, the parallel capacitance of the above element is
It is orders of magnitude smaller than conventional ZnO varistors. This means that when this element is used as an active element in liquid crystal matrix drive, there is no loss due to capacitance, making it suitable for high-duty drive. This method makes it possible to form varistor elements on liquid crystal ITO substrates by appropriately selecting the bonding material.
【０００７】また，従来のバリスタ素子は，１０００℃
以上の高温プロセスを不可欠としていたので，直接基板
上にバリスタを形成することができなかった。しかし，
上記素子の製造方法では，あらかじめ作成したバリスタ
粒子を用いて，結合材で硬化，結合しさえすればよいわ
けである。バリスタ粒子を結合材と混ぜてペースト化し
，これを基板に印刷して，焼付け，硬化してバリスタを
形成することも可能である。バリスタを液晶のアクティ
ブマトリックス駆動用素子として使う試みは，種々検討
されてきた。しかし，実用化を阻んでいる問題は，バリ
スタ電圧の低いものが出来にくいということと，特性の
バラツキがあげられる。[0007] Furthermore, the conventional varistor element
Since the above-mentioned high-temperature process was essential, it was not possible to form varistors directly on the substrate. but,
In the above device manufacturing method, it is only necessary to use varistor particles prepared in advance and to harden and bond them with a bonding material. It is also possible to form a varistor by mixing varistor particles with a binder to form a paste, printing this on a substrate, baking and hardening. Various attempts have been made to use varistors as active matrix driving elements for liquid crystals. However, the problems that are hindering its practical application are that it is difficult to create a varistor with a low voltage, and that characteristics vary.
【０００８】バリスタ電圧は電極間距離に比例するから
，低いバリスタ電圧を得ようとすれば，電極間隔を短く
すれば良い。電極間隔が同じであっても，電極間に直列
に並ぶバリスタ粒子の数を制御することによって，バリ
スタ電圧を変えることができる。即ち，バリスタ粒子の
粒径を変えると，バリスタ電圧はそれに伴って変動する
。例えば，粒径が倍になると，バリスタ電圧は半分にな
る。電極間距離と粒径の制御によって，上記方法で得ら
れるバリスタ素子は，液晶のアクティブマトリックス駆
動素子として有用である。また，電極間距離１０〜数１
００μｍの範囲でもバリスタ電圧１０Ｖ以上で特性の優
れたものを，自由に得ることができる。Since the varistor voltage is proportional to the distance between the electrodes, in order to obtain a low varistor voltage, the distance between the electrodes can be shortened. Even if the electrode spacing is the same, the varistor voltage can be changed by controlling the number of varistor particles arranged in series between the electrodes. That is, when the particle size of the varistor particles is changed, the varistor voltage changes accordingly. For example, if the particle size doubles, the varistor voltage will be halved. By controlling the distance between the electrodes and the particle size, the varistor element obtained by the above method is useful as an active matrix driving element for liquid crystal. In addition, the distance between the electrodes is 10 to several 1
Even in the range of 00 μm, it is possible to freely obtain a varistor with excellent characteristics at a voltage of 10 V or more.
【０００９】[0009]
【解決しようとする課題】しかしながら，上記従来方法
（後者の公報）で得られる電圧非直線性素子は，次の問
題点がある。即ち，電圧非直線性素子を液晶のマトリッ
クス駆動用素子として使う場合は，駆動する画素１個に
１個ずつのバリスタをＩＴＯ基板上に形成しなければな
らない。たとえば，６４０×４８０の画素数であれば，
それだけの数のバリスタアレイを基板上に形成する必要
がある。そのため，これだけの数のバリスタを歩留まり
良く，バラツキを抑えて，作ることが要求される。その
ため，バリスタの粒子集合体を用いる上記従来の製造方
法は，バリスタ電圧のバラツキにはバリスタ粒子の粒径
のバラツキが直接に関係する。[Problem to be Solved] However, the voltage nonlinear element obtained by the above-mentioned conventional method (the latter publication) has the following problems. That is, when a voltage nonlinear element is used as a liquid crystal matrix driving element, one varistor must be formed on the ITO substrate for each pixel to be driven. For example, if the number of pixels is 640 x 480,
It is necessary to form that many varistor arrays on the substrate. Therefore, it is necessary to manufacture this many varistors at a high yield and with little variation. Therefore, in the conventional manufacturing method using a varistor particle aggregate, the variation in the varistor voltage is directly related to the variation in the particle size of the varistor particles.
【００１０】即ち，バリスタ粒子の粒径は，あらかじめ
高温で焼結させたＺｎＯ焼結体を粉砕したものを分級し
て用いるから，分級の精度によって決定される。更に，
粒径と同様に，粒形状も重要であることは言うまでもな
い。しかし，上記公報記載の従来の製造方法は，ＺｎＯ
焼結体の粉砕を機械的な強制解砕方法に頼っているため
，粉砕した粉体の粒形は雑多であり，必然的に角張って
いる。角取りの工程を入れても，基本的には粒形を大幅
に変えることは不可能である。そして，電圧非直線性素
子は，上記のごとく，その構成原理から言っても，粒形
は出来る限り球形に近いことが望ましい。That is, the particle size of the varistor particles is determined by the accuracy of the classification, since a pulverized ZnO sintered body that has been sintered in advance at a high temperature is classified and used. Furthermore,
It goes without saying that the particle shape is as important as the particle size. However, the conventional manufacturing method described in the above publication uses ZnO
Because the sintered body is crushed by a forced mechanical crushing method, the grain shape of the crushed powder is irregular and inevitably angular. Even if a corner cutting process is included, it is basically impossible to significantly change the grain shape. As mentioned above, it is desirable that the particle shape of the voltage nonlinear element be as close to a spherical shape as possible, considering its construction principle.
【００１１】以上より知られるごとく，従来の電圧非直
線性素子の製造方法においては，ＺｎＯ焼結体を粉砕す
る際に，強制的な機械粉砕を行わなければならない。そ
のため，これにより，得られた粉末は，角張った形状を
なしている。それ故，該粉末より得られる電圧非直線性
素子は，バリスタ電圧のバラツキが大きいという欠点が
ある。そこで，ＺｎＯ焼結体の粉砕に際しては，強制的
な機械的粉砕でなく，焼結体が容易にほぐれて粉末とな
る方法が必要である。これにより，表面が比較的円滑で
球形に近い粉末が得られるからである。本発明者らは，
かかる問題点を解決すべく鋭意検討を重ね，本発明をな
すに至ったのである。本発明は，ＺｎＯ焼結体がその粉
砕時に容易にほぐれて粉末となり，またバリスタ電圧の
バラツキが少ない電圧非直線性素子の製造方法を提供し
ようとするものである。As is known from the above, in the conventional manufacturing method of voltage nonlinear elements, forced mechanical pulverization must be performed when pulverizing the ZnO sintered body. Therefore, the powder obtained has an angular shape. Therefore, the voltage nonlinear element obtained from the powder has a drawback of large variations in varistor voltage. Therefore, when pulverizing the ZnO sintered body, it is necessary to use a method in which the sintered body is easily loosened into powder, rather than forced mechanical pulverization. This is because a powder with a relatively smooth surface and a nearly spherical shape can be obtained. The inventors
In order to solve these problems, we have made extensive studies and have come up with the present invention. The present invention aims to provide a method for manufacturing a voltage nonlinear element in which a ZnO sintered body is easily loosened into powder during pulverization, and in which variation in varistor voltage is small.
【００１２】0012
【課題の解決手段】本発明は，ＺｎＯを主成分とする酸
化亜鉛基材粒子を加熱焼成し，次いでその焼結体をほぐ
して粉末となし，更に該粉末に絶縁性の結合材を添加混
合して，これを複数の電極の間に配置し，その後熱処理
することにより電圧非直線性素子を製造する方法におい
て，上記酸化亜鉛基材粒子の加熱焼成は，該酸化亜鉛基
材粒子に対してＣｌ，Ｂｒ，Ｉ，またはこれらのいずれ
かのハロゲン化合物の少なくとも１種類以上を添加混合
して行うことを特徴とする電圧非直線性素子の製造方法
にある。本発明においても最も注目すべきことは，Ｚｎ
Ｏを主成分とする酸化亜鉛基材粒子を加熱焼成する工程
において，Ｃｌ（塩素），Ｂｒ（臭素），Ｉ（ヨウ素）
，又はこれらのハロゲン化合物の存在下で焼成すること
にある。[Means for solving the problem] The present invention heats and sinteres zinc oxide base material particles containing ZnO as a main component, then loosens the sintered body to form a powder, and further adds and mixes an insulating binder to the powder. In the method of manufacturing a voltage nonlinear element by disposing the zinc oxide base particles between multiple electrodes and then heat-treating them, the heating and sintering of the zinc oxide base particles has a A method of manufacturing a voltage nonlinear element is characterized in that the method includes adding and mixing at least one of Cl, Br, I, or any of these halogen compounds. The most noteworthy thing in the present invention is that Zn
In the process of heating and firing zinc oxide base particles containing O as a main component, Cl (chlorine), Br (bromine), I (iodine)
, or by firing in the presence of these halogen compounds.
【００１３】上記Ｃｌ，Ｂｒ，Ｉ，ハロゲン化合物は１
種類又は２種類以上を用いる。上記ハロゲン化合物とし
ては，ＺｎＣｌ２ （塩化亜鉛），ＺｎＢｒ２ （臭化
亜鉛），ＺｎＩ２ （ヨウ化亜鉛）などがあり，これら
の１種以上を用いる。また，この中，ＺｎＣｌ２ はＺ
ｎＯに対して，０．０２〜０．５モル（ｍｏｌ）％添加
することが好ましい。また，ＺｎＢｒ２ はＺｎＯに対
して０．１〜０．５モル％添加することが好ましい。更
に，ＺｎＩ２ はＺｎＯに対して０．２〜２．０モル％
添加することが好ましい。これらにより，バリスタ電圧
のバラツキが低い電圧非直線性素子を得ることができる
（実施例参照）。The above Cl, Br, I, halogen compound is 1
Use one type or two or more types. Examples of the halogen compound include ZnCl2 (zinc chloride), ZnBr2 (zinc bromide), and ZnI2 (zinc iodide), and one or more of these may be used. Also, among these, ZnCl2 is Z
It is preferable to add 0.02 to 0.5 mol% of nO. Further, ZnBr2 is preferably added in an amount of 0.1 to 0.5 mol% relative to ZnO. Furthermore, ZnI2 is 0.2 to 2.0 mol% relative to ZnO.
It is preferable to add. As a result, a voltage nonlinear element with low variation in varistor voltage can be obtained (see Examples).
【００１４】また，ハロゲン化合物は，沸点が５００〜
１２５０℃の範囲にあるものを用いることが好ましい。
５００℃未満では本発明の効果が少なく，一方１２５０
℃を越えると酸化亜鉛粒子の加熱焼成温度の上限が１３
００℃程度であり，また，ハロゲン化合物があまり分解
せず，効果が少ないからである。かかるハロゲン化合物
としては，ＺｎＣｌ２ ，ＺｎＢｒ２ ，ＺｎＩ２ ，
ＳｎＣｌ２ ，ＰｂＣｌ２ ，ＭｎＣｌ２ などがある
。なお，上記ハロゲン化合物のうち，ＺｎＣｌ２ ，Ｚ
ｎＢｒ２ 及びＺｎＩ２ は，その沸点が７３２℃，６
５０℃及び６２５℃である。[0014] Furthermore, the halogen compound has a boiling point of 500 to
It is preferable to use a temperature within the range of 1250°C. Below 500°C, the effect of the present invention is small;
If the temperature exceeds 13°C, the upper limit of the firing temperature for zinc oxide particles is 13°C.
This is because the temperature is about 00°C, and the halogen compound does not decompose much, resulting in little effect. Such halogen compounds include ZnCl2, ZnBr2, ZnI2,
Examples include SnCl2, PbCl2, MnCl2, etc. Furthermore, among the above halogen compounds, ZnCl2, Z
The boiling point of nBr2 and ZnI2 is 732℃, 6
50°C and 625°C.
【００１５】また，酸化亜鉛基材粒子の加熱焼成は，Ｃ
ｌ，Ｂｒ，Ｉの少なくとも１種類以上のガスイオンを含
む雰囲気中，例えばＨＣｌ，ＨＢｒ，ＨＩのガス中で行
うことが好ましい。この場合には，酸化亜鉛基材粒子内
に，充分に上記ハロゲンを供給できるので，得られた焼
結体が一層粉砕性に優れ，ほぐし易い。また，酸化亜鉛
基材粒子は，ＺｎＯ粒子のみならず，これにＢｉ，Ｃｏ
，Ｍｎ，Ｐｒ（プルトニウム）のいずれかを含む高抵抗
層用化合物の１種類以上を混合したものとすることもで
きる。また，高抵抗層用化合物は，前記従来のごとく，
一旦ＺｎＯ焼結体を作り，これをほぐしたＺｎＯ粉末に
添加して，再焼成に供することもできる。そして，この
再焼結体をほぐした粉末に結合材を加える。[0015] Furthermore, the heating and sintering of the zinc oxide base material particles
It is preferable to carry out the process in an atmosphere containing gas ions of at least one of l, Br, and I, for example, in a gas of HCl, HBr, and HI. In this case, the halogen can be sufficiently supplied into the zinc oxide base particles, so that the obtained sintered body has better crushability and is easier to loosen. In addition, the zinc oxide base particles contain not only ZnO particles but also Bi and Co
, Mn, and Pr (plutonium) may be mixed. In addition, the compound for the high resistance layer is, as mentioned above,
It is also possible to once create a ZnO sintered body, add it to the loosened ZnO powder, and use it for re-firing. A binder is then added to the loosened powder of this resintered body.
【００１６】上記高抵抗層用化合物としては，Ｂｉ２
Ｏ３ ，Ｃｏ２ Ｏ３ ，ＭｎＯ２ ，Ｐｒ６ Ｏ１１
などがある。また，これらに，添加副成分として，Ａｌ
（アルミニウム），Ｔｉ（チタン），Ｓｒ（ストロンチ
ウム），Ｍｇ（マグネシウム），Ｎｉ（ニッケル），Ｃ
ｒ（クロム），Ｓｉ（ケイ素）等の金属酸化物，または
これらの金属の有機化合物を用いることもできる。上記
のごとく高抵抗層用化合物，或いは副成分を，当初より
ＺｎＯに添加混合して焼成した場合にも，得られた焼結
体はほぐし易く，その粉末も球状形である。そして，粉
末の表面に高抵抗層化合物が被覆されている。[0016] As the compound for the high resistance layer, Bi2
O3, Co2 O3, MnO2, Pr6 O11
and so on. In addition, as an added subcomponent, Al
(aluminum), Ti (titanium), Sr (strontium), Mg (magnesium), Ni (nickel), C
Metal oxides such as r (chromium) and Si (silicon), or organic compounds of these metals can also be used. As mentioned above, even when the high-resistance layer compound or subcomponent is added and mixed with ZnO from the beginning and fired, the obtained sintered body is easy to loosen and the powder is also spherical. The surface of the powder is coated with a high-resistance layer compound.
【００１７】また，上記焼結体を粉砕した粉末には，絶
縁性の結合材を添加混合してペイント材となし，該ペイ
ント材を絶縁基板上に設けた複数の電極間に塗布し，そ
の後熱処理して，電圧非直線性素子を得る。上記絶縁性
の結合材としては，例えば，低融点ガラスがある。該絶
縁性結合材は，エチルセルロース等の有機バインダーと
混合して，上記粉末に添加混合する。有機バインダーは
，上記熱処理時に焼失する。また，上記絶縁性結合材は
，ＺｎＯ粉末に対して１０〜１００重量％添加すること
が好ましい。１０％未満では結合が不充分で，１００％
を越えると電圧非直線性素子の機能が低下するおそれが
ある。[0017] Furthermore, an insulating binder is added and mixed to the powder obtained by crushing the sintered body to form a paint material, the paint material is applied between a plurality of electrodes provided on an insulating substrate, and then A voltage nonlinear element is obtained by heat treatment. Examples of the above-mentioned insulating bonding material include low melting point glass. The insulating binder is mixed with an organic binder such as ethyl cellulose, and the mixture is added to the powder. The organic binder is burned away during the heat treatment. Further, it is preferable that the insulating binder is added in an amount of 10 to 100% by weight based on the ZnO powder. If it is less than 10%, the binding is insufficient, and if it is 100%
If the value exceeds 1, the function of the voltage nonlinear element may deteriorate.
【００１８】[0018]
【作用及び効果】本発明においては，酸化亜鉛基材粒子
を加熱焼成するに当たり，Ｃｌ，Ｂｒ，Ｉ又はこれらの
ハロゲン化合物を添加混合している。そのため，得られ
た焼結体は，焼結微結晶粒の相互間の結合が弱く，溶易
に解砕でき，ほぐし易い。そして，解砕された粉末は，
強制的な機械的粉砕によるものではないため，より球状
に近い形状を呈している。また，そのため，粉末の分級
も精度が良く，得られる電圧非直線性素子のバラツキも
非常に小さく，例えばバリスタ電圧のバラツキを５％以
内に抑えることも可能である。[Operations and Effects] In the present invention, Cl, Br, I, or a halogen compound thereof is added and mixed when heating and baking the zinc oxide base particles. Therefore, in the obtained sintered body, the bond between the sintered microcrystalline grains is weak, and the sintered body can be easily disintegrated and loosened. Then, the crushed powder is
Because it is not caused by forced mechanical crushing, it has a more spherical shape. Furthermore, the powder can be classified with high precision, and the variation in the voltage nonlinear elements obtained is very small. For example, it is possible to suppress the variation in varistor voltage to within 5%.
【００１９】また，本発明により得られる電圧非直線性
素子は，低電流領域で電圧非直線指数αが大きく特性の
バラツキの小さいものである。そのため，消費電流の小
さい液晶，ＥＬなどのデバイスのスイッチング素子とし
て最適な素子である。また，バリスタ電圧の低いものが
得られ，上記電圧非直線指数αが大きいことと相まって
，従来のＺｎＯバリスタでは対応することが出来なかっ
た低電圧用ＩＣの保護素子や低電圧における電圧安定化
として使用することができる。Further, the voltage nonlinear element obtained by the present invention has a large voltage nonlinearity index α in a low current region and small variations in characteristics. Therefore, it is an optimal element as a switching element for devices such as liquid crystals and EL devices with low current consumption. In addition, the low varistor voltage can be obtained, and the above-mentioned high voltage non-linearity index α makes it possible to use it as a protection element for low voltage ICs and for voltage stabilization at low voltages, which conventional ZnO varistors could not handle. can be used.
【００２０】さらに，低融点ガラス等の低融点の結合材
により固結して素子形成を行うために，高温プロセスを
必要とすることなく簡単に作ることができる。そのため
，回路基板やガラス基板上に素子を直接形成することが
できる。上記のごとく，本発明によれば，ＺｎＯ焼結体
が容易に解砕されて粉末となり，またバリスタ電圧のバ
ラツキが少ない電圧非直線性素子の製造方法を提供する
ことができる。Furthermore, since the element is formed by solidifying with a low-melting point bonding material such as low-melting point glass, it can be easily manufactured without requiring a high-temperature process. Therefore, elements can be directly formed on circuit boards or glass substrates. As described above, according to the present invention, it is possible to provide a method for manufacturing a voltage nonlinear element in which a ZnO sintered body is easily crushed into powder and the variation in varistor voltage is small.
【００２１】[0021]
実施例１
本発明の実施例にかかる電圧非直線性素子の製造方法に
つき説明する。まず，初めに，本発明により得ようとす
る電圧非直線性素子につき，図１〜図３につき説明する
。まず，図１に示す電圧非直線性素子１は，絶縁体とし
てのガラス基板３，３の間に，ＩＴＯ（インジウム−錫
酸化物）電極２，２を介して素子本体１０を形成したも
のである。該素子本体１０は，ＺｎＯ粉末１１と低融点
ガラス１２との混合物からなる。またＺｎＯ粉末１１の
表面にはＭｎＯ２ 等の高抵抗層１５が被覆されている
。また，図２は，上記図１に示した電圧非直線性素子１
における，素子本体周囲の全体を示す側面図である。
また，図３は，他の構造の電圧非直線性素子４を示して
いる。該電圧非直線性素子４は，１枚のガラス基板３の
上に電極２１，２１を設け，該電極２１，２１の間に上
記と同様の素子本体１０を形成したものである。Example 1 A method for manufacturing a voltage nonlinear element according to an example of the present invention will be described. First, a voltage nonlinear element to be obtained by the present invention will be explained with reference to FIGS. 1 to 3. First, the voltage nonlinear element 1 shown in FIG. 1 has an element body 10 formed between glass substrates 3, 3 as insulators, with ITO (indium-tin oxide) electrodes 2, 2 interposed therebetween. be. The element body 10 is made of a mixture of ZnO powder 11 and low melting point glass 12. Further, the surface of the ZnO powder 11 is coated with a high resistance layer 15 made of MnO2 or the like. In addition, Figure 2 shows the voltage nonlinear element 1 shown in Figure 1 above.
FIG. 3 is a side view showing the entire periphery of the element body. Further, FIG. 3 shows a voltage nonlinear element 4 having another structure. The voltage nonlinear element 4 has electrodes 21, 21 provided on one glass substrate 3, and an element main body 10 similar to the above-described element body 10 formed between the electrodes 21, 21.
【００２２】次に，上記図１に示した電圧非直線性素子
１を製造するに当たっては，まずＺｎＯを主成分とする
酸化亜鉛基材粒子を上記Ｃｌ，Ｂｒ等のハロゲンの存在
下で加熱焼成し，得られた焼結体をほぐして粉末とする
。その後，該粉末に低融点ガラスと有機バインダーとか
らなる結合材を添加混合し，ペイント状とする。次いで
，該ペイントを，図１に示すごとく，ガラス基板３上に
形成したＩＴＯ電極２の上に，スクリーン印刷等により
塗布する。そして，該ペイント層の上に，同様に別途ガ
ラス基板３上に形成してあるＩＴＯ電極２を載置する。Next, in manufacturing the voltage nonlinear element 1 shown in FIG. Then, the obtained sintered body is loosened to form a powder. Thereafter, a binder consisting of low melting point glass and an organic binder is added and mixed to the powder to form a paint. Next, as shown in FIG. 1, the paint is applied onto the ITO electrode 2 formed on the glass substrate 3 by screen printing or the like. Then, on the paint layer, an ITO electrode 2, which is also separately formed on a glass substrate 3, is placed.
【００２３】その後，これらを例えば３００〜５００℃
，１０〜３０分間，大気中で熱処理し，結合材中の有機
バインダーを焼失させる。また，これにより低融点ガラ
スを溶融させ，ＺｎＯ粉末を固結すると共に，これらを
ＩＴＯ電極２に結合する。なお，上記ＺｎＯの焼成時に
高抵抗層形成用のＭｎＯ２ 粉末を同時添加し，上記ハ
ロゲンの存在下で焼成した場合には，ＺｎＯ粉末の表面
にＭｎＯ２ の高抵抗層被膜が数１０〜数１００オング
ストロームの厚みで被覆されている（図１参照）。また
，上記ＭｎＯ２ 粉末の添加は，ＺｎＯ焼結時ではなく
，ＺｎＯ焼結体をほぐした粉末に添加して，再焼成する
方法もある。[0023] Thereafter, these are heated to, for example, 300 to 500°C.
, for 10 to 30 minutes in the air to burn off the organic binder in the binding material. Moreover, this melts the low melting point glass, solidifies the ZnO powder, and connects them to the ITO electrode 2. Note that if MnO2 powder for forming a high resistance layer is simultaneously added during the firing of the ZnO and the firing is performed in the presence of the halogen, a high resistance layer coating of MnO2 with a thickness of several tens to hundreds of angstroms is formed on the surface of the ZnO powder. (See Figure 1). Alternatively, the above-mentioned MnO2 powder may be added to the loosened powder of the ZnO sintered body and then re-sintered, instead of being added during ZnO sintering.
【００２４】実施例２
種々の割合のＺｎＣｌ２ の存在下で，ＺｎＯの焼成を
行い，その焼結体をほぐした粉末にＭｎＯ２ を添加混
合して再焼成し，再びほぐし，結合材を加えてペイント
状になし，実施例１と同様にして電圧非直線性素子を作
製した。また，焼結体のほぐれ，バリスタ電圧バラツキ
などにつき表１に示した。即ち，粒径０．０５〜１μｍ
の，酸化亜鉛基材粒子としての，ＺｎＯ粒子に，表１に
示す種々の割合で塩化亜鉛（ＺｎＣｌ２ ）を添加混合
し，１０００℃で加熱焼成して，焼結体を得た。次いで
，該焼結体を，らいかい機などによる軽い振動により，
容易にほぐして，０．５〜５０μｍのＺｎＯ粉末となし
た。更に，このＺｎＯ粉末（平均粒径７μｍ）に，高抵
抗層用化合物としてＭｎＯ２ を０．０５ｗｔ％添加し
，空気中で，１２５０℃で再焼成した。再焼成物を再び
上記と同様にほぐした。この場合も，簡単に粉末にほぐ
れた。また，この粉末は，表面に高抵抗層としてのＭｎ
Ｏ２ が，数１０〜数１００μｍで被覆されていた。Example 2 ZnO was fired in the presence of various proportions of ZnCl2, and MnO2 was added to the loosened powder of the sintered body, mixed, refired, loosened again, and a binder was added to paint. A voltage nonlinear element was fabricated in the same manner as in Example 1. In addition, Table 1 shows the loosening of the sintered body, variations in varistor voltage, etc. That is, particle size 0.05-1 μm
Zinc chloride (ZnCl2) was added and mixed in various ratios shown in Table 1 to ZnO particles as zinc oxide base particles, and the mixture was heated and fired at 1000°C to obtain a sintered body. Next, the sintered body is subjected to light vibration using a sintering machine or the like.
It was easily loosened to form ZnO powder of 0.5 to 50 μm. Further, 0.05 wt% of MnO2 was added as a compound for a high resistance layer to this ZnO powder (average particle size: 7 μm), and the powder was refired at 1250° C. in air. The refired product was loosened again in the same manner as above. In this case as well, it was easily broken down into powder. This powder also has Mn as a high resistance layer on the surface.
O2 was coated with a thickness of several tens to several hundreds of micrometers.
【００２５】次に，このＭｎＯ２ が被覆されたＺｎＯ
粉末に，結合材として軟化点３７０℃の低融点ガラス粉
末３０ｗｔ％と，有機バインダーとしてのエチルセルロ
ースとを添加混合し，ペイント状にした。次に，このペ
イントを実施例１に示したごとく，ガラス基板に接合し
た電極上にスクリーン印刷塗布し，同様にガラス基板上
に設けた電極を重ね，４４０℃で６０分間，大気中で熱
処理し，電圧非直線性素子を得た。Next, this MnO2-coated ZnO
30 wt % of low melting point glass powder with a softening point of 370° C. as a binder and ethyl cellulose as an organic binder were added and mixed to the powder to form a paint. Next, as shown in Example 1, this paint was applied by screen printing onto the electrodes bonded to the glass substrate, and the electrodes similarly provided on the glass substrate were stacked and heat treated at 440°C for 60 minutes in the air. , a voltage nonlinear element was obtained.
【００２６】この電圧非直線性素子につき，表１に示す
ごとく，電気特性，バリスタ電圧のバラツキを測定した
。また，同表には，ＺｎＯ焼結体のほぐれ状態，得られ
た粉末の状態も併示した。また，ＺｎＣｌ２ は，酸化
亜鉛基材粒子としてのＺｎＯに対するモル％で示し，０
〜３０モル％の間で種々の割合で添加した。同表におい
て，「焼結体のほぐれ」の欄の×は，解砕が困難で機械
的強制解砕が必要なことを，△は比較的容易なほぐれ，
○は極めて容易なほぐれ状態であったことを示す。また
，「粉末」の欄において，「小」とは５μｍ以下の粒を
，「良好」とは５〜１０μｍ程度の粒を，「異状粒成長
」とは１０μｍ以上の大きい粒子が混在する場合を示す
。また，「電気特性」とはバリスタ電圧を示し，□は粒
子が「小」及び「良好」の範囲で，そのバラツキが５〜
２０％のものを，○は最も優れたバラツキ５％未満を，
△は上記「異常粒成長」の範囲でバラツキが２０％未満
を，×はバラツキが２０％以上の場合を示す。As shown in Table 1, the electrical characteristics and variations in varistor voltage of this voltage nonlinear element were measured. The table also shows the loosened state of the ZnO sintered body and the state of the obtained powder. In addition, ZnCl2 is expressed as mol% relative to ZnO as zinc oxide base particles, and 0
It was added in various proportions between ~30 mol%. In the same table, the × in the “Loosening of the sintered body” column indicates that it is difficult to crush and requires forced mechanical crushing, and the △ indicates that it is relatively easy to loosen.
○ indicates that it was extremely easy to unravel. In addition, in the "Powder" column, "Small" refers to particles of 5 μm or less, "Good" refers to particles of about 5 to 10 μm, and "abnormal grain growth" refers to cases where large particles of 10 μm or more are mixed. show. In addition, "electrical characteristics" indicates the varistor voltage, and □ indicates the range of "small" and "good" particles, and the variation is 5 to 5.
20%, ○ indicates the best variation of less than 5%,
Δ indicates that the variation is less than 20% within the range of the above-mentioned "abnormal grain growth", and × indicates that the variation is 20% or more.
【００２７】表１より知られるごとく，ＺｎＯ粒子の焼
結に当たってＺｎＣｌ２ を添加した場合，焼結体のほ
ぐれは良く，特に０．０２モル％以上では優れたほぐれ
性を示していた。これらのほぐれ容易性は，ＺｎＯ焼結
体，該焼結体をほぐした粉末にＭｎＯ２ を添加焼成し
た再焼結体についても同様であった。これに比して，Ｚ
ｎＣｌ２ を添加していない場合（試料Ｎｏ．１）は，
ほぐれは不可能で，機械的な強制解砕が必要であった。
上記の焼結体ほぐれ性から推察されるごとく，得られた
ＺｎＯ２ 粉末は，ＺｎＣｌ２ ０．００５モル５％以
上では，ほぼ球形状を有し，良好であった。また，Ｚｎ
Ｃｌ２ ５％以上では異状粒成長が見られた。As can be seen from Table 1, when ZnCl2 was added during sintering of ZnO particles, the sintered body loosened well, and especially when the amount was 0.02 mol % or more, excellent loosening properties were exhibited. These eases of loosening were the same for the ZnO sintered body and the resintered body obtained by adding MnO2 to the loosened powder of the sintered body and firing it. In comparison, Z
When nCl2 is not added (sample No. 1),
Unraveling was impossible, and forced mechanical crushing was required. As inferred from the above-mentioned loosening properties of the sintered body, the obtained ZnO2 powder had a nearly spherical shape and was good when ZnCl2 was 0.005 mol 5% or more. Also, Zn
Abnormal grain growth was observed at Cl2 of 5% or more.
【００２８】次に，電気特性はＺｎＣｌ２ ０．０２〜
０．５モル％が最も優れている。また，バリスタ電圧の
バラツキは，ＺｎＣｌ２ が０．００１〜２．０モル％
であれば，１０％以内に抑えることができる。また，Ｚ
ｎＣｌ２ が０．０２〜０．５モル％であれば，バラツ
キを５％以内に抑えることができ，より優れた電圧非直
線性素子が得られる。なお，本例において，焼成後のＺ
ｎＯ粉末にＭｎＯ２ とＣｏＯとをそれぞれ０．０５ｗ
ｔ％添加，混合して１２５０℃で再焼成した場合も，そ
の再焼結体のほぐれ性も良く，上記と同様の結果を得る
ことができた。[0028] Next, the electric characteristics are ZnCl2 0.02~
0.5 mol% is the best. In addition, the variation in varistor voltage is 0.001 to 2.0 mol% of ZnCl2.
If so, it can be suppressed to within 10%. Also, Z
If nCl2 is 0.02 to 0.5 mol%, the variation can be suppressed to within 5%, and a more excellent voltage nonlinear element can be obtained. In addition, in this example, Z after firing
0.05w each of MnO2 and CoO to nO powder
Even when t% was added and mixed and refired at 1250°C, the resintered body had good loosening properties and the same results as above could be obtained.
【００２９】[0029]
【表１】[Table 1]
【００３０】実施例３
種々の割合の臭化亜鉛（ＺｎＢｒ２ ）の存在下で，Ｚ
ｎＯの焼成を行った。そして，実施例２と同様にしてそ
の焼結体の粉末にＭｎＯ２ を添加混合して再焼成し，
電圧非直線性素子を作製した。その結果を実施例２と同
様にして表２に示した。なお，本例はＺｎＢｒ２ を用
いる他は実施例２と同様の条件である。表２より知られ
るごとく，ＺｎＢｒ２ を用いた場合も，実施例２とほ
ぼ同様の結果が得られる。また，バリスタ電圧のバラツ
キについては，ＺｎＢｒ２ が０．０１〜１０モル％で
あれば１０％以内であり，０．１〜０．５モル％であれ
ば５％以内のバラツキに抑えることができる。Example 3 In the presence of various proportions of zinc bromide (ZnBr2), ZnBr2
nO was calcined. Then, in the same manner as in Example 2, MnO2 was added and mixed to the powder of the sintered body, and the mixture was re-sintered.
A voltage nonlinear element was fabricated. The results are shown in Table 2 in the same manner as in Example 2. Note that this example has the same conditions as Example 2 except that ZnBr2 is used. As can be seen from Table 2, almost the same results as in Example 2 are obtained when ZnBr2 is used. Furthermore, the variation in varistor voltage can be suppressed to within 10% if ZnBr2 is 0.01 to 10 mol%, and within 5% if ZnBr2 is 0.1 to 0.5 mol%.
【００３１】[0031]
【表２】[Table 2]
【００３２】実施例４
種々の割合のヨウ化亜鉛（ＺｎＩ２ ）の存在下でＺｎ
Ｏの焼成を行った。そして，実施例２と同様にして，そ
の焼結体の粉末にＭｎＯ２ を添加混合し，再焼成し，
電圧非直線性素子を作製した。その結果を同様にして表
３に示した。なお，本例はＺｎＩ２ を用いる他は実施
例２と同様の条件である。表３より知られるごとく，Ｚ
ｎＩ２ を用いた場合は，０．００５モル％以下では，
焼結体のほぐれ性が悪かったが電気特性は良好であった
。０．０１モル％以上では焼結体のほぐれた性も良く，
粉末も良好で，電気特性も良い。なお，ＺｎＩ２ ２０
％以上では，電気特性が若干悪くなっている。そして，
バリスタ電圧のバラツキについては，ＺｎＩ２ が０．
０２〜１０モル％であれば１０％以下に抑えることがで
き，０．２〜２モル％であれば５％以下のバラツキに抑
えることができる。Example 4 Zn in the presence of various proportions of zinc iodide (ZnI2)
O was fired. Then, in the same manner as in Example 2, MnO2 was added to and mixed with the powder of the sintered body, and re-sintered.
A voltage nonlinear element was fabricated. The results are similarly shown in Table 3. Note that this example had the same conditions as Example 2 except that ZnI2 was used. As is known from Table 3, Z
When nI2 is used, at 0.005 mol% or less,
Although the sintered body had poor unraveling properties, its electrical properties were good. At 0.01 mol% or more, the sintered body has good loosening properties,
The powder is good and the electrical properties are also good. In addition, ZnI2 20
% or more, the electrical characteristics become slightly worse. and,
Regarding the variation in varistor voltage, ZnI2 is 0.
If it is 0.02 to 10 mol%, the variation can be suppressed to 10% or less, and if it is 0.2 to 2 mol%, the variation can be suppressed to 5% or less.
【００３３】[0033]
【表３】[Table 3]
【００３４】実施例５
本例は，上記実施例２〜４に示したＺｎＣｌ２ ，Ｚｎ
Ｂｒ２ ，ＺｎＩ２ の他に，ハロゲン化合物としてＳ
ｎＣｌ２ ，ＰｂＣｌ２ ，ＭｎＣｌ２ を用いたもの
である。また，上記６種類のハロゲン化合物は，いずれ
もその沸点が５００〜１２５０℃という低温度のもので
ある（表４参照）。また，これら化合物は，ＺｎＯに対
して０．５モル％添加混合し，その後は実施例２と同様
にして電圧非直線性素子を作製した。表４より知られる
ごとく，上記いずれのハロゲン化合物を用いた場合も，
電気特性は良く，また非直線性指数α（実施例８及び図
４参照）も大きい。Example 5 In this example, ZnCl2 and ZnCl2 shown in Examples 2 to 4 above were used.
In addition to Br2 and ZnI2, S as a halogen compound
This uses nCl2, PbCl2, and MnCl2. Furthermore, all of the six types of halogen compounds mentioned above have boiling points as low as 500 to 1250°C (see Table 4). Further, these compounds were added and mixed in an amount of 0.5 mol % with respect to ZnO, and thereafter a voltage nonlinear element was produced in the same manner as in Example 2. As is known from Table 4, when using any of the above halogen compounds,
The electrical characteristics are good, and the nonlinearity index α (see Example 8 and FIG. 4) is also large.
【００３５】[0035]
【表４】[Table 4]
【００３６】実施例６
酸化亜鉛基材粒子として，ＺｎＯ粒子と高抵抗層用化合
物との混合物を用い，これにＺｎＣｌ２ ０．１モル％
を混合し，焼成して焼結体を得た。この焼結体をほぐし
，結合材を加え，ペイント状にし，実施例２と同様に電
圧非直線性素子を作製した。即ち，本例は，高抵抗層用
化合物を当初より添加し，焼成するものである（実施例
２〜５は，一旦ＺｎＯを焼成し，その焼結体の粉末に上
記化合物を添加し，再焼成している）。上記化合物とし
ては，酸化ビスマス（Ｂｉ２ Ｏ３ ），酸化コバルト
（ＣｏＯ），酸化マンガン（ＭｎＯ２ ），酸化プルト
ニウム（Ｐｒ６ Ｏ１１）を用いた。その他の条件は実
施例２と同様である。表５より，ＺｎＯ焼成の当初より
，Ｂｉ２ Ｏ３ 等の高抵抗層化合物を添加混合してお
いても，焼結体のほぐれ性も良く，優れた電圧非直線性
素子が得られることが分かる。Example 6 A mixture of ZnO particles and a high-resistance layer compound was used as the zinc oxide base particles, and 0.1 mol% of ZnCl2 was added to the mixture.
A sintered body was obtained by mixing and firing. This sintered body was loosened, a binding material was added, it was made into a paint shape, and a voltage nonlinear element was produced in the same manner as in Example 2. That is, in this example, the compound for the high-resistance layer is added from the beginning and fired (in Examples 2 to 5, ZnO is fired once, the above compound is added to the powder of the sintered body, and then the compound is fired again). firing). As the above-mentioned compounds, bismuth oxide (Bi2 O3), cobalt oxide (CoO), manganese oxide (MnO2), and plutonium oxide (Pr6 O11) were used. Other conditions are the same as in Example 2. Table 5 shows that even if a high resistance layer compound such as Bi2 O3 is added and mixed from the beginning of ZnO firing, the sintered body has good loosening properties and an excellent voltage nonlinear element can be obtained.
【００３７】[0037]
【表５】[Table 5]
【００３８】実施例７
本例は，ハロゲンガス雰囲気中でＺｎＯの焼成を行った
ものである。即ち，るつぼの底に１モル／ｌの塩酸水溶
液を入れ，蓋をした後，その上にＺｎＯ粉末とＭｎＯ２
粉末（０．５モル％）との混合物を置き，１０００℃
で焼成した。得られた焼結体はほぐれ性も良く，粉末も
良好であった。また，この粉末を用いて実施例６と同様
にして電圧非直線性素子を作製した。この電圧非直線性
素子も，実施例６の資料Ｎｏ．７３と同様に優れた性質
を示した。Example 7 In this example, ZnO was fired in a halogen gas atmosphere. That is, after putting a 1 mol/l aqueous solution of hydrochloric acid in the bottom of the crucible and putting a lid on it, ZnO powder and MnO2 are placed on top of it.
Place the mixture with powder (0.5 mol%) and heat at 1000°C.
It was fired in The obtained sintered body had good loosening properties and powder quality. Further, a voltage nonlinear element was fabricated using this powder in the same manner as in Example 6. This voltage nonlinear element is also used in Material No. 6 of Example 6. Similar to No. 73, it showed excellent properties.
【００３９】実施例８
次に，電圧非直線性素子の電圧−電流特性について，図
４を用いて説明する。同図において，特性Ａは本発明の
電圧非直線性素子の，特性Ｂは従来のＺｎＯバリスタ（
比較例１）の，特性Ｃは従来の電圧非直線性素子（比較
例２）の特性を示している。また，上記本発明の電圧非
直線性素子は，前記実施例２における試料Ｎｏ．７（Ｚ
ｎＣｌ２ が０．１モル％）の条件で作製したものであ
る。この電圧非直線性素子は，素子面積１ｍｍ２ ，電
極間距離３０μｍである。Embodiment 8 Next, the voltage-current characteristics of the voltage nonlinear element will be explained using FIG. 4. In the figure, characteristic A is that of the voltage nonlinear element of the present invention, and characteristic B is that of the conventional ZnO varistor (
Characteristic C of Comparative Example 1) shows the characteristic of the conventional voltage nonlinear element (Comparative Example 2). Further, the voltage nonlinear element of the present invention is the sample No. 1 in Example 2. 7 (Z
It was produced under conditions where nCl2 was 0.1 mol %). This voltage nonlinear element has an element area of 1 mm2 and a distance between electrodes of 30 μm.
【００４０】比較例２は，次の条件で作成したものであ
る。即ち，粒径０．０５〜１μｍのＺｎＯを７００℃で
加熱焼成し，その焼結体を０．５〜５０μｍの粒径に粉
砕し，これにＭｎＯ２ を０．５モル％添加し，９００
℃，６０分間熱処理した。これにより，表面に数１０〜
数１００μｍの厚さで，ＭｎＯ２ の高抵抗層が形成さ
れるたＺｎＯ粉末を得た。その後，平均粒径５〜１０μ
ｍのＺｎＯ粉末に３０ｗｔ％低融点ガラスと有機バイン
ダとを添加混合して，ペイント状となした。そして，こ
れを実施例１と同様にして電極間に配置し，熱処理し，
上記本発明にかかる電圧非直線性素子と同様の大きさの
電圧非直線性素子とした。Comparative Example 2 was prepared under the following conditions. That is, ZnO with a particle size of 0.05 to 1 μm is heated and fired at 700°C, the sintered body is pulverized to a particle size of 0.5 to 50 μm, 0.5 mol% of MnO2 is added, and 900
℃ for 60 minutes. As a result, several tens to
A ZnO powder was obtained in which a high resistance layer of MnO2 was formed with a thickness of several 100 μm. After that, the average particle size is 5~10μ
30 wt % of low melting point glass and an organic binder were added to and mixed with m ZnO powder to form a paint-like product. Then, this was placed between the electrodes in the same manner as in Example 1, and heat treated.
A voltage nonlinear element having the same size as the voltage nonlinear element according to the present invention was prepared.
【００４１】さて，電圧非直線性素子の電圧−電流特性
は，良く知られているように，近似的に，〔Ｉ−ＫＶα
〕なる計算式で示されている。ここで，Ｉは素子に流れ
る電流，Ｖは素子の電極間の電圧，Ｋは固有抵抗の抵抗
値に相当する定数，αは上述した電圧非直線性特性の指
数を示している。また，この電圧非直線指数αが大きい
程，電圧非直線性が優れていることになる。また，通常
，ＺｎＯバリスタではバリスタ特性を表すのに，例えば
素子に１ｍＡの電流を流した時の電極間に現れる電圧を
バリスタ電圧Ｖ（ｌｍＡ）と呼び，このバリスタ電圧Ｖ
（ｌｍＡ）と上記電圧非直線指数αとを使用している。Now, as is well known, the voltage-current characteristic of a voltage nonlinear element is approximately expressed as [I-KVα
] is shown by the calculation formula. Here, I is the current flowing through the element, V is the voltage between the electrodes of the element, K is a constant corresponding to the resistance value of the specific resistance, and α is the exponent of the voltage nonlinearity characteristic described above. Further, the larger the voltage nonlinearity index α, the better the voltage nonlinearity. In addition, normally, in order to express the varistor characteristics of a ZnO varistor, for example, the voltage that appears between the electrodes when a current of 1 mA flows through the element is called the varistor voltage V (lmA), and this varistor voltage V
(lmA) and the above-mentioned voltage nonlinearity index α are used.
【００４２】そして，図４の特性に示されるように，ま
ず特性Ｂで示される従来のＺｎＯバリスタ（比較例１）
は，低電圧域において，電圧非直線指数αが小さく，１
０−４Ａ以下の電流では，良好な電圧非直線性素子とし
ての機能を発揮しえない。一方，上記従来の電圧非直線
性素子（比較例２）は，特性Ｃで示されるように，低電
流域においても電圧非直線指数αが大きく，１０−１０
Ａ程度の電流域でも十分に電圧非直線性素子としての
機能を発揮することができることを示している。次に，
本発明における電圧非直線性素子（試料Ｎｏ．７）の電
圧−電流特性は，特性Ａで示すごとく，ＺｎＣｌ２ を
用いていない上記比較例２に比して，更に低電流領域に
おける特性が向上していることが分かる。それ故，バリ
スタ電圧Ｖ（１ｍＡ）も更に低くすることができること
が分かる。As shown in the characteristics of FIG. 4, first, the conventional ZnO varistor (comparative example 1) shown by characteristic B
In the low voltage region, the voltage nonlinearity index α is small and 1
At a current of 0-4 A or less, it cannot function as a good voltage nonlinear element. On the other hand, the conventional voltage nonlinear element (comparative example 2) has a large voltage nonlinear index α even in the low current range, as shown by characteristic C, and is 10-10
This shows that the device can sufficiently function as a voltage nonlinear element even in a current range of approximately A. next,
As shown in characteristic A, the voltage-current characteristics of the voltage nonlinear element (sample No. 7) in the present invention show that the characteristics in the low current region are further improved compared to Comparative Example 2, which does not use ZnCl2. I can see that Therefore, it can be seen that the varistor voltage V (1 mA) can also be lowered further.
【００４３】なお，図４の特性は，上述したように電極
間距離を３０μｍとした素子についてのものであるが，
これはＺｎＯ粉末の平均粒径が５〜１０μｍという比較
的大きな粒径のためにこれ以上狭くすることが出来ない
からである。電極間距離を狭くすれば，バリスタ電圧を
低くすることができる。即ち，もしも，ＺｎＯ粉末とし
て平均粒径が０．３〜３μｍのものを使えば，電極間距
離が１０μｍ程度もしくは以下の素子を作成することが
でき，図４と同じような良好な特性が得られる。Note that the characteristics shown in FIG. 4 are for an element with an inter-electrode distance of 30 μm as described above.
This is because the average particle size of ZnO powder is relatively large, 5 to 10 μm, and cannot be made any narrower. By narrowing the distance between the electrodes, the varistor voltage can be lowered. In other words, if ZnO powder with an average particle size of 0.3 to 3 μm is used, it is possible to create an element with an interelectrode distance of about 10 μm or less, and the same good characteristics as shown in Fig. 4 can be obtained. It will be done.
【図１】実施例１の電圧非直線性素子の拡大断面図。FIG. 1 is an enlarged cross-sectional view of a voltage nonlinear element of Example 1.
【図２】実施例１の電圧非直線性素子の側面図。FIG. 2 is a side view of the voltage nonlinear element of Example 1.
【図３】実施例１の他の電圧非直線性素子を示す側面図
。FIG. 3 is a side view showing another voltage nonlinear element of Example 1.
【図４】実施例８における，本発明の電圧非直線性素子
及び比較例１，２の，電圧−電流特性線図。FIG. 4 is a voltage-current characteristic diagram of the voltage nonlinear element of the present invention and Comparative Examples 1 and 2 in Example 8.
１．．．電圧非直線性素子， １１．．．ＺｎＯ粉末， ２．．．ＩＴＯ電極， 1. ．． ．． voltage nonlinear element, 11. ．． ．． ZnO powder, 2. ．． ．． ITO electrode,
Claims (6)
子を加熱焼成し，次いでその焼結体をほぐして粉末とな
し，更に該粉末に絶縁性の結合材を添加混合して，これ
を複数の電極の間に配置し，その後熱処理することによ
り電圧非直線性素子を製造する方法において，上記酸化
亜鉛基材粒子の加熱焼成は，該酸化亜鉛基材粒子に対し
てＣｌ，Ｂｒ，Ｉ，またはこれらのいずれかのハロゲン
化合物の少なくとも１種類以上を添加混合して行うこと
を特徴とする電圧非直線性素子の製造方法。[Claim 1] Zinc oxide base material particles containing ZnO as a main component are heated and fired, the sintered body is then loosened to form a powder, an insulating binder is added and mixed to the powder, and this is mixed. In the method of manufacturing a voltage nonlinear element by disposing the zinc oxide base particles between a plurality of electrodes and then heat-treating them, the heating and baking of the zinc oxide base particles causes Cl, Br, and I to be added to the zinc oxide base particles. , or at least one of these halogen compounds is added and mixed.
，ＺｎＣｌ２ ，ＺｎＢｒ２ ，ＺｎＩ２ のいずれか
１種以上を用いることを特徴とする電圧非直線性素子の
製造方法。2. The method of manufacturing a voltage nonlinear element according to claim 1, wherein the halogen compound is one or more of ZnCl2, ZnBr2, and ZnI2.
，沸点が５００〜１２５０℃の範囲にあるものを用いる
ことを特徴とする電圧非直線性素子の製造方法。3. The method of manufacturing a voltage nonlinear element according to claim 1, wherein the halogen compound has a boiling point in the range of 500 to 1250°C.
の加熱焼成はＣｌ，Ｂｒ，Ｉの少なくとも１種類以上の
ガスイオンを含む雰囲気中で行うことを特徴とする電圧
非直線性素子の製造方法。4. The method according to claim 1, wherein the heating and baking of the zinc oxide base particles is performed in an atmosphere containing at least one type of gas ion of Cl, Br, and I. Method.
は，ＺｎＯ粒子と，Ｂｉ，Ｃｏ，Ｍｎ，Ｐｒのいずれか
を含む高抵抗層用化合物の１種類以上とを混合してなる
ものであることを特徴とする電圧非直線性素子の製造方
法。[Claim 5] In claim 1, the zinc oxide base particles are formed by mixing ZnO particles and one or more types of high-resistance layer compounds containing any one of Bi, Co, Mn, and Pr. A method for manufacturing a voltage nonlinear element, characterized by the following.
の焼結体をほぐしてＺｎＯ粉末となし，該ＺｎＯ粉末に
Ｂｉ，Ｃｏ，Ｍｎ，Ｐｒのいずれかを含む高抵抗層用化
合物の１種類以上を混合し，再度焼結を行い，その焼結
体をほぐし，その後該粉末に絶縁性の結合材を添加混合
することを特徴とする電圧非直線性素子の製造方法。6. In claim 1, a sintered body of zinc oxide base particles is loosened to form a ZnO powder, and the ZnO powder contains one of the compounds for a high resistance layer containing any one of Bi, Co, Mn, and Pr. 1. A method of manufacturing a voltage nonlinear element, which comprises mixing at least one type of powder, sintering it again, loosening the sintered body, and then adding and mixing an insulating binder to the powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3112514A JPH04318902A (en) | 1991-04-17 | 1991-04-17 | Manufacture of voltage nonlinear element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3112514A JPH04318902A (en) | 1991-04-17 | 1991-04-17 | Manufacture of voltage nonlinear element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04318902A true JPH04318902A (en) | 1992-11-10 |
Family
ID=14588557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3112514A Pending JPH04318902A (en) | 1991-04-17 | 1991-04-17 | Manufacture of voltage nonlinear element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04318902A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017199765A (en) * | 2016-04-26 | 2017-11-02 | 住友ベークライト株式会社 | High voltage protective particles, method for producing high voltage protective particles, and semiconductor device |
-
1991
- 1991-04-17 JP JP3112514A patent/JPH04318902A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017199765A (en) * | 2016-04-26 | 2017-11-02 | 住友ベークライト株式会社 | High voltage protective particles, method for producing high voltage protective particles, and semiconductor device |
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