CN1595551A - Method for preparing ZnO ceramic film low-voltage piezoresistor - Google Patents

Method for preparing ZnO ceramic film low-voltage piezoresistor Download PDF

Info

Publication number
CN1595551A
CN1595551A CN 200410013447 CN200410013447A CN1595551A CN 1595551 A CN1595551 A CN 1595551A CN 200410013447 CN200410013447 CN 200410013447 CN 200410013447 A CN200410013447 A CN 200410013447A CN 1595551 A CN1595551 A CN 1595551A
Authority
CN
China
Prior art keywords
zno
ion
colloidal sol
low voltage
sol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200410013447
Other languages
Chinese (zh)
Other versions
CN100394517C (en
Inventor
姜胜林
曾亦可
李秀峰
刘梅冬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CNB2004100134479A priority Critical patent/CN100394517C/en
Publication of CN1595551A publication Critical patent/CN1595551A/en
Application granted granted Critical
Publication of CN100394517C publication Critical patent/CN100394517C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Compositions Of Oxide Ceramics (AREA)

Abstract

Disclosed is a manufacture method of ZnO ceramics film low voltage dependent resistor, comprising bismuth ion Bi 3+,antimony ion Sb3+, manganese ion Mn2+, chrome ion Cr3+ and cobalt ion Co3+ distributing in ZnO sol , and their mol ratio is: Zn2+ Bi3+ Sb3+ Mn2+ Cr3+ Co3+ =100: (0.6~1.4) : (1.6~3.0) : (0.2~1.0) : (0.5~3.0) : (1.0~3.0). The temperature of sol of 60~80% is raised to 550deg.C~650deg.C after baking to decompose organic matter, then ZnO crystal formed is milled to be ZnO nanometer powder whose diameter is 30nm~70nm, add dispersion agent into the ZnO powder and then they are added into the remain sol after mixing, at last ZnO ceramics film low voltage voltage dependent resistor is made on monocrystalline sillicon substrate. The production made by the invention has excellent electric performance, voltage dependent voltage lower than 4V, nonlinear coefficient of 22 and density of leakage current smaller than 0.4uA/nm2.

Description

The preparation method of ZnO ceramic membrane low voltage varistor
Technical field
The present invention relates to a kind of preparation method of ZnO ceramic membrane piezo-resistance.
Background technology
At present, in the preparation ZnO ceramic membrane piezo-resistance, employed film thickness is generally tens of to hundreds of nm, and too small because of thickness, voltage-dependent characteristic and stability thereof are just poor, make piezo-resistance be difficult to reach application request.Make its performance optimization need increase thickness, and crackle appears in thickness increase easily, film performance is reduced.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art part, a kind of preparation method of ZnO ceramic membrane low voltage varistor is provided.This method is by doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+, cobalt ions Co 3+, prepared ZnO ceramic membrane, thereby prepared ZnO low voltage varistor with excellent electrical properties with excellent electrical properties.
For achieving the above object, the technical solution used in the present invention is: the preparation method of ZnO ceramic membrane low voltage varistor comprises
(1) in ZnO colloidal sol, doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+With cobalt ions Co 3+, its mol ratio is: Zn 2+: Bi 3+: Sb 3+: Mn 2+: Cr 3+: Co 3+=100: (0.6～1.4): (1.6～3.0): (0.2～1.0): (0.5～3.0): (1.0～3.0);
(2) get above-mentioned 60～80% colloidal sol, be warming up to 550 ℃～650 ℃, organic substance is decomposed, obtain ZnO crystal, milling is prepared into the ZnO nano-powder again, and its particle diameter is at 30nm～70nm;
(3) in above-mentioned ZnO powder, add dispersant, after mixing, join in the remaining colloidal sol;
(4) on monocrystalline silicon substrate, adopt dc sputtering or evaporation deposition method to prepare hearth electrode, above-mentioned colloidal sol is spun on the hearth electrode, form film, film 500 ℃～850 ℃ annealing, is carried out lithography process, adopt chemical corrosion method to erode the part film, with the exposed portions serve hearth electrode, carry out the preparation of top electrode afterwards, thereby make ZnO ceramic membrane low voltage varistor.
Advantage of the present invention is:
(1) by doping bismuth ion Bi in ZnO colloidal sol 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+, cobalt ions Co 3+, to have prepared ZnO ceramic membrane, thereby prepared ZnO low voltage varistor with excellent electrical properties with excellent electrical properties, its pressure sensitive voltage is lower than 4V, and non linear coefficient can reach 22, and leakage current density is less than 0.4 μ A/mm 2
(2) owing to added nano-powder, and by dispersing technology powder is evenly mixed and stable dispersion with colloidal sol, its film forming is fast, realizes film thickness monitoring easily, helps the release of membrane stress, can prepare the film from 2000nm～5000nm, and flawless.
(3) annealing temperature (500 ℃～850 ℃) is lower more than 400 ℃ than the preparation temperature of existing ZnO ceramic material, has realized the low temperature preparation of ZnO pressure sensitive.
Description of drawings
Fig. 1 is the structural representation of the ZnO ceramic membrane low voltage varistor of use the present invention preparation.
Embodiment
The preparation method of 1 one kinds of ZnO ceramic membranes of embodiment low voltage varistor comprises
(1) prepares ZnO colloidal sol by usual way: get 5.4 gram (0.0247mol) zinc acetate Zn (CH 3COO) 22H 2O is dissolved in 10～12 milliliters of EGMEs, adds 1～2 milliliter of glacial acetic acid, and 1～2 milliliter of monoethanolamine under 50 ℃～60 ℃ conditions, stirred 3～4 hours, forms the colloidal sol of stable transparent;
In above-mentioned colloidal sol, doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+With cobalt ions Co 3+, press Zn +: Bi 3+: Sb 3+: Mn 2+: Cr 3+: Co 3+=100: 0.6: 2.0: 1.0: 0.5: 1.0 mol ratio can add bismuth nitrate Bi (NO 3) 3, antimony chloride SbCl 3, manganese acetate Mn (CH 3COO) 2, chromic nitrate Cr (NO 3) 3With cobalt nitrate Co (NO 3) 3, form uniform and stable colloidal sol;
(2) get 60% of above-mentioned colloidal sol, can dry earlier, slowly be warming up to 650 ℃ then, organic substance is decomposed, milling is prepared into the ZnO nano-powder again, and its particle diameter is at 30nm～70nm;
(3) add dispersant in above-mentioned ZnO powder, dispersant can be hydroxyl and poly-alkoxy grp Compound P OR, and (structural formula is: R-(OC 2H 4) nOH, R are organic chain) or polyethylene glycol (structural formula is: H (OCH 2CH 2) 2OH), its quality can be 1～4% of ZnO powder, after mixing, joins in the remaining colloidal sol, forms colloidal sol even, good stability;
(4) on monocrystalline silicon substrate 1, adopt common dc sputtering or evaporation deposition method to prepare hearth electrode 2, the material of hearth electrode 2 can be selected platinum Pt for use, gold Au, silver Ag, above-mentioned colloidal sol is spun on the hearth electrode 2, form film 3, its thickness generally is controlled at 2000nm～5000nm, film 3 annealing temperatures are 500 ℃, and annealing time can be 2～3 hours, carry out lithography process then, adopt common chemical corrosion method to erode the part thin layer, with exposed portions serve hearth electrode 2, carry out the preparation of top electrode 4 afterwards, through cutting, after the encapsulation, hearth electrode 2, top electrode 4 is exposed to both sides respectively, thereby makes ZnO ceramic membrane low voltage varistor.
The preparation method of 2 one kinds of ZnO ceramic membranes of embodiment low voltage varistor comprises
(1) prepares ZnO colloidal sol by usual way;
In above-mentioned colloidal sol, doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+With cobalt ions Co 3+, press Zn 2+: Bi 3+: Sb 3+: Mn 2+: Cr 3+: Co 3+=100: 1.4: 1.6: 0.6: 3.0: 2.0 mol ratio can add bismuth chloride BiCl 3, antimony acetate Sb (CH 3COO) 3, manganese nitrate Mn (NO 3) 2, chromic acetate Cr (CH 3COO) 3With cobalt acetate Co (CH 3COO) 3, form uniform and stable colloidal sol;
(2) get above-mentioned colloidal sol 70%, can dry earlier, slowly be warming up to 600 ℃ then, organic substance is decomposed, milling is prepared into the ZnO nano-powder again, and its particle diameter is at 30nm～70nm;
(3) with (3) among the embodiment 1;
(4) change (4) among the embodiment 1 described film 3 annealing temperatures into 750 ℃, other together
(4) among the embodiment 1.
The preparation method of 3 one kinds of ZnO ceramic membranes of embodiment low voltage varistor comprises
(1) prepares ZnO colloidal sol by usual way;
In above-mentioned colloidal sol, doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+With cobalt ions Co 3+, press Zn 2+: Bi 3+: Sb 3+: Mn 2+: Cr 3+: Co 3+=100: 1.0: 3.0: 0.2: 2.0: 3.0 mol ratio can add bismuth nitrate Bi (NO 3) 3, antimony chloride SbCl 3, manganese acetate Mn (CH 3COO) 2, chromic acetate Cr (CH 3COO) 3With cobalt acetate Co (CH 3COO) 3, form uniform and stable colloidal sol;
(2) get above-mentioned colloidal sol 80%, can dry earlier, slowly be warming up to 550 ℃ then, organic substance is decomposed, milling is prepared into the ZnO nano-powder again, and its particle diameter is at 30nm～70nm;
(3) with (3) among the embodiment 1;
(4) change (4) among the embodiment 1 described film 3 annealing temperatures into 850 ℃, other together
(4) among the embodiment 1.

Claims (1)

1. the preparation method of a ZnO ceramic membrane low voltage varistor is characterized in that: comprise
(1) in ZnO colloidal sol, doping bismuth ion Bi 3+, antimony ion Sb 3+, manganese ion Mn 2+, chromium ion Cr 3+With cobalt ions Co 3+, its mol ratio is: Zn 2+: Bi 3+: Sb 3+: Mn 2+: Cr 3+: Co 3+=100: (0.6～1.4): (1.6～3.0): (0.2～1.0): (0.5～3.0): (1.0～3.0);
(2) get above-mentioned 60～80% colloidal sol, be warming up to 550 ℃～650 ℃, organic substance is decomposed, obtain ZnO crystal, milling is prepared into the ZnO nano-powder again, and its particle diameter is at 30nm～70nm;
(3) in above-mentioned ZnO powder, add dispersant, after mixing, join in the remaining colloidal sol;
(4) on monocrystalline silicon substrate, adopt dc sputtering or evaporation deposition method to prepare hearth electrode, above-mentioned colloidal sol is spun on the hearth electrode, form film, film 500 ℃～850 ℃ annealing, is carried out lithography process, adopt chemical corrosion method to erode the part film, with the exposed portions serve hearth electrode, carry out the preparation of top electrode afterwards, thereby make ZnO ceramic membrane low voltage varistor.
CNB2004100134479A 2004-07-10 2004-07-10 Method for preparing ZnO ceramic film low-voltage piezoresistor Expired - Fee Related CN100394517C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100134479A CN100394517C (en) 2004-07-10 2004-07-10 Method for preparing ZnO ceramic film low-voltage piezoresistor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100134479A CN100394517C (en) 2004-07-10 2004-07-10 Method for preparing ZnO ceramic film low-voltage piezoresistor

Publications (2)

Publication Number Publication Date
CN1595551A true CN1595551A (en) 2005-03-16
CN100394517C CN100394517C (en) 2008-06-11

Family

ID=34662985

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100134479A Expired - Fee Related CN100394517C (en) 2004-07-10 2004-07-10 Method for preparing ZnO ceramic film low-voltage piezoresistor

Country Status (1)

Country Link
CN (1) CN100394517C (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102300832A (en) * 2009-02-03 2011-12-28 埃普科斯股份有限公司 Varistor ceramic, multi-layer structural element comprising said varistor ceramic, production method for said varistor ceramic
CN101786874B (en) * 2010-01-15 2012-02-22 清华大学 Process method for preparing low residual voltage ZnO varistor ceramic
CN103073302A (en) * 2013-01-21 2013-05-01 聊城大学 Low-temperature sintering method of high potential gradient voltage-sensitive ceramic material
CN105198402A (en) * 2015-09-15 2015-12-30 苏州亿馨源光电科技有限公司 Nano zinc oxide voltage-dependent resistor material and preparation method thereof
CN105913987A (en) * 2016-05-30 2016-08-31 苏州米盟智能装备科技有限公司 Zinc oxide pressure sensitive resistor
CN108231998A (en) * 2017-12-31 2018-06-29 中国科学院声学研究所 One kind mixes vanadium ZnO thick films and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811084B2 (en) * 1977-12-28 1983-03-01 株式会社明電舎 Voltage nonlinear resistor
CN1030121C (en) * 1992-04-23 1995-10-18 中国科学院新疆物理研究所 Low-voltage piezo-resistance material and making method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102300832A (en) * 2009-02-03 2011-12-28 埃普科斯股份有限公司 Varistor ceramic, multi-layer structural element comprising said varistor ceramic, production method for said varistor ceramic
CN105622088A (en) * 2009-02-03 2016-06-01 埃普科斯股份有限公司 Varistor ceramic, multi-layer structural element comprising said varistor ceramic, production method for said varistor ceramic
CN101786874B (en) * 2010-01-15 2012-02-22 清华大学 Process method for preparing low residual voltage ZnO varistor ceramic
CN103073302A (en) * 2013-01-21 2013-05-01 聊城大学 Low-temperature sintering method of high potential gradient voltage-sensitive ceramic material
CN105198402A (en) * 2015-09-15 2015-12-30 苏州亿馨源光电科技有限公司 Nano zinc oxide voltage-dependent resistor material and preparation method thereof
CN105198402B (en) * 2015-09-15 2018-01-02 湖南双创部落信息咨询服务有限责任公司 A kind of Nanocrystalline Zno-based Varistor material and preparation method thereof
CN105913987A (en) * 2016-05-30 2016-08-31 苏州米盟智能装备科技有限公司 Zinc oxide pressure sensitive resistor
CN108231998A (en) * 2017-12-31 2018-06-29 中国科学院声学研究所 One kind mixes vanadium ZnO thick films and preparation method thereof

Also Published As

Publication number Publication date
CN100394517C (en) 2008-06-11

Similar Documents

Publication Publication Date Title
Wang et al. Electrochemical deposition of Eu3+-doped CeO2 nanobelts with enhanced optical properties
CN1918672B (en) Thin film transistor, thin film transistor substrate, liquid crystal display device, sputtering target, transparent conductive film, transparent electrode, and method for producing same
Yu et al. Catalytic synthesis and structural characteristics of high-quality tetrapod-like ZnO nanocrystals by a modified vapor transport process
JP5376117B2 (en) ZnO sputtering target and manufacturing method thereof
DE102004050382A1 (en) Electrode catalyst fine particles, dispersion thereof and methods for preparing the dispersion
CN1595551A (en) Method for preparing ZnO ceramic film low-voltage piezoresistor
EP2398935A1 (en) Compositions containing indium alkoxide, method for the production thereof, and use thereof
CN110649160B (en) Inorganic charge transport layer, preparation method thereof and application of perovskite solar cell
DE112009002056T5 (en) Transparent electrically conductive film for solar cells, composition for transparent electrically conductive films and multiple solar cells
CN111410525B (en) High-performance zinc oxide resistance ceramic material and preparation method thereof
KR20190049276A (en) Pt-CoO NANO PARTICLE, MANUFACTURING METHOD OF THE SAME AND CATALYST COMPRISING THE SAME
CN101776632B (en) Water dispersible polyaniline nano-particle gas-sensitive element and method for preparing same
CN110498440A (en) A kind of zinc oxide air-sensitive membrane material, preparation method and applications
Schildhammer et al. Synthetic access to cubic rare earth molybdenum oxides RE6MoO12− δ (RE= Tm–Lu) representing a new class of ion conductors
CN1746130A (en) Nanometer gas-sensing material of ternary composite metal oxide and production thereof
CN106830078B (en) A kind of vanadic anhydride micron order film and preparation method thereof
CN1737558A (en) Stannic oxide based nanometer rod air-sensitive material and process for preparing the same
CN1093979C (en) Pressure sensitive nonlinear resistor, method for producing pressure sensitive nonlinear resistor and lighting arrester
CN108205002B (en) L aFeO with high gas response and selectivity3Ethanol-based gas sensor element and method for manufacturing same
EP0354769B1 (en) Zinc oxide sintered body and preparation process thereof
CN101824613A (en) Method for growing zinc oxide nanowire array on zinc aluminum oxide conductive film
CN105869807A (en) Preparation method of zinc oxide-bismuth oxide thin film varistor
CN112374528A (en) Graphene surface-loaded zinc oxide nanoparticle composite material and preparation method and application thereof
CN1924095A (en) Oxide based diluted magnetic semiconductor thin film with room temperature ferromagnetism and preparation method thereof
CN102690655A (en) Europium-doped yttrium borate red light emitting film and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: Xiangyang TTE Electric Co., Ltd.

Assignor: Huazhong University of Science and Technology

Contract fulfillment period: 2009.4.10 to 2014.4.10 contract change

Contract record no.: 2009420010026

Denomination of invention: Method for preparing ZnO ceramic film low-voltage piezoresistor

Granted publication date: 20080611

License type: Exclusive license

Record date: 2009.5.30

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.10 TO 2014.4.10; CHANGE OF CONTRACT

Name of requester: XIANGFAN SANSAN ELECTRIC CO., LTD.

Effective date: 20090530

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080611

Termination date: 20150710

EXPY Termination of patent right or utility model