CN104478428B - Zinc oxide piezoresistor material with high electric potential gradient - Google Patents
Zinc oxide piezoresistor material with high electric potential gradient Download PDFInfo
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Abstract
The invention discloses a zinc oxide piezoresistor material with a high electric potential gradient and belongs to the field of semiconductor electronic materials. The zinc oxide piezoresistor material is characterized in that nanoscale zinc oxide is taken as a main body, is added with micron-sized additives including bismuth oxide, antimony oxide, chromic oxide and cobalt oxide, is also added with a trace amount of manganese dioxide and 2-3 types of rare-earth oxides; all the components are fully mixed, dried, pre-roasted, granulated, compression-molded and then subjected to low-temperature glue discharging and high-temperature sintering to prepare a zinc oxide resistor valve plate, wherein the zinc oxide resistor valve plate is small in average grain size (less than 4 microns), has an electric potential gradient between 750V/mm and 1150V/mm, has a nonlinear coefficient being greater than 25, has leak current being smaller than 5 microamps and also has excellent electrical properties.
Description
Technical field
The invention belongs to semiconductor electronic Material Field, it is related to a kind of high-potential gradient zinc oxide piezoresistive material.
Background technology
Zinc-oxide piezoresistor assumes excellent nonlinear wind vibration and receives significant attention.Zinc-oxide piezoresistor is made
For overvoltage protection device, voltage limiter and arrester, it is widely used in the fields such as electronics, electric, communication and building.At present, exist
The application such as high-tension circuit and lightning-arrest device, piezo-resistance develops to high-pressure trend, miniaturization, big through-current capacity direction, to oxidation
The combination property of zinc piezoresistive material is put forward higher requirement.Traditional zinc oxide piezoresistive material, voltage gradient exists
200 ~ 400 V/mm are it is difficult to meet the application requirement of high pressure and super-pressure resistance device.
Chinese scholars are had to carry out numerous studies for high potential gradient pressure-sensitive resistance material.Patent CN
The electric potential gradient of the high voltage ZnO resistors valve block that 101383208B is announced reaches 400 V/mm, but its coarse grains（>
7.0 μm）, and its dumping, sintering process are complicated.The high-potential gracient material that patent CN 100382205C announces, current potential ladder
Degree reaches 820 ~ 900 V/mm, but its method of adopting high-energy ball milling, and too high to equipment requirement, energy consumption is big, is unfavorable for that energy-conservation pushes away
Extensively.Patent CN 1181502C discloses the preparation technology that part nano zine oxide substitutes micron zinc oxide, obtains electric potential gradient and reaches
To 580 V/mm, method is simply effective, but its electric potential gradient still has much room for improvement.Therefore, in order to overcome prior art defect, grind
Study carefully that crystallite dimension is tiny, high-potential gracient, good combination property ZnO resistors valve block is most important with exploitation, and have wide
Wealthy application prospect.
Content of the invention
It is an object of the invention to provide a kind of high potential gradient pressure-sensitive resistance material, the resistor valve sheet tool that this material makes
There are the performances such as high-voltage gradient, higher nonlinear factor, less leakage current, can be applicable to the protection device of power system,
And be conducive to the miniaturization of varistor device.
Technical scheme：A kind of high-potential gradient zinc oxide piezoresistive valve block, calculates according to molar ratio, it
It is made up of following material powder：Nano-ZnO 94.0 ~ 97.0%, Bi2O30.35~0.8%、Sb2O31.0~2.0%、Cr2O3
0.4~0.7%、Co2O30.35~0.7%、MnO20.5 ~ 0.7%, rare earth oxide 0.02 ~ 1.1%.
The preparation method of described high voltage varistor valve block, comprises the following steps：
（1）Ball mill mixing
The micron powder of multielement additive is proportionally weighed, is placed in agate pot, add absolute ethyl alcohol or acetone to make
Lubricant, wet ball grinding 2 ~ 4 h in planetary ball mill, then it is proportionally added into nano-zinc oxide powder, wet ball grinding 24 h,
Absolute ethyl alcohol or acetone is added to be limited with mixed powder sufficient lubrication；
（2）Drying, pre-burning
Mixed powder after ball milling is dried through 60 ~ 80 DEG C, and in 400 ~ 450 DEG C of pre-burning 1 ~ 2 h；
（3）Granulation, shaping
Add 3 ~ 6 wt% polyvinyl alcohol（PVA）Granulation, forcing press shaping afterwards, disk a size of Φ 15 mm, thickness 1.5
mm；
（4）Sintering
Using continuous tunnel furnace or batch-type furnace, temperature is incubated 1 h dumping at 400 DEG C, is then incubated 2 h in 1100 ~ 1200 DEG C；
（5）By silver electrode
Using continuous tunnel furnace or batch-type furnace, 850 ~ 870 DEG C of temperature 0.5 ~ 1 h.
Compared with prior art, the zinc oxide varistor valve average grain size that the present invention obtains is tiny（< 4 μ
m）, there is Width funtion gradient scope（750~1150 V/mm）, nonlinear factor α>25, leakage current IL<5 μ A, combination property is good
Good.Product can obtain the voltage gradient of demand by adjusting sintering temperature and food ingredient, and voltage gradient has larger tune
Between main plot.
Brief description
Fig. 1 is the preparation technology flow chart of high-potential gradient zinc oxide pressure sensitive；
Fig. 2 is the SEM spectrum of the zinc oxide pressure-sensitive material of embodiment 1；
Fig. 3 is the SEM spectrum of the zinc oxide pressure-sensitive material of embodiment 2；
Fig. 4 is the XRD spectrum of the zinc oxide pressure-sensitive material of embodiment 1；
Fig. 5 is the XRD spectrum of the zinc oxide pressure-sensitive material of embodiment 2.
Specific embodiment：
Embodiment 1
The formula of the present embodiment is as follows：
Nano-ZnO 96.6%, micron Bi2O30.7%、Sb2O31.0%、Cr2O30.5%、Co2O30.5%、MnO20.5%、
La2O30.1% 、Sm2O30.1%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 2 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 60 DEG C of temperature, and in 400 DEG C of pre-burning 2 h.4% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1100 DEG C, cools to room temperature with the furnace after heat preservation sintering 2 h, and in 850 DEG C of insulation 1 h by silver electricity
Pole.Through performance test, voltage gradient is 780 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 46, electric leakage
Flow for 1.7 μ A.
Embodiment 2
The formula of the present embodiment is as follows：
Nano-ZnO 96.2%, micron Bi2O30.7%、Sb2O31.0%、Cr2O30.5%、Co2O30.5%、MnO20.5%、
La2O30.1% 、Sm2O30.5%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 3 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 80 DEG C of temperature, and in 450 DEG C of pre-burning 1 h.3% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1100 DEG C, cools to room temperature with the furnace after heat preservation sintering 2 h, and silver-colored in 870 DEG C of insulation 0.5 h
Electrode.Through performance test, voltage gradient is 1100 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 70, leakage
Electric current is 4.3 μ A.
Embodiment 3
The formula of the present embodiment is as follows：
Nano-ZnO 97.0%, micron Bi2O30.35%、Sb2O31.3%、Cr2O30.45%、Co2O30.35%、MnO2
0.53%、Nd2O30.01%、Y2O30.01%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 4 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 60 DEG C of temperature, and in 400 DEG C of pre-burning 2 h.5% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1100 DEG C, cools to room temperature with the furnace after heat preservation sintering 2h, and in 870 DEG C of insulation 0.5 h by silver electricity
Pole.Through performance test, voltage gradient is 950 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 27, electric leakage
Flow for 2.6 μ A.
Embodiment 4
The formula of the present embodiment is as follows：
Nano-ZnO 95.5%, micron Bi2O30.55%、Sb2O31.7%、Cr2O30.6%、Co2O30.5%、MnO20.6%、
Eu2O30.25%、Y2O30.3%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 3 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 60 DEG C of temperature, and in 450 DEG C of pre-burning 1 h.5% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1100 DEG C, cools to room temperature with the furnace after heat preservation sintering 2 h, and in 850 DEG C of insulation 1 h by silver electricity
Pole.Through performance test, voltage gradient is 1000 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 30, electric leakage
Flow for 2.1 μ A.
Embodiment 5
The formula of the present embodiment is as follows：
Nano-ZnO 94.5%, micron Bi2O30.75%、Sb2O31.8%、Cr2O30.65%、Co2O30.6%、MnO2
0.65%、Dy2O30.45%、Y2O30.35%、Er2O30.25%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 2 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 70 DEG C of temperature, and in 400 DEG C of pre-burning 2 h.6% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1150 DEG C, cools to room temperature with the furnace after heat preservation sintering 2 h, and silver-colored in 870 DEG C of insulation 0.5 h
Electrode.Through performance test, voltage gradient is 920 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 33, leakage
Electric current is 1.9 μ A.
Embodiment 6
The formula of the present embodiment is as follows：
Nano-ZnO 94.0%, micron Bi2O30.8%、Sb2O32.0%、Cr2O30.7%、Co2O30.7%、MnO20.7%、
Er2O30.55%、Pr6O110.45%、CeO20.1%；
The micron powder of multielement additive is proportionally weighed and adds after mixing in agate grinding pot, add absolute ethyl alcohol
Or acetone makees lubricant, wet ball grinding 4 h in planetary ball mill, add absolute ethyl alcohol or the amount of acetone to fill with mixed powder
Cunning of sharing in the benefit is limited.Press proportioning in additive powder upon mixing and add nano-zinc oxide powder, wet ball grinding 24 h.By powder
Dry at 70 DEG C of temperature, and in 450 DEG C of pre-burning 1 h.4% is added after powder pre-burning（Mass fraction）Polyvinyl alcohol（PVA）
As bonding agent, dry-pressing becomes Φ 15 mm, the green compact of thickness 1.5 mm.Green compact are positioned in stove and are to slowly warm up to 400 DEG C of insulations 1
H carries out dumping, then is warming up to 1200 DEG C, cools to room temperature with the furnace after heat preservation sintering 2 h, and silver-colored in 870 DEG C of insulation 0.5 h
Electrode.Through performance test, voltage gradient is 850 V/mm to the zinc oxide varistor valve of gained, and nonlinear factor is 37, leakage
Electric current is 1.2 μ A.
Claims (2)
1. a kind of high-potential gradient zinc oxide piezoresistive material is it is characterised in that with Nano-class zinc oxide as material of main part, add
Plus micron order additive, concrete component comprises：
Nanoscale ZnO 94.0～97.0%
Micron order additive Bi2O30.35～0.8%
Sb2O31.0～2.0%
Cr2O30.4～0.7%
Co2O30.35～0.7%
MnO20.5～0.7%
Rare earth oxide 0.02～1.1%
Wherein, rare earth oxide is Pr6O11、La2O3、Y2O3、Sm2O3、Nd2O3、CeO2、Eu2O3、Dy2O3、Er2O3In 2～3
Kind.
2. a kind of preparation method of high-potential gradient zinc oxide piezoresistive material as claimed in claim 1, its concrete steps is such as
Under：
(1) ball mill mixing
The micron powder of multielement additive is proportionally weighed, is placed in agate pot, add absolute ethyl alcohol or acetone to lubricate
Agent, wet ball grinding 2～4h in planetary ball mill, then it is proportionally added into nano-zinc oxide powder, and wet ball grinding 24h, add
Absolute ethyl alcohol or acetone are limited with mixed powder sufficient lubrication；
(2) drying, pre-burning
Mixed powder after ball milling is dried through 60～80 DEG C, and in 400～450 DEG C of pre-burning 1～2h；
(3) granulation, shaping
3～6wt% polyvinyl alcohol (PVA) is added to granulate afterwards, forcing press is molded, disk a size of Φ 15mm, thickness 1.5mm；
(4) sinter
Using continuous tunnel furnace or batch-type furnace, temperature is incubated 1h dumping at 400 DEG C, is then incubated 2h in 1100～1200 DEG C；
(5) by silver electrode
Using continuous tunnel furnace or batch-type furnace, 850～870 DEG C of temperature 0.5～1h.
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| CN105139986B (en) * | 2015-09-23 | 2018-04-03 | 南京先正电子股份有限公司 | Explosion-proof type zinc oxide varistor and preparation method thereof |
| CN105272208B (en) * | 2015-11-07 | 2018-04-27 | 汕头高新区松田实业有限公司 | A kind of zinc oxide varistor dielectric material and preparation method thereof |
| CN106024231B (en) * | 2016-05-27 | 2018-07-10 | 辰硕电子(九江)有限公司 | A kind of preparation method of zinc oxide varistor tile |
| CN107021751A (en) * | 2017-04-10 | 2017-08-08 | 湖北工业大学 | A kind of high-potential gracient arrester zinc oxide piezoresistor ceramic |
| CN108264343A (en) * | 2018-02-07 | 2018-07-10 | 合肥安力电力工程有限公司 | A kind of modified nano zinc oxide piezoresistive material and preparation method thereof |
| CN108794036A (en) * | 2018-05-23 | 2018-11-13 | 宁夏中科天际防雷研究院有限公司 | A kind of lightning protection electrical chip and its preparation method and application based on zinc oxide |
| CN108484158A (en) * | 2018-05-23 | 2018-09-04 | 江苏时瑞电子科技有限公司 | A kind of dielectric material of piezoresistor and preparation method thereof |
| CN108774061B (en) * | 2018-06-26 | 2021-06-01 | 东莞市瓷谷电子科技有限公司 | High-performance zinc oxide piezoresistor dielectric material and preparation method thereof |
| CN109734435A (en) * | 2018-11-19 | 2019-05-10 | 西安交通大学 | A kind of Nanocrystalline Zno-based Varistor material and preparation method |
| CN110423110B (en) * | 2019-09-01 | 2021-11-05 | 烟台大学 | Ultrahigh nonlinear ZnO-Bi2O3Base pressure sensitive ceramic and preparation method thereof |
| CN116835975B (en) * | 2023-07-05 | 2024-05-14 | 广东电网有限责任公司 | ZnO polycrystalline ceramic with high breakdown field strength, preparation method and cable sheath protector |
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| CN1181502C (en) * | 2002-09-13 | 2004-12-22 | 四川大学 | Material for producing voltage sensitive zine oxide resistor |
| CN102515741A (en) * | 2011-12-07 | 2012-06-27 | 中国科学院过程工程研究所 | Zinc oxide varistor material and preparation method thereof |
| CN103951415B (en) * | 2014-04-01 | 2016-04-27 | 西安电子科技大学 | A kind of high voltage gradient zinc oxide varistor and preparation method thereof |
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