CN1342985A - Material for over-voltage protecting element and its making method - Google Patents
Material for over-voltage protecting element and its making method Download PDFInfo
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- CN1342985A CN1342985A CN 00124765 CN00124765A CN1342985A CN 1342985 A CN1342985 A CN 1342985A CN 00124765 CN00124765 CN 00124765 CN 00124765 A CN00124765 A CN 00124765A CN 1342985 A CN1342985 A CN 1342985A
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- ceramic powders
- overvoltage protection
- protection element
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- powder
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- 239000000463 material Substances 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 17
- 239000000843 powder Substances 0.000 claims abstract description 76
- 239000000919 ceramic Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910002113 barium titanate Inorganic materials 0.000 claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 230000004044 response Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000001012 protector Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 13
- 239000004020 conductor Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- 210000003850 cellular structure Anatomy 0.000 description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000222640 Polyporus Species 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- Thermistors And Varistors (AREA)
- Emergency Protection Circuit Devices (AREA)
Abstract
An over-voltage protector is prepared through mixing at least two kinds of ceramic powder together, calcining to obtain powder with P-N interface, dispersing it in a solution containing adhesive to obtain paste, filling the paste in the space between two electrodes and sintering to form porous structural body. Its advantages are low leakage current, low capacitance and high response speed.
Description
The present invention relates to a kind of material and manufacture method thereof of overvoltage protection element.
The material of existing zinc oxide varistor and structure thereof, constituted with oxides such as zinc oxide and B, Bi, Ba, Si, Sr, Pb, Pr, Co, Mn, Sb or Cr or its composite material, bismuth oxides etc. are to form a grain boundary layer between the particle of zinc oxide, the structural requirement of this kind material is that density of material is made into structure near solid density, generally be at more than 90% of theoretical density, be a kind of commercial product, but this kind element have the shortcoming of high capacity.Grain boundary layer is similar a kind of capacitor in electrical performance, and therefore the made rheostat of this material has higher capacitance, is not suitable in the high-frequency circuit, and this is the rheostatic great shortcoming of this kind.The material of overvoltage protection element of the present invention is a cellular structure, if therefore use identical materials to form and the components identical structure, also because of the genus polyporus material structure, and has lower capacitance and leakage current, therefore can be applicable in the high-frequency circuit.
The breakdown voltage of zinc oxide resistance device is relevant with two interelectrode zinc oxide grains, the rheostatic microstructure of conventional oxidation zinc as shown in Figure 1, there is one deck grain boundary layer between zinc oxide grain, this grain boundary layer is oxides such as bismuth oxide, is commonly referred to as rich bismuth district, the interval P-N interface that forms of zinc oxide and rich bismuth, if end to end from electrode, represent zinc oxide semi-conductor with N, represent rich bismuth district with P, therefore rheostatic P-N structure can be expressed as
E-P-N-P-N-……-N-P-N-P-E
Wherein, E is a conductor electrode, and all there is a breakdown voltage Vb1 in each P-N interface, supposes always to co-exist between electrode X P-N interface, and breakdown voltage Vb can be described as Vb=∑ Vb1.
The material of the overvoltage protection element of delivering in the past; once at US Pat.4; 726; 991 have delivered a kind of material; its material structure is semiconductor or the semiconductor powder layer insulating that is covered; this insulating barrier is less than the thickness of hundreds of dusts (angstroms); there are some shortcomings in this kind material structure in practicality, at first, the thickness of insulating barrier is only within hundreds of dusts; the degree of difficulty of the manufacturing process of this thickness is high; when the thickness of insulating layer of lining when too thin, easily cause the short circuit of element, when thickness of insulating layer thick slightly; but can improve breakdown voltage, this is to use insulating barrier to be coated on the shortcoming on conductor or semiconductor powder surface.
Belong to the incrusting type material equally, US Pat.5,294,374 have delivered a kind of material, its material structure is the semi-conductive mixture that conductor powder is covered a layer insulating and is not covered, its lining thickness is between between 70 dusts and 1 micron, its coating material can be used semiconductor, basically, these materials all are to block passing through of electric current with insulating material or semi-conducting material, and reach high-resistance purpose, but the thickness of coating directly influences the breakdown voltage of element, so the uniformity of thickness is very important.
The object of the present invention is to provide a kind of material and manufacture method thereof of overvoltage protection element; material according to overvoltage protection element of the present invention; it is a kind of powder body material; the particle of powder body material itself possesses the P-N interface; existence because of this interface; make powder body material itself possess low leakage characteristic; when the situation of surging generation is arranged in the circuit; voltage increases suddenly; material just can instant failure; material moment becomes conductor, and can be used as the material of overvoltage protection element, and this is an one object of the present invention.
The present invention is the porous material at P-N interface; material structure such as Fig. 2 or shown in Figure 3 from the end to end of electrode, represent zinc oxide semi-conductor with P; represent that with N coating layer is the oxide of bismuth oxide-containing, therefore the P-N structure of overvoltage protection element of the present invention can be expressed as
E-P-N-P-S-P-N-P-……-P-N-P-S-P-N-P-E
Wherein, P-N-P represents a crystal grain; S represents the wall of crystal grain and intergranule; S can be the insulator of air or glass etc., and breakdown voltage is therebetween represented with Vs, also can make S not exist because of crystal grain contacts with crystal grain; there is a breakdown voltage Vb2 in each P-N-P; be made up of several crystal grain between electrode, so the breakdown voltage of element can be expressed as Vb=∑ Vb2+ ∑ Vs, therefore the principle of overvoltage protection element of the present invention is different from traditional overvoltage protection element.
Be uniformly distributed in the solvent with this powder body material, or be uniformly distributed in the solvent that contains binding agent (binder), or be uniformly distributed in the solvent with glass powder, or be uniformly distributed in the solvent that contains binding agent with glass powder, and the suitable paste of furnishing, insert between the electrode of spacing, drying again, behind the sintering, make material sinter the cellular structure body into, the density of this cellular structure body (or being referred to as the porous material body) is controlled between the 30-90% of solid density, possessed the advantage of low capacitance and low-leakage current with this element of making, this is an another object of the present invention.
Existing overvoltage protection material; the element that is constituted with insulating material isolated conductor or semiconductor powder is arranged; these elements are on making; when very easily being distributed in insulating material because of conductor powder; the generation conductor powder flocks together; and the generation situation of short circuit; powder body material of the present invention itself possesses the P-N-P interface; therefore resistance is very high; powder and powder flock together, and do not influence any characteristic of element, do not have similar short circuit phenomenon and take place; therefore be a kind of manufacturing process of making the very high and characteristic quite stable of acceptance rate, this is an another object of the present invention.
Existing overvoltage protection material; having with insulating material coated conductor or semiconductor powder surface is the element that overvoltage protection material was constituted; also having with isolated conductor of insulating material or semiconductor powder is the element that overvoltage protection material was constituted; the thickness of these insulating material directly influences the breakdown voltage of element; overvoltage protection material of the present invention; itself possesses grain boundary layer powder body material; therefore the breakdown voltage of element and the thickness of coating there is no direct relation; and with the quantity at P-N-P interface; the breakdown voltage at interface is relevant; therefore element breakdown voltage of the present invention Be Controlled very easily, this is an another object of the present invention.
, be described in further detail structure of the present invention, manufacture method, application principle, effect and effect below with reference to embodiment and accompanying drawing.
Fig. 1 is the rheostatic material structure key diagram of conventional oxidation zinc;
Fig. 2 is the material microstructure key diagram of overvoltage protection element of the present invention;
Fig. 3 is another microstructure key diagram of material of overvoltage protection element of the present invention;
Fig. 4 is the manufacturing flow chart of overvoltage protection element of the present invention;
The enforcement illustration of the overvoltage protection element that Fig. 5 makes for the present invention;
Fig. 6 is another manufacturing flow chart of overvoltage protection element of the present invention;
Fig. 7 is the electron micrograph of overvoltage protection material of the present invention;
Fig. 8 is the electrostatic discharge (ESD) protection voltage response curve of overvoltage protection element of the present invention;
Fig. 9 is the electrostatic discharge (ESD) protection current response curve of overvoltage protection element of the present invention.
[one of specific embodiment]
Fig. 2; Figure 3 shows that the microstructure of powder body material; 10 is Zinc oxide powder; zinc oxide is originally as N type semiconductor; resistance coefficient during room temperature has only Ω-cm; coating 12 its compositions comprise B; Bi; Ba; Si; Sr; Pb; Pr; Co; Mn; oxide such as Sb or Cr or its mixture; this is a P type semiconductor; form a P-N interface between this coating and zinc oxide; powder presents the situation of P type semiconductor lining N type semiconductor; therefore be the structure of P-N-P, therefore under usual operating voltage, present high-resistance situation; when surging occurs; voltage increases sharply, when the sum total of the breakdown voltage that reaches the interface, and the material instant failure; the resistance of this moment is only between number Ω-cm; allow big electric current to pass through, and the surging energy is imported ground wire, after the surging energy passes through; original high resistance state is got back at the interface, and this process just can reach the purpose of protective circuit.
The manufacture method of overvoltage protection material of the present invention, as shown in Figure 4, being described as follows of its each step:
(1), (2) step: P type semiconductor powder such as even mixed oxidization zinc powder and bismuth oxide, wherein, the percentage by weight of preferable oxide powder and zinc is 50-97.
(3), (4) step: with the mixed oxide powder of (2) step, with 800-1600 ℃ temperature calcining, after calcining (3) and grinding (4), the crystal particle structure of material promptly becomes shown in Figure 2,10 states that form the P-N interface of P type semiconductors such as bismuth oxide 12 and zinc oxide.
(5) step: the powder body material and the glass powder of (4) step gained are uniformly distributed in the solvent that contains binding agent, and obtain pastes.
(6) step: the pastes through (5) step gained can be covered on electrode 21,22 and the matrix 30 as shown in Figure 5; Through super-dry (7), burning attached (8), promptly obtain the finished product of overvoltage protection element again.
[specific embodiment two]
Another kind of material is formed still the material of overvoltage protection element for this reason; wherein two kinds of ceramic powders are respectively the ceramic powders of barium titanate, strontium titanates, calcium titanate or its mixture; be called the A powder; another kind can be oxide or its mixtures such as containing Nb, Mn, Cu, Co, Si; be called the B powder; its manufacture method, as shown in Figure 6, being described as follows of its each step:
(1), (2) step: even A powder and B powder, wherein, the percentage by weight of preferable A powder is 70-95.
(3), (4) step:,, after calcining (3) and grinding (4), form the P-N interface between two semiconductors with 800-1500 ℃ temperature calcining with the mixed oxide powder of (2) step.
(5) step: the material of (4) step gained is uniformly distributed in the solvent that contains binding agent, and obtains pastes.
(6) step: the pastes through (5) step gained can be covered on electrode 21,22 and the matrix 30 as shown in Figure 5; Through super-dry (7), burning attached (8), promptly obtain the finished product of overvoltage protection element again.
Powder body material is made overvoltage protection element thus; the structure of material is a cellular structure, and electron micrograph as shown in Figure 7 is a powder body material 40 than the light colour person wherein; than the dark colour person is air chamber 50, and this density of material is controlled in the 30-90% into solid density.
Fig. 8 is the voltage response curve of static discharge of the present invention, Fig. 9 is the current response curve of static discharge of the present invention, the static source is 8kV, shown in this figure, can clearly find out the situation after the material collapse, allow this moment a large amount of electric currents by this element, current curve as shown in Figure 9, and voltage peak (peak voltage) also only below 300V, voltage curve as shown in Figure 8.
Overvoltage protection material of the present invention; the novelty and the practicality that possess overvoltage protection material, the change of this overvoltage protection material structure makes the overvoltage protection element of gained; have more the characteristics of making stable and stability of characteristics, also have the advantage that leakage current is lower, electric capacity is little simultaneously.
Need to prove; above-described content is the concrete most preferred embodiment of the present invention, thus the change of doing according to conception of the present invention, the function of its generation; when not exceeding spiritual that specification and accompanying drawing contain, all should be within protection scope of the present invention.
Claims (17)
1, a kind of material of overvoltage protection element is characterized in that, at least two kinds of ceramic powders are fully mixed the back calcining, makes its formation contain the powder body material of P-N interface.
2, the material of overvoltage protection element as claimed in claim 1; it is characterized in that; ceramic powders in the described powder body material wherein a kind of for containing the ceramic powders of zinc oxide, another kind of for containing the ceramic powders that oxide such as B, Bi, Ba, Si, Sr, Pb, Pr, Co, Mn, Sb or Cr or its mixture are formed.
3, the material of overvoltage protection element as claimed in claim 1; it is characterized in that; ceramic powders in the described powder body material wherein a kind of for containing the ceramic powders of barium titanate, strontium titanates, calcium titanate or its mixture, another kind of for containing the ceramic powders that oxide such as Nb, Mn, Cu, Co or Si or its mixture are formed.
4, the material of overvoltage protection element as claimed in claim 1 is characterized in that, the average grain diameter of described powder body material is between 0.1-100 μ m.
5, a kind of overvoltage protection element is characterized in that being made by the following step:
At first be that at least two kinds of ceramic powders are fully mixed the back calcining; make its formation contain the powder body material of P-N interface; then powder body material is uniformly distributed in the solvent; obtain pastes, this pastes is inserted between two electrodes of spacing again, make pastes contact two electrodes simultaneously; final drying is also burnt attached this pastes; the material powder is engaged, obtain the porous material body, promptly obtain overvoltage protection element.
6, overvoltage protection element as claimed in claim 5; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powders of zinc oxide, another kind of for containing the ceramic powders that oxide such as B, Bi, Ba, Si, Sr, Pb, Pr, Co, Mn, Sb or Cr or its mixture are formed.
7, overvoltage protection element as claimed in claim 5; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powders of barium titanate, strontium titanates or calcium titanate or its mixture, another kind of for containing the ceramic powders that oxide such as Nb, Mn, Cu, Co or Si or its mixture are formed.
8, overvoltage protection element as claimed in claim 5 is characterized in that, the density of material of described porous material body is between the 30-90% of theoretical density.
9, a kind of manufacture method of overvoltage protection element is characterized in that, comprises the following steps:
At least two kinds of ceramic powders are fully mixed the back calcining; make its formation contain the powder body material of P-N interface; evenly the distribution powder body material is in solvent; obtain pastes, this pastes is inserted between two electrodes of spacing, make pastes contact two electrodes simultaneously; drying is also burnt attached this pastes; the material powder is engaged, obtain the porous material body, promptly obtain overvoltage protection element.
10, the manufacture method of overvoltage protection element as claimed in claim 9 is characterized in that, contains binding agent in the described solvent.
11, as the manufacture method of claim 9 or 10 described overvoltage protection elements, it is characterized in that, be added with glass powder in the described powder body material.
12, as the manufacture method of claim 9 or 10 described overvoltage protection elements; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powders of zinc oxide, another kind of for containing the ceramic powders that oxide such as B, Bi, Ba, Si, Sr, Pb, Pr, Co, Mn, Sb or Cr or its mixture are formed.
13, as the manufacture method of claim 9 or 10 described overvoltage protection elements; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powders of barium titanate, strontium titanates or calcium titanate or its mixture, another kind of for containing the ceramic powders that oxide such as Nb, Mn, Cu, Co or Si or its mixture are formed.
As the manufacture method of claim 9 or 10 described overvoltage protection elements, it is characterized in that 14, the density of material of described porous material body is between the 30-90% of theoretical density.
15, the manufacture method of overvoltage protection element as claimed in claim 11; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powders of zinc oxide, another kind of for containing the ceramic powders that oxide such as B, Bi, Ba, Si, Sr, Pb, Pr, Co, Mn, Sb or Cr or its mixture are formed.
16, the manufacture method of overvoltage protection element as claimed in claim 11; it is characterized in that; described ceramic powders wherein a kind of for containing the ceramic powder of barium titanate, strontium titanates or calcium titanate or its mixture, another kind of for containing the ceramic powders that oxide such as Nb, Mn, Cu, Co or Si or 3 its mixtures are formed.
17, the manufacture method of overvoltage protection element as claimed in claim 11 is characterized in that, the density of material of described porous material body is between the 30-90% of theoretical density.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00124765 CN1342985A (en) | 2000-09-14 | 2000-09-14 | Material for over-voltage protecting element and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00124765 CN1342985A (en) | 2000-09-14 | 2000-09-14 | Material for over-voltage protecting element and its making method |
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| Publication Number | Publication Date |
|---|---|
| CN1342985A true CN1342985A (en) | 2002-04-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00124765 Pending CN1342985A (en) | 2000-09-14 | 2000-09-14 | Material for over-voltage protecting element and its making method |
Country Status (1)
| Country | Link |
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| CN (1) | CN1342985A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071666B (en) * | 2007-06-22 | 2010-06-09 | 赑丰生技股份有限公司 | Low-capacitance layered wafer rheostat and overvoltage protection material thereof |
| WO2010083727A1 (en) * | 2009-01-23 | 2010-07-29 | Shang-Yo Lee | Surge arrester |
-
2000
- 2000-09-14 CN CN 00124765 patent/CN1342985A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071666B (en) * | 2007-06-22 | 2010-06-09 | 赑丰生技股份有限公司 | Low-capacitance layered wafer rheostat and overvoltage protection material thereof |
| WO2010083727A1 (en) * | 2009-01-23 | 2010-07-29 | Shang-Yo Lee | Surge arrester |
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