CN1369572A - Electrically conducting transparent oxide film - Google Patents
Electrically conducting transparent oxide film Download PDFInfo
- Publication number
- CN1369572A CN1369572A CN 01112276 CN01112276A CN1369572A CN 1369572 A CN1369572 A CN 1369572A CN 01112276 CN01112276 CN 01112276 CN 01112276 A CN01112276 A CN 01112276A CN 1369572 A CN1369572 A CN 1369572A
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- film
- sno
- electrically conducting
- oxide film
- conducting transparent
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Abstract
An electrically conducting transparent oxide film is a Zn2SnO4 or ZnSnO3 film to which the B, Al and In is osmosized by spray, sputtering, thermal evaporating, or ion plating. Its advantages are high mechanical performance and chemical stability, no poison and no pollution.
Description
The invention belongs to photoelectron technology, relate to a kind of transparent conductive film, be useful in ELD, as liquid-crystal display, electroluminescent display, plasma display, solar cell, photoswitch, camera device etc. reach aspects such as glass anti-fog frost-prevention well heater, electrostatic shielding film, energy-conservation infrared reflection film, solar energy collector, gas sensing.
The oxidic transparent conductive film is a kind of transparent conductive semiconductor film, has high conductivity and high visible light transmission, and infrared light is had very high reflectivity, and the material that can prepare such nesa coating is a lot, and modal is the In that mixes Sn
2O
3Conducting film, i.e. ITO film.The ITO film is at visible light 400nm～800nm transmitance height, and resistivity is low, but the used material of ITO film is a precious metal, the prices of raw and semifnished materials are higher, and secondly its chemical stability is relatively poor, in addition the mechanical property of film, just the hardness of film is relatively poor, and impaired back influences the quality of film.Except the ITO film, also has SnO
2(TO) film, CdIn
2O
4(CIO) film, Cd
2SnO
4(CTO) film, ZnO (ZO) film.SnO
2Membrance chemistry good stability, but poorly conductive, the preparation difficulty; CdIn
2O
4Film and CdSnO
4The membrance chemistry good stability, but Cd is poisonous, is not easy to use; Though the ZnO film material source is abundant, price is low, resistivity height, poor electric conductivity.
It is good to the purpose of this invention is to provide a kind of chemical stability, and conductivity is good, nontoxic transparent conductive film material.
The present invention is with one or more the Zn that is mixed with in the middle of the boron, aluminium, indium
2SnO
4Or ZnSnO
3As transparent conductive film material, singly to mix or the ratio of mixing 0.2%～20% more, molecular formula can be write as M:Zn
2SnO
4Or M:ZnSnO
3, wherein M is In, B, Al or their combination.
The present invention is according to Cd
2SnO
4Or CdSnO
3Material structure replaces cadmium to prepare the Zn that is used for electrically conducting transparent with zinc
2SnO
4Or ZnSnO
3Film.With producing transparent conductive film zinc of the present invention is that form with oxide compound exists.Zinc and cadmium belong to same subgroup element, than the little one-period of cadmium, so same Cd
2SnO
4Or CdSnO
3Has good electrical conductivity, light transmission and strong mechanical property after the same film forming.
The present invention is at Zn
2SnO
4Or ZnSnO
3The purpose of middle doped with boron, aluminium and indium is that the basis that reduces material absorbs, and increases light transmission.
Preparation method of the present invention mainly contains spraying method, sputter coating method, thermal evaporation, secondly is ion plating method, chemical deposition.
It can be the compound of metallic zinc or zinc and the compound of tin or tin that starting material of the present invention are chosen.
Realize that a method of the present invention is that selection purity is 99% ZnO and SnO
2Powder, mol ratio are 2: 1, and the ratio of doping In is 3%, are pressed into diameter behind the thorough mixing and are 20 millimeters cylinder.Use thermal evaporation, adopt vacuum electronic rifle reactive evaporation technology, utilize the cold-cathode ion source oxonium ion auxiliary simultaneously, evaporation goes out to be mixed with the ZnSnO of In
4Or ZnSnO
3The nesa coating of material.Using the auxiliary purpose of cold-cathode ion source oxonium ion is to supply with the material molecule energy in evaporate process.In thermal evaporation, material is directly put into the pincers pot of electron beam gun, utilize improved GDM-450B type electron beam gun coating equipment to carry out evaporation, base reservoir temperature is about 200 ℃, vacuum tightness is 1～3 * 10
-2Pa.In evaporation, carry out cold cathode ion assisted evaporative simultaneously, the cold-cathode ion source line is 100 milliamperes～300 milliamperes, 200 volts～1000 volts of extraction voltages, working gas is an oxygen.Utilize the blooming controller to carry out thickness and vaporator rate monitoring.Thickness is 200nm～600nm.
In evaporate process, oxonium ion plays two effects, and the one, the zinc-tin of decomposition is regrouped, form normal stoichiometric zinc, two provide to the film molecular energy, form lattice, improve the gather density of film, and make surface smoothing.
Implementing another method of the present invention is spraying method.Use ZnCl
2And SnCl
4Be raw material, add water decomposition reaction and spray and produce.Substrate temperature can generate ZnSnO below 700 ℃ the time
3Film is generating Zn more than 800 ℃
2SnO
4Film.Obtaining ZnSnO below 700 ℃
3Film, average transmittance are 80%.
It is the sputter coating method that enforcement the present invention also has a method.Use Zn
2SnO
4The ratio of target and Zn/Sn is 2: 1 a Zn-Sn alloy target material, in purity oxygen, carry out the RF spatter film forming after, utilize heat treating method, make Zn with high conductivity
2SnO
4Film will generate ZnO and ZnSnO in film
3Phase.Thermal treatment after the sputter is after film surface covers one deck thinly with the ZnS powder earlier, in the Ar air-flow about 690 ℃ the time about processing 10min.Adopt this Ar-ZnS heat treating method, the electroconductibility of film will be higher about 2 times than only handling in the Ar air-flow, and this can think because the generation in oxygen room and SnO in film
2Decomposition, generated Sn alms giver's cause.And, use Zn
2SnO
4During target, under 500-600 ℃ substrate temperature, the rete characteristic that obtains is: ρ is about 10
-4Ω .cm.In addition, employing Zn/Sn ratio is 2: 1 a Zn-Sn alloys target, 3 * 10
-2The Ar-O of Torr
2In when carrying out the DC reactive sputtering, to the characteristic and the O of film
2The relation of concentration is studied, and its result is O
2Concentration was at 6% o'clock, and the value of ρ is minimum.
The substrate material of conducting film is transparent sheet glass.
Effect of the present invention is as follows:
1, conductivity
With preparing ITO, TO with quadrat method and mixing the ZO of aluminium, compare with the present invention.Ito surface resistance is 200～300 Ω/, and TO face resistance is 800～900 Ω/, and ZO face resistance is 1100～1300 Ω/, mixes the ZTO (Zn of Zn
2SnO
4Or ZnSnO
3) face resistance is 500～600 Ω/.Face resistance of the present invention is slightly larger than ITO, and electroconductibility is only second to ITO, and resistivity is about 10
-4Magnitude.
2, optical transmittance
Fig. 1 mixes the ZTO film visible light transmissive rate curve of In for the present invention.From figure curve as seen, its transmitance in visible-range, surpass 80% and ITO basic identical.Lower in 400nm～500nm transmitance, its reason has part divalence Sn ion to replace the Zn lattice to cause, and is however, high a lot of than the transmitance of CTO film.
3, crystalline structure
Fig. 2 is substrate＜150 ℃, and x-ray diffraction pattern, Fig. 3 are substrate＞150 ℃, x-ray diffraction pattern.
The present invention is done X-ray diffraction experiment, in membrane prepare, underlayer temperature＜150 ℃, diffraction peak a little less than, show that crystallization is not obvious, as shown in Figure 2; When underlayer temperature＞150 ℃, diffraction peak is stronger, and as shown in Figure 3, the surface forms crystalline structure, and can prove that the composition of film mainly is ZnSnO
3
The very smooth densification in the surface of film as can be seen from the atomic force microscope measuring result, smooth 10 times than ITO, the face type is better.Its root of dividing equally is 0.946nm, and mean value is 0.746nm.
The present invention is if adopt sputtering method or low pressure gegenion plating method, and the main component of formed conducting film is Zn
2SnO
4
The zinc nesa coating of doped with boron, aluminium, indium is a kind of nesa coating that does not appear in the newspapers, nontoxic pollution-free, and the starting material source is abundant, low price, machinery and chemical stability are good, and therefore, the present invention is a kind of ideal electrically conducting transparent mould material.
Claims (4)
1, a kind of electrically conducting transparent oxide film is characterized in that being mixed with one or more the Zn in the middle of boron, aluminium, the indium
2SnO
4Or ZnSnO
3, with spraying method, sputter coating method, thermal evaporation, ion plating method or chemical deposition, the preparation transparent conductive film, the molecular formula of film is expressed as M:Zn
2SnO
4Or M:ZnSnO
3, wherein M is one or more in the middle of B, Al, the In; The amount of doped with boron, aluminium, indium is 0.2%～20%.
2, electrically conducting transparent oxide film according to claim 1, it is characterized in that selecting purity is 99% ZnO and SnO
2Powder, mol ratio are 2: 1, and the ratio of doping In is 3%, prepares with thermal evaporation.
3, electrically conducting transparent oxide film according to claim 1 is characterized in that using ZnCl
2And SnCl
4For raw material adds the water decomposition reaction, spray and produce.
4, electrically conducting transparent oxide film according to claim 1 is characterized in that using Zn
2SnO
4The ratio of target and Zn/Sn is 2: 1 a Zn-Sn alloy target material, carries out the RT spatter film forming in purity oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01112276 CN1369572A (en) | 2001-04-03 | 2001-04-03 | Electrically conducting transparent oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01112276 CN1369572A (en) | 2001-04-03 | 2001-04-03 | Electrically conducting transparent oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1369572A true CN1369572A (en) | 2002-09-18 |
Family
ID=4659238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01112276 Pending CN1369572A (en) | 2001-04-03 | 2001-04-03 | Electrically conducting transparent oxide film |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398195C (en) * | 2005-08-18 | 2008-07-02 | 清华大学 | Synthesis method of boron-doped nanometer oxide and use thereof |
| US20110240934A1 (en) * | 2006-03-15 | 2011-10-06 | Sumitomo Metal Co., Ltd. | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| CN102278043A (en) * | 2010-02-17 | 2011-12-14 | 法国圣-戈班玻璃公司 | Method for obtaining a heated glazing |
| CN101994103B (en) * | 2009-08-17 | 2012-03-28 | 中国科学院理化技术研究所 | Preparation method of photoassisted sol-gel of yttrium doped zinc oxide transparent conductive film |
| CN101496117B (en) * | 2006-07-28 | 2012-04-18 | 株式会社爱发科 | Method for forming transparent conductive film |
| CN102582149A (en) * | 2012-02-21 | 2012-07-18 | 浙江大学 | Multilayer transparent electroconductive thin film |
| CN101541701B (en) * | 2006-08-29 | 2013-07-17 | 皮尔金顿集团有限公司 | Method of making a low-resistivity, doped zinc oxide coated glass article and the coated glass article made thereby |
| CN103415488A (en) * | 2011-03-02 | 2013-11-27 | 株式会社钢臂功科研 | Oxide sintered compact and sputtering target |
| CN103957346A (en) * | 2014-04-23 | 2014-07-30 | 徐继胜 | Monitoring equipment lens ITO heating and de-icing device |
| CN104254495A (en) * | 2012-04-25 | 2014-12-31 | 东曹精细化工株式会社 | Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film |
| CN104991294A (en) * | 2015-06-18 | 2015-10-21 | 中国科学院国家天文台南京天文光学技术研究所 | Extremely-low temperature environment large-aperture reflecting-type telescope frost-prevention film system and preparing method thereof |
| CN105131949A (en) * | 2015-08-27 | 2015-12-09 | 浙江大学 | Method for improving near-infrared luminescence intensity of SrSnO3 through Al doping |
| CN105154077A (en) * | 2015-08-27 | 2015-12-16 | 浙江大学 | Method for improving near-infrared luminescence intensity of BaSnO<3> by means of Al doping |
| JP2016507004A (en) * | 2013-02-05 | 2016-03-07 | ソレラス・アドヴァンスト・コーティングス・ビーヴイビーエー | (Ga) ZnSn oxide sputtering target |
| CN108709915A (en) * | 2018-09-01 | 2018-10-26 | 罗杰雄 | A kind of harmful gas in vehicle detection device |
-
2001
- 2001-04-03 CN CN 01112276 patent/CN1369572A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398195C (en) * | 2005-08-18 | 2008-07-02 | 清华大学 | Synthesis method of boron-doped nanometer oxide and use thereof |
| US8349220B2 (en) * | 2006-03-15 | 2013-01-08 | Sumitomo Metal Mining Co., Ltd. | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| US20110240934A1 (en) * | 2006-03-15 | 2011-10-06 | Sumitomo Metal Co., Ltd. | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| EP1835511B1 (en) * | 2006-03-15 | 2017-09-13 | Sumitomo Metal Mining Co., Ltd. | Oxide sintered body, manufacturing method and use as a target for transparent conductive film |
| US8551370B2 (en) | 2006-03-15 | 2013-10-08 | Sumitomo Metal Mining Co., Ltd. | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| CN101496117B (en) * | 2006-07-28 | 2012-04-18 | 株式会社爱发科 | Method for forming transparent conductive film |
| CN101541701B (en) * | 2006-08-29 | 2013-07-17 | 皮尔金顿集团有限公司 | Method of making a low-resistivity, doped zinc oxide coated glass article and the coated glass article made thereby |
| CN101994103B (en) * | 2009-08-17 | 2012-03-28 | 中国科学院理化技术研究所 | Preparation method of photoassisted sol-gel of yttrium doped zinc oxide transparent conductive film |
| CN102278043B (en) * | 2010-02-17 | 2015-04-01 | 法国圣-戈班玻璃公司 | Method for obtaining a heated glass window and resulting heated glass window |
| CN102278043A (en) * | 2010-02-17 | 2011-12-14 | 法国圣-戈班玻璃公司 | Method for obtaining a heated glazing |
| CN103415488A (en) * | 2011-03-02 | 2013-11-27 | 株式会社钢臂功科研 | Oxide sintered compact and sputtering target |
| CN103415488B (en) * | 2011-03-02 | 2015-01-28 | 株式会社钢臂功科研 | Oxide sintered compact and sputtering target |
| CN102582149A (en) * | 2012-02-21 | 2012-07-18 | 浙江大学 | Multilayer transparent electroconductive thin film |
| CN104254495A (en) * | 2012-04-25 | 2014-12-31 | 东曹精细化工株式会社 | Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film |
| JP2016507004A (en) * | 2013-02-05 | 2016-03-07 | ソレラス・アドヴァンスト・コーティングス・ビーヴイビーエー | (Ga) ZnSn oxide sputtering target |
| US9758856B2 (en) | 2013-02-05 | 2017-09-12 | Soleras Advanced Coatings Bvba | (Ga) Zn Sn oxide sputtering target |
| CN103957346A (en) * | 2014-04-23 | 2014-07-30 | 徐继胜 | Monitoring equipment lens ITO heating and de-icing device |
| CN104991294A (en) * | 2015-06-18 | 2015-10-21 | 中国科学院国家天文台南京天文光学技术研究所 | Extremely-low temperature environment large-aperture reflecting-type telescope frost-prevention film system and preparing method thereof |
| CN105154077A (en) * | 2015-08-27 | 2015-12-16 | 浙江大学 | Method for improving near-infrared luminescence intensity of BaSnO<3> by means of Al doping |
| CN105131949A (en) * | 2015-08-27 | 2015-12-09 | 浙江大学 | Method for improving near-infrared luminescence intensity of SrSnO3 through Al doping |
| CN108709915A (en) * | 2018-09-01 | 2018-10-26 | 罗杰雄 | A kind of harmful gas in vehicle detection device |
| CN108709915B (en) * | 2018-09-01 | 2021-11-19 | 山东多瑞电子科技有限公司 | Harmful gas detection device in car |
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