JPS62190816A - Manufacture of voltage nonlinear device - Google Patents
Manufacture of voltage nonlinear deviceInfo
- Publication number
- JPS62190816A JPS62190816A JP61034653A JP3465386A JPS62190816A JP S62190816 A JPS62190816 A JP S62190816A JP 61034653 A JP61034653 A JP 61034653A JP 3465386 A JP3465386 A JP 3465386A JP S62190816 A JPS62190816 A JP S62190816A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- powder
- zno
- inorganic
- fine
- 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 description 6
- 239000000843 powder Substances 0.000 claims description 40
- 239000004065 semiconductor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 8
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 67
- 239000011787 zinc oxide Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- -1 bis-vs oxide (B12o3) Chemical compound 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material 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
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
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
らにはマトリウクス駆動の液晶、ＫＬ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。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a voltage nonlinear element whose resistance value changes depending on an applied voltage, and is useful for voltage stabilization, abnormal voltage control, and matrix-driven liquid crystal, KL, etc. It is used in switching elements of display devices, etc.
従来の技術
従来の電圧非直線性素子は、酸化亜鉛（ＺｎＯ）に酸化
ビス−ｖス（Ｂ１２ｏ３）、酸化コバルト（Ｃｊｏ ２
０３ ）、酸化マンガン（Ｍｎ０２）、酸化アンチモン
（３１）２０ｓ）などの酸化物を添加して、１０ｏＯ〜
１３５０℃で焼結したＺｎＯ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）
発明が解決しようとする問題点
このような従来の電圧非直線性素子は、ＺｎＯバリスタ
を初めとして、素子厚みを薄く（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１
ｍＡ’ｉ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の保護素子や低い電
圧における電圧安定化素子として使えないものであった
。また、上述したように焼成する際に１０００’Ｃ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、例えば液晶などのスイッチング素子としては
不適当なものであるなどの問題点を有していた。Prior Art Conventional voltage nonlinear elements are made of zinc oxide (ZnO), bis-vs oxide (B12o3), cobalt oxide (Cjo2), etc.
03), manganese oxide (Mn02), antimony oxide (31) 20s), etc.
There are various types such as ZnO varistors sintered at 1350°C. Among them, the ZnO varistor has a voltage nonlinearity index α
, is the most commonly used because of its high surge resistance. (Refer to Japanese Patent Publication No. 46-19472) Problems to be Solved by the Invention Conventional voltage non-linear elements such as these, including ZnO varistors, have limitations in making the element thickness thin (several tens of μm or less). Therefore, the varistor voltage (current 1 in the varistor)
There is a limit to lowering the voltage V1mA when mA'i flows, and it cannot be used as a protection element for low voltage ICs or a voltage stabilizing element at low voltages. Further, as mentioned above, since a high temperature process of 1000'C or more is required during firing, there is a problem 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 for use as switching elements for liquid crystals, for example.
問題点を解決するための手段
この問題点を解決するために本発明は、無機質半導体の
微粉末にＢｉを含有する無機または有機化合物を添加し
、混合した後、６００〜１３６０℃で熱処理を行い、無
機質半導体微粉末の表面に無機質絶縁被膜を形成させる
と共に、その絶縁被膜を表面に有した微粉末状の上記無
機質半導体の全部またはほとんどがそれぞれ複数個集ま
った状態となるようにし、その後微粉末状の無機質半導
体が複数個集まった状態の粉末または一部に上記微粉末
を含む粉末に絶縁性の有機接着剤かまたはガラス粉末と
有機バインダーを加え、ペイント状にし、次いで上記ペ
イントを電極を配した絶縁基板上に印刷、スプレーまた
は浸漬などによって塗布した後、熱処理を行って硬化さ
せることを特徴とするものである。Means for Solving the Problem In order to solve this problem, the present invention adds an inorganic or organic compound containing Bi to a fine powder of an inorganic semiconductor, and after mixing, performs heat treatment at 600 to 1360°C. , an inorganic insulating film is formed on the surface of the inorganic semiconductor fine powder, and all or most of the fine powdered inorganic semiconductors having the insulating film on the surface are gathered together, and then the fine powder is An insulating organic adhesive or glass powder and an organic binder are added to a powder in which a plurality of inorganic semiconductors are assembled or a part of the powder contains the above-mentioned fine powder to form a paint, and then the paint is applied to an electrode. It is characterized in that it is applied onto an insulated substrate by printing, spraying, dipping, etc., and then heat-treated to harden it.
作用
この方法によれば、低電流域においても電圧非直線指数
αの大きなものが得られ、かつ電極間距離を狭く（数十
μｍ以下）して素子を形成することができ、低電圧化に
適した素子がきわめて容易に得られることとなる。また
、塗布したペイントを低い温度で硬化させて作ることが
できるため、回路基板上に素子を直接形成することがで
き、ＺｎＯバリスタなどでは考えられない幅広い用途が
期待できるものである。さらに、得られた素子は微粉末
状の半導体物質を固めたものであるため、それぞれの半
導体物質の微粉末間は点接触となり、接触面積が小さい
ことから並列静電容量の小さなものが得られ、液晶など
のデバイスのスイッチング素子として最適な素子が提供
できることとなる。Effect: According to this method, a large voltage non-linearity index α can be obtained even in a low current range, and an element can be formed with a narrow distance between electrodes (several tens of μm or less), making it possible to reduce the voltage. A suitable element can be obtained very easily. Furthermore, since it can be made by curing the applied paint at a low temperature, it is possible to form elements directly on a circuit board, and it is expected to have a wide range of applications unimaginable for ZnO varistors and the like. Furthermore, since the obtained device is made of solidified semiconductor material in the form of fine powder, there is point contact between the fine powders of each semiconductor material, and the contact area is small, making it possible to obtain a device with a small parallel capacitance. , it is possible to provide an element that is optimal as a switching element for devices such as liquid crystals.
実施例 以下、本発明を実施例にもとすいて詳細に説明する。Example Hereinafter, the present invention will be explained in detail using examples.
第１図は本発明の製造方法による製造工程の一実施例を
示している。まず、粒子径がＯ，ＯＳ〜１μｍの微粒子
状の酸化亜鉛を７００〜１３００℃で焼成した後、その
焼結されたＺｎＯを０．５〜５０μｍの粒子径（平均粒
子径１〜１０μｍ）に粉砕し、そのＺｎＯ微粉末に酸化
ビスマスを０．０５〜１０ｍｏ１チ添加し、６００〜１
３５０℃で１０〜６０分間、熱処理し、そのＺｎＯ微粉
末表面に酸化ビスマスの絶縁被膜を形成した。この時、
微粉末状のＺｎＯの表面にはＢｉ２Ｏ５絶縁被膜がほぼ
数十〜数百人の厚さで薄く形成されていることが認めら
れた。次いで、このようにして作成したＢｉ２Ｏ３絶縁
被膜が表面についたＺｎＯ微粉末は弱い力で互いに接着
しているので、これを乳鉢あるいはポヮト°ミルでほぐ
し上記ＺｎＯ微粉末がそれぞれ複数個集まった微粉末群
の状態とした（以下、この状態のものを粉末状という）
。この時、一部に上記ＺｎＯ微粉末が単独で存在しても
差支えないものであり、このようなＺｎＯ微粉末を一部
に含んでの状態のものも粉末状という。次に、上記のよ
うにして得られたＢｉｚＯ老縁被腰縁被膜に形成された
粉末状のＺｎＯに、粉末間の結合を図る結合剤（バイン
ダー）としてポリイミド樹脂を添加し、混合した。ここ
で、結合剤としてはポリイミド樹脂の固形分が溶剤（例
えばｎ−メチル−２−ピロリドン）に対して５ｗｔ％と
なるように薄めたものとし、それをＺｎＯ粉末と例えば
等重量で混合し、ペイント状とした。次いで、上記のよ
うにして得られたペイントを第３図に示すようにＩＴＯ
（≧ンジウム・スズ酸化物）電極１の設けられたガラス
基板３上に例えばスクリーン印刷で塗布し、その上に同
じ（ＩＴＯ電極２の設けられたガラス基板４を載置し、
２８０〜４００℃で３０分間、大気中で硬化させ、電極
１．２間に電圧非直線性素子６を設けた。第２図は、電
圧非直線性素子５の拡大断面図であシ、６はＺｎＯ粉末
、７はＺｎＯ粉末６の表面に施されたＢｉｚＯｓ絶縁被
膜、８はそれらＺｎＯ粉末６間を機械的に結合している
結合剤であり、この結合剤８でもってＺｎＯ粉末６の間
は互いに固められている。第４図はＩＴＯ電極１ａ、１
ｂが設けられたガラス基板３２Ｌ上に電圧非直線性素子
５を構成した場合を示している。FIG. 1 shows an embodiment of the manufacturing process according to the manufacturing method of the present invention. First, fine particulate zinc oxide with a particle size of O,OS ~ 1 μm is fired at 700 to 1300°C, and then the sintered ZnO is reduced to a particle size of 0.5 to 50 μm (average particle size of 1 to 10 μm). 0.05 to 10 mol of bismuth oxide was added to the ZnO fine powder, and 600 to 1 mol of bismuth oxide was added.
A heat treatment was performed at 350° C. for 10 to 60 minutes to form an insulating film of bismuth oxide on the surface of the ZnO fine powder. At this time,
It was observed that a thin Bi2O5 insulating film was formed on the surface of the finely powdered ZnO to a thickness of approximately several tens to several hundreds of layers. Next, since the ZnO fine powders with the Bi2O3 insulating film created in this way adhere to each other with weak force, they are loosened in a mortar or pot mill to form fine powders in which a plurality of the above-mentioned ZnO fine powders are collected. (Hereinafter, this state will be referred to as powder)
. At this time, there is no problem even if the above-mentioned ZnO fine powder is present alone in a part, and a state containing such ZnO fine powder in a part is also referred to as powder. Next, a polyimide resin was added as a binder for bonding the powders to the powdered ZnO formed on the BizO old edge lumbar edge coating obtained as described above, and mixed. Here, the binder is a polyimide resin diluted so that the solid content is 5 wt% with respect to the solvent (for example, n-methyl-2-pyrrolidone), and mixed with ZnO powder in an equal weight, for example, It was made into a paint form. Next, the paint obtained as described above was coated with ITO as shown in FIG.
(≧Indium tin oxide) It is coated on the glass substrate 3 provided with the electrode 1 by screen printing, and the same glass substrate 4 provided with the ITO electrode 2 is placed on top of it,
It was cured in the air at 280 to 400°C for 30 minutes, and a voltage nonlinear element 6 was provided between the electrodes 1.2. FIG. 2 is an enlarged cross-sectional view of the voltage nonlinear element 5, in which 6 is a ZnO powder, 7 is a BizOs insulating coating applied to the surface of the ZnO powder 6, and 8 is a mechanical layer between the ZnO powders 6. This binder 8 binds the ZnO powders 6 together. Figure 4 shows ITO electrodes 1a, 1
A case is shown in which the voltage nonlinear element 5 is configured on a glass substrate 32L provided with the voltage nonlinear element 5.b.
次に、上記のようにして作成された電圧非直線性素子の
電圧−電流特性について説明する。まず、第５図は第３
図の構成における電圧−電流特性を従来のＺｎＯバリス
タのそれと比較して示している。本発明の素子は、まず
酸化亜鉛２！ｌ−７ｏｏ″Ｃで焼成し、これにＢｉ２Ｏ
，を０．５ ｍｏｌ ％添加したものを９００’Ｃ，８
０分間熱処理した後、この平均粒子径６〜１０μｍのＺ
ｎＯ粉末と結合剤とを等重量で混合したものにおいて、
素子面積を１−９電極間距離を３０μｍとした場合にお
ける特性を示している。さて、電圧非直線性素子の電圧
−電流特性は、よく知られているように近似的に次式で
示されている。Next, the voltage-current characteristics of the voltage nonlinear element created as described above will be explained. First, Figure 5 shows the 3rd
The voltage-current characteristics of the configuration shown in the figure are compared with those of a conventional ZnO varistor. The element of the present invention first has zinc oxide 2! Baked at l-7oo''C, and added with Bi2O
, to which 0.5 mol % was added was heated at 900'C, 8
After heat treatment for 0 minutes, Z with an average particle size of 6 to 10 μm
In a mixture of equal weights of nO powder and binder,
The characteristics are shown when the element area is 1-9 and the distance between the electrodes is 30 μm. Now, as is well known, the voltage-current characteristics of a voltage nonlinear element are approximately expressed by the following equation.
工＝に’／Ｃ１
ここで、工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
た電圧非直線特性の指数を示してお９、この電圧非直線
指数αは大きい程、電圧非直線性が優れていることにな
る。k=N'/C1 Here, k 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 nonlinear characteristic mentioned above. 9. The larger the voltage nonlinearity index α, the better the voltage nonlinearity.
第５図の特性に示されるように、特性Ｂで示される従来
のＺｎＯバリスタは低電流域において電圧非直線指数α
が小さく、１０＝Ａ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得ない。−力、特性ムで示さ
れる本発明の素子では低電流域においても電圧非直線指
数αが大きく、１ｏ−１０ム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。また、通常、ＺｎＯバリスタにおいて
はバリスタ特性を表わすのに、例えば素子に１ｍムの電
流を流した時の電極間に現れる電圧をバリスタ電圧Ｖ１
１１１Ａと呼び、このバリスタ電圧Ｙ１ｍＡと上記電圧
非直線指数αとを使用している。本発明の素子では、上
述したように、低電流域においても電圧非直線指数αが
大きく、バリスタ電圧を第６図に示すように、例えばｖ
１μ人で表わすことができる。As shown in the characteristics in Figure 5, the conventional ZnO varistor shown in characteristic B has a voltage nonlinearity index α in the low current region
is small, and cannot function as a good voltage nonlinear element at a current of 10 A or less. - The device of the present invention, which is expressed in terms of force and characteristic μ, has a large voltage nonlinearity index α even in the low current range, and can sufficiently function as a voltage nonlinear device even in the current range of about 10-10 μm. It shows what can be done. 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 mm is passed through the element is called the varistor voltage V1.
111A, and this varistor voltage Y1mA and the voltage non-linearity index α are used. As mentioned above, in the device of the present invention, the voltage non-linearity index α is large even in the low current range, and the varistor voltage is changed, for example, to v as shown in FIG.
It can be expressed in 1μ person.
このように本発明において、バリスタ電圧を低いものと
することができるのは、電極間距離を狭くして素子を形
成することができるためである。In this way, in the present invention, the varistor voltage can be made low because the element can be formed by narrowing the distance between the electrodes.
また、本発明素子釦おいて低電流域でも電圧非直線指数
αが大きい理由は、現在のところ理由は明確とはなって
いないが、粉末状の半導体物質（ＺｎＯ）を結合剤でも
って固めたものであるため、それぞれの半導体物質の間
は点接触となシ、接触面積が小さいこと、また結合剤が
絶縁性のため、漏れ電流が小さくなっていることによる
ものと考えられる。In addition, the reason why the voltage nonlinearity index α is large even in the low current range in the element button of the present invention is not clear at present, but the reason is that powdered semiconductor material (ZnO) is hardened with a binder. This is thought to be due to the fact that since there is no point contact between the respective semiconductor materials, the contact area is small, and the bonding agent is insulating, so the leakage current is small.
ここで、第５図の特性は上述したように電極間距離を３
０μｍとした素子についてのものであるが、これはＺｎ
Ｏ粉末の平均粒子径が５〜１０μｍという比較的大きな
粒子径のためにこれ以上狭くすることができないからで
ある。すなわち、ＺｎＯ粉末の平均粒子径が０．３〜３
μｍのものを使えば、電極間距離が１０μｍ程度もしく
はそれ以下の素子を作ることができるのであり、その場
合においても第５図に示すような良好な特性が得られる
ことを本発明者らは実験により確認した。Here, the characteristics shown in FIG. 5 are obtained by changing the distance between the electrodes by 3
This is for an element with a thickness of 0 μm;
This is because the average particle diameter of the O powder is relatively large, 5 to 10 μm, and cannot be made any narrower. That is, the average particle diameter of the ZnO powder is 0.3 to 3
The inventors have found that if a micrometer electrode is used, it is possible to create an element with an interelectrode distance of about 10 μm or less, and even in that case, good characteristics as shown in FIG. 5 can be obtained. Confirmed by experiment.
第６図は本発明において、酸化ビスマスの添加量を変え
た場合のバリスタ電圧ｖ１μＡ２電圧非直線指数αおよ
び並列静電容量Ｃの変化する様子を示している。ここで
、酸化亜鉛の焼成温度など、その他の条件は第６図の場
合の条件と同一とした。FIG. 6 shows how the varistor voltage v1 μA2 voltage nonlinear index α and parallel capacitance C change when the amount of bismuth oxide added is changed in the present invention. Here, other conditions such as the firing temperature of zinc oxide were the same as those in the case of FIG. 6.
第６図に示されるように、本発明素子においては並列静
電容量が従来のＺｎＯバリスタが１ｏＯ０〜２００００
ＰＦであるのに対して非常に小さいものとなっている
。この並列静電容量Ｃが本発明素子において小さい理由
は、上述したように半導体物質間の接触面積が小さいこ
とによるものである。また第１表は、本発明において酸
化ビスマスの添加量と熱処理温度を変えた場合のバリス
タ電圧ｖ、ハ、電圧非直線指数αおよび並列静電容量Ｃ
の変化する様子を示した表である。As shown in FIG. 6, in the device of the present invention, the parallel capacitance is 1oO0 to 20,000 compared to that of the conventional ZnO varistor.
Although it is a PF, it is very small. The reason why this parallel capacitance C is small in the device of the present invention is that the contact area between the semiconductor materials is small, as described above. Table 1 also shows the varistor voltage v, c, voltage nonlinearity index α, and parallel capacitance C when the amount of bismuth oxide added and the heat treatment temperature are changed in the present invention.
This is a table showing the changes in .
く第 １ 表〉
上記第１表および第６図よシ明らかなように、各特性値
は酸化ビスマスの添加量と熱処理温度に依存しているこ
とがわかる。ここで、酸化ビスマスの添加量はＯ，ＯＳ
〜３ｍｏ１％で特に良好な特性を示した。また、熱処理
温度は酸化ビスマスの添加量にもよるが６００〜１３５
０’Ｃの範囲で良好な特性を示した。この熱処理温度が
上記温度範囲以外、例えば６００℃未満では十分な絶縁
被膜の形成が困難であることや１３５０’Ｃを超えた温
度では電圧非直線指数αが必要とする値以下になるなど
の原因で良好な特性が得られないのである。Table 1 As is clear from Table 1 and FIG. 6 above, each characteristic value is dependent on the amount of bismuth oxide added and the heat treatment temperature. Here, the amount of bismuth oxide added is O, OS
Particularly good characteristics were shown at ~3 mo1%. In addition, the heat treatment temperature is 600 to 135, depending on the amount of bismuth oxide added.
It showed good characteristics in the 0'C range. If the heat treatment temperature is outside the above temperature range, for example below 600°C, it may be difficult to form a sufficient insulating film, and if the temperature exceeds 1350'C, the voltage non-linearity index α will be below the required value. Therefore, good characteristics cannot be obtained.
なお、上記の実施例においては、半導体物質としては、
ＺｎＯを例にとり説明したが、それ以外の半導体物質
であっても差支えないことはもちろんである。また、同
様に絶縁被膜を構成する材料としては、Ｂｉ２Ｏ５単独
に限られることはなく、Ｂｉ２Ｏ３＠主成分として、ム
ｌ 、Ｔｉ 、３ｒ 、Ｍｇ。In addition, in the above embodiment, the semiconductor material is
Although ZnO has been described as an example, it goes without saying that other semiconductor materials may be used. Similarly, the material constituting the insulating film is not limited to Bi2O5 alone, but may include Bi2O3 as main components such as Mul, Ti, 3r, and Mg.
Ｎｉ、ｃｒ 、ｓｉなどの金属酸化物またはこれら金属
の有機金属化合物を単独または組合せて使用することが
できるものである。Metal oxides such as Ni, cr, si, etc. or organometallic compounds of these metals can be used alone or in combination.
さらに、粉末状の半導体物質を固める結合剤としては、
ポリイミド樹脂以外の絶縁性の有機接着剤でもよく、熱
硬化性樹脂、たとえばフェノール樹脂、フラン樹脂、エ
リア樹脂、メラミン樹脂。Furthermore, as a binder for solidifying powdered semiconductor materials,
Insulating organic adhesives other than polyimide resins may also be used, such as thermosetting resins such as phenolic resins, furan resins, area resins, and melamine resins.
不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エ
ポキシ樹脂、ポリウレタン樹脂、ケイ素樹脂などでも良
いものであり、さらにはガラス粉末と有機バインダーと
を組合せた形で用いてもよいものである。Unsaturated polyester resins, diallyl phthalate resins, epoxy resins, polyurethane resins, silicone resins, and the like may also be used, and furthermore, a combination of glass powder and an organic binder may be used.
また、上記の実施例では素子の形成をスクリーン印刷法
により行ったが、それ以外の塗布法、例えばスプレー、
浸漬などの方法で行ってもよいものである。In addition, although the elements were formed by screen printing in the above examples, other coating methods such as spraying,
A method such as immersion may also be used.
さらにまた、上記実施例による製造方法では、まず最初
に無機質半導体である微粒子状のＺｎＯを熱処理、粉砕
し、粉末とした後に、絶縁性の無機質化合物であるＢｉ
２Ｏ３を添加し、その後熱処理を行ったが、これは無機
質半導体の微粉末に直接無機質化合物を添加するように
し、上記無機質半導体微粒子の焼成、粉砕という処理工
程を省略しても差支えないものである。Furthermore, in the manufacturing method according to the above embodiment, first, ZnO in the form of fine particles, which is an inorganic semiconductor, is heat-treated and pulverized to powder, and then Bi, which is an insulating inorganic compound, is
2O3 was added and then heat treatment was performed, but it is possible to add the inorganic compound directly to the inorganic semiconductor fine powder and omit the processing steps of firing and pulverizing the inorganic semiconductor fine particles. .
発明の効果
以上の説明よシ明らかなように本発明方法によシ得られ
た電圧非直線性素子は、低電流域における電圧非直線指
数αが犬きく、また並列静電容量の小さな素子が得られ
ることから、消費電流の小さい液晶、ＸＬ；４どのデバ
イスのスイッチング素子として最適な素子を提供できる
ものである。また、電極間距離を狭くして素子を形成す
ることができるため、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のできなかった低電圧
用ＩＣの保護素子や低い電圧における電圧安定化素子と
して使用することができる。さらに、塗布したペイント
を低い温度で硬化させて簡単にして作ることができるた
め、回路基板上やガラス基板上に素子を直接形成するこ
とができるものである。このように種々の特徴を有する
本発明の電圧非直線性素子は、今までのＺｎＯバリスタ
などでは考えられない幅広い用途が期待できるものであ
り、その産業性は犬なるものである。Effects of the Invention As is clear from the above explanation, the voltage nonlinear device obtained by the method of the present invention has a high voltage nonlinearity index α in the low current region, and the device has a small parallel capacitance. As a result, it is possible to provide an element that consumes low current and is optimal as a switching element for any device such as a liquid crystal or XL4. In addition, since the device can be formed with a narrow distance between the electrodes, a low varistor voltage can be obtained, which, combined with the large voltage nonlinearity index α mentioned above, cannot be achieved with conventional ZnO varistors. It can be used as a protection element for low voltage ICs or as a voltage stabilizing element at low voltages. Furthermore, since the applied paint can be cured at low temperatures and easily manufactured, elements can be directly formed on circuit boards or glass substrates. The voltage non-linear element of the present invention having such various characteristics can be expected to have a wide range of applications unimaginable for conventional ZnO varistors and the like, and its industrial applicability is excellent.
第１図は本発明方法による電圧非直線性素子の製造方法
の工程を示す図、第２図は本発明方法により得られた電
圧非直線性素子の一実施例を示す拡大断面図、第３図お
よび第４図はそれぞれ本発明の素子をガラス基板上に設
けた実施例を示す断面図、第５図は本発明方法により得
られた素子と従来のＺｎＯバリスタの電圧−電流特性を
示す図、第６図は本発明方法による素子においてＢｉ２
Ｏ５の添加量を変えた場合の電圧非直線指数α、バリス
タ電圧ｖ１μＡおよび並列静電容量Ｇの変化する様子を
示す図である。
１ 、 ｆ ＩＬ 、 １ ｂ 、 ２−−−−−４Ｔ
Ｏ電極、３，３１Ｌ。
４・・・・・・ガラス基板、６・・・・・・電圧非直線
性素子、ｅ・・・・・・ＺｎＯ粉末、Ｔ・・・・・・Ｂ
ｉ ２０５絶縁被膜、８・・・・・・結合剤。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
第２図
電極 ５
第５図
一力 電圧（Ｖ）FIG. 1 is a diagram showing the steps of a method for manufacturing a voltage nonlinear element according to the method of the present invention, FIG. 2 is an enlarged sectional view showing an example of a voltage nonlinear element obtained by the method of the present invention, and FIG. 4 and 4 are cross-sectional views showing examples in which the device of the present invention is provided on a glass substrate, respectively, and FIG. 5 is a diagram showing the voltage-current characteristics of the device obtained by the method of the present invention and a conventional ZnO varistor. , FIG. 6 shows Bi2 in the device according to the method of the present invention.
FIG. 3 is a diagram showing how the voltage non-linearity index α, the varistor voltage v1 μA, and the parallel capacitance G change when the amount of O5 added is changed. 1, fIL, 1b, 2-----4T
O electrode, 3,31L. 4...Glass substrate, 6...Voltage nonlinear element, e...ZnO powder, T...B
i 205 Insulating coating, 8...Binder. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2 Electrode 5 Figure 5 Power Voltage (V)
Claims (1)
機化合物を添加し、混合した後、６００〜１３５０℃で
熱処理を行い、無機質半導体微粉末の表面に無機質絶縁
被膜を形成させると共に、その絶縁被膜を表面に有した
微粉末状の上記無機質半導体の全部またはほとんどがそ
れぞれ複数個集まった状態となるようにし、その後微粉
末状の無機質半導体が複数個集まった状態の粉末または
一部に上記微粉末を含む粉末に絶縁性の有機接着剤かま
たはガラス粉末と有機バインダーを加え、ペイント状に
し、次いで上記ペイントを電極を配した絶縁基板上に印
刷、スプレーまたは浸漬などによって塗布した後、熱処
理を行って硬化させることを特徴とする電圧非直線性素
子の製造方法。After adding and mixing an inorganic or organic compound containing Bi to a fine powder of an inorganic semiconductor, heat treatment is performed at 600 to 1350°C to form an inorganic insulating film on the surface of the fine inorganic semiconductor powder. All or most of the above inorganic semiconductors in the form of fine powder on the surface are brought into a state where a plurality of pieces are gathered together, and then the above fine powder is applied to the powder or a part of the state in which a plurality of the inorganic semiconductors in the form of fine powder are gathered. An insulating organic adhesive or glass powder and an organic binder are added to the powder containing the powder to form a paint, and the paint is then applied by printing, spraying or dipping onto an insulating substrate on which electrodes are arranged, followed by heat treatment. A method for manufacturing a voltage nonlinear element, the method comprising curing the element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61034653A JPS62190816A (en) | 1986-02-18 | 1986-02-18 | Manufacture of voltage nonlinear device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61034653A JPS62190816A (en) | 1986-02-18 | 1986-02-18 | Manufacture of voltage nonlinear device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62190816A true JPS62190816A (en) | 1987-08-21 |
Family
ID=12420397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61034653A Pending JPS62190816A (en) | 1986-02-18 | 1986-02-18 | Manufacture of voltage nonlinear device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62190816A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010521058A (en) * | 2006-09-24 | 2010-06-17 | ショッキング テクノロジーズ，インコーポレイテッド | Composition of voltage-switchable dielectric material having step voltage response and method of manufacturing the dielectric material |
-
1986
- 1986-02-18 JP JP61034653A patent/JPS62190816A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010521058A (en) * | 2006-09-24 | 2010-06-17 | ショッキング テクノロジーズ，インコーポレイテッド | Composition of voltage-switchable dielectric material having step voltage response and method of manufacturing the dielectric material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS62190816A (en) | Manufacture of voltage nonlinear device | |
| JPS62190817A (en) | Manufacture of voltage nonlinear device | |
| JPS62193227A (en) | Manufacture of voltage nonlinear device | |
| JPS62190815A (en) | Manufacture of voltage nonlinear device | |
| JPS62190802A (en) | Manufacture of voltage nonlinear device | |
| JPS62190820A (en) | Manufacture of voltage nonlinear device | |
| JPS62190811A (en) | Voltage nonlinear device | |
| JPS62190821A (en) | Manufacture of voltage nonlinear device | |
| JPS62190807A (en) | Manufacture of voltage nonlinear device | |
| JPS62190803A (en) | Manufacture of voltage nonlinear device | |
| JPS62190810A (en) | Voltage nonlinear device | |
| JPS62190801A (en) | Manufacture of voltage nonlinear device | |
| JPS62193209A (en) | Voltage nonlinear device | |
| JPS62242310A (en) | Voltage nonlinear device | |
| JPS62242307A (en) | Voltage nonlinear device | |
| JPS62193221A (en) | Manufacture of voltage nonlinear device | |
| JPS62190812A (en) | Voltage nonlinear device | |
| JPS62242304A (en) | Voltage nonlinear device | |
| JPS62193217A (en) | Manufacture of voltage nonlinear device | |
| JPS62242302A (en) | Voltage nonlinear device | |
| JPS62193210A (en) | Manufacture of voltage nonlinear device | |
| JPS62242306A (en) | Voltage nonlinear device | |
| JPS62242303A (en) | Voltage nonlinear device | |
| JPS62193224A (en) | Manufacture of voltage nonlinear device | |
| JPS62193215A (en) | Manufacture of voltage nonlinear device |