CN105603400A - Preparation method of ZnO transparent conductive film - Google Patents
Preparation method of ZnO transparent conductive film Download PDFInfo
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- CN105603400A CN105603400A CN201610040004.1A CN201610040004A CN105603400A CN 105603400 A CN105603400 A CN 105603400A CN 201610040004 A CN201610040004 A CN 201610040004A CN 105603400 A CN105603400 A CN 105603400A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
- C23C20/06—Coating with inorganic material, other than metallic material
- C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
Abstract
The invention relates to the technical field of transparent conductive films and discloses a preparation method of a ZnO transparent conductive film. The preparation method includes the steps of a, using Zn(Ac)2.2H2O, Al(NO3)3.9H2O and FeCl3.6H2O as raw materials, ethylene glycol monomethyl ether as solvent, ethanolamine as stabilizer to prepare sol; b, cleaning a glass substrate; c, using a spin-coating method to form a film on the glass substrate; heating in a drying oven of 150-250 DEG C for 9-11 minutes, naturally cooling to room temperature, and repeatedly spin coating the sol for multiple times to form a film; d, performing thermal treatment on the film obtained in the step c to obtain the ZnO transparent conductive film. The preparation method using a sol-gel method to synthesize the ZnO transparent conductive film has the advantages that the method is simple to operate, economical and convenient, capable of achieving large-scale production, and the like, and the prepared ZnO transparent conductive film is uniform.
Description
Technical field
The present invention relates to the technical field of transparent conductive film, relate in particular to the preparation of ZnO transparent conductive filmMethod.
Background technology
ZnO is the direct band gap group Ⅱ-Ⅵ compound semiconductor that one has broad-band gap (3.3eV under room temperature),The exciton binding energy of ZnO is 60meV, and has hexagonal wurtzite structure. ZnO film has good lightPermeability, piezoelectricity, photo electric, gas sensing property and pressure-sensitive, and be easy to realize with multiple semi-conducting materialIntegrated. Based on these excellent performances, ZnO has practical application widely in many fields, as thoroughlyPrescribed electrode, ultra-violet light-emitting device, transistor, chemical sensor, gas sensor and solar cell etc.Meanwhile, adopt different adulterants, change the doped level of adulterant, can effectively change ZnOElectricity, optical property, to meet the demand of zno-based material in the different practical application scenes of different field.
Transparent conductive film is that a class has the material in visible ray high permeability and high conductivity, at flat boardThe fields such as demonstration, solar cell and transistor have a wide range of applications. Now widely used transparent leadingConductive film is ITO, but high to equipment and environmental requirement because of the preparation of ITO, and its preparation cost is high,Limited ITO and used on a large scale, meanwhile, indium metal belongs to rare metal, and its reserves are limited and to environmentUnfriendly, the substitute of finding ITO is the important research direction of transparent conductive film.
Than ITO, ZnO has broad application prospects in the application in transparent conductive film field, becauseZnO not only has excellent photoelectricity performance, the simple various and environmental friendliness of its synthetic method, and,By changing adulterant and doped level, can change the photoelectricity performance of ZnO transparent conductive film, fullThe requirement of sufficient different application is important potential replacer.
Summary of the invention
The object of the present invention is to provide the preparation method of ZnO transparent conductive film, be intended to solve prior artIn transparent conductive film be ITO, exist preparation cost high, use restricted, ask environment is disagreeablenessTopic.
The present invention is achieved in that 1, the preparation method of ZnO transparent conductive film, comprises following preparationStep:
A), with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2O is raw material, ethylene glycol first
Ether is solvent, and monoethanolamine is stabilizing agent, configuration colloidal sol;
B), substrate of glass is cleaned;
C) colloidal sol, step being obtained in a) adopts in the substrate of glass of spin-coating method after step b) is cleanedSpin-coating film; Substrate of glass after gluing is placed on to heat treatment 9min～11 in the baking oven of 150 DEG C～250 DEG CMin, after taking-up, naturally cools to room temperature, then spin coating colloidal sol film forming repeatedly;
D), film that step c) is made heat-treats in atmospheric environment, obtains that ZnO is transparent to be ledConductive film.
Compared with prior art, the preparation method of ZnO transparent conductive film provided by the invention, adopts colloidal solGel method synthesizes ZnO transparent conductive film, has simple to operate, economic convenient and easy realization extensiveChange the advantage such as production, being expected in various substrates large area deposition, to have the ZnO of excellent photoelectricity performance transparentConductive film, and the ZnO transparent conductive film obtaining is even, for ZnO transparent conductive film groupThe regulation and control that become are also simpler and practical.
Brief description of the drawings
Fig. 1 is the visible light wave range transmitance figure of the ZnO transparent conductive film prepared of the embodiment of the present invention oneSpectrum;
Fig. 2 is the XRD diffracting spectrum of the ZnO transparent conductive film prepared of the embodiment of the present invention one;
Fig. 3 is the visible light wave range transmitance figure of the ZnO transparent conductive film prepared of the embodiment of the present invention twoSpectrum.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and realityExecute example, the present invention is further elaborated. Only should be appreciated that specific embodiment described hereinOnly, in order to explain the present invention, be not intended to limit the present invention.
Below in conjunction with specific embodiment, realization of the present invention is described in detail.
Shown in Fig. 1～3, it is preferred embodiment provided by the invention.
Embodiment mono-
The preparation method of the ZnO transparent conductive film that the present embodiment provides, comprises following preparation process:
A), with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2O is raw material, ethylene glycol firstEther is solvent, and monoethanolamine is stabilizing agent, is configured to according to a certain percentage colloidal sol;
B), substrate of glass is cleaned;
C) colloidal sol, step being obtained in a) adopts in the substrate of glass of spin-coating method after step b) is cleanedSpin-coating film; Substrate of glass after gluing is placed on to heat treatment 9min～11 in the baking oven of 150 DEG C～250 DEG CMin, after taking-up, naturally cools to room temperature, then spin coating colloidal sol film forming repeatedly;
D), film that step c) is made heat-treats in atmospheric environment, can obtain visible rayThe ZnO transparent conductive film of wave band high permeability.
In the preparation method of above-mentioned ZnO transparent conductive film, carry out repeatedly colloidal sol in step in c) and revolveBe coated with, can obtain the film of different-thickness. Certainly, the number of times of concrete spin coating can depend on the needs.
The preparation method of the above-mentioned ZnO transparent conductive film providing, adopts the synthetic ZnO of sol-gal process saturatingBright conductive film, has simple to operate, economical convenient and easily realizes the advantages such as large-scale production, hasPrestige large area deposition in various substrates has the ZnO transparent conductive film of excellent photoelectricity performance, and,The ZnO transparent conductive film obtaining is even, also simpler for the regulation and control of ZnO transparent conductive film compositionAnd practical.
In the present embodiment, step a) in, with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2OFor raw material, EGME is solvent, and monoethanolamine is stabilizing agent, adopts electromagnetic agitation 4h～12h, obtainsThe colloidal sol of transparence, and by the colloidal sol essence of the clarification obtaining put store stand-by. Wherein, rubbing of Zn and monoethanolamineYou are than being 1:1, and concentration is 0.45mol/L, the concentration 0.0068mol/L of Al ion, Fe ion concentrationFor 0.005mol/L. The mol ratio of Al and Zn is 0～5%. The mol ratio of Fe and Zn is 0～8%.
Step b) in, substrate of glass is respectively through washing agent, deionized water, ethanol, acetone ultrasonic cleaning10min～15min or through washing agent clean after again through Piranha washing lotion soak 0.5h～1h, then, through oxygen from10min～15min is cleaned in daughter, can directly use.
Step c) in, with the rotating speed of 1500 revs/min～3000 revs/min, colloidal sol is spin-coated on to clean glass-basedAt at the end.
In steps d) in, finally by the film obtaining 450 DEG C～600 DEG C heat treatments in Muffle furnace or tube furnace0.8h～1.2h, obtains ZnO transparent conductive film.
ZnO transparent conductive film surfacing after above-mentioned concrete preparation, has hexagonal wurtzite structure, mixesAssorted Fe does not change the phase structure of ZnO transparent conductive film, meanwhile, and shown in Fig. 1 and Fig. 2,ZnO transparent conductive film has the light transmittance up to 90% in limit of visible spectrum.
Embodiment bis-
The difference of the present embodiment and embodiment mono-is:
In the present embodiment, step a) in, with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2OAnd CoCl26H2O is raw material, wherein, Co ion concentration is 0.005mol/L～0.035mol/L,And the total concentration of Fe ion and Co ion remains on 0.01～0.07mol/L scope, other preparation conditionsRemain unchanged.
Shown in Fig. 3, ZnO transparent conductive film reaches more than 90% in visible light wave range transmitance.
Embodiment tri-
The difference of the present embodiment and embodiment bis-is:
Step c) in, in substrate of glass, repeat spin coating seven times, obtain transparent the leading of ZnO that thickness is thickerConductive film.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.
Claims (10)
- The preparation method of 1.ZnO transparent conductive film, is characterized in that, comprises following preparation process:A), with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2O is raw material, ethylene glycol firstEther is solvent, and monoethanolamine is stabilizing agent, configuration colloidal sol;B), substrate of glass is cleaned;C) colloidal sol, step being obtained in a) adopts in the substrate of glass of spin-coating method after step b) is cleanedSpin-coating film; Substrate of glass after gluing is placed on to heat treatment 9min～11 in the baking oven of 150 DEG C～250 DEG CMin, after taking-up, naturally cools to room temperature, then spin coating colloidal sol film forming repeatedly;D), film that step c) is made heat-treats in atmospheric environment, obtains that ZnO is transparent to be ledConductive film.
- 2. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that,Described step a) in, with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2O is raw material, secondGlycol methyl ether is solvent, and monoethanolamine is stabilizing agent, adopts electromagnetic agitation 4h～12h, obtains the colloidal sol of transparence.
- 3. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that,Described step a) in, the mol ratio of Zn and monoethanolamine is 1:1.
- 4. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that,Described step a) in, the concentration 0.0068mol/L of Al ion.
- 5. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that, FeIon concentration is 0.005mol/L～0.035mol/L.
- 6. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that, AlWith the mol ratio of Zn be 0～5%.
- 7. the preparation method of ZnO transparent conductive film as claimed in claim 1, is characterized in that, FeWith the mol ratio of Zn be 0～8%.
- 8. the preparation method of the ZnO transparent conductive film as described in claim 1 to 7 any one, its spyLevy and be, described step c) in, colloidal sol is spin-coated on clean with the rotating speed of 1500 revs/min～3000 revs/minSubstrate of glass on.
- 9. the preparation method of the ZnO transparent conductive film as described in claim 1 to 7 any one, its spyLevy and be, in steps d) in, by the film obtaining 450 DEG C～600 DEG C heat treatments in Muffle furnace or tube furnace0.8h～1.2h, obtains ZnO transparent conductive film.
- 10. the preparation method of the ZnO transparent conductive film as described in claim 1 to 7 any one, its spyLevy and be, step a) in, with Zn (Ac)2·2H2O，Al(NO3)3·9H2O，FeCl3·6H2O andCoCl26H2O is raw material, and EGME is solvent, and monoethanolamine is stabilizing agent, configuration colloidal sol, andCo ion concentration is 0.005mol/L.
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| CN201610040004.1A CN105603400A (en) | 2016-01-21 | 2016-01-21 | Preparation method of ZnO transparent conductive film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229037A (en) * | 2016-08-10 | 2016-12-14 | 深圳市国华光电科技有限公司 | A kind of flexible composite transparent conductive film and preparation method thereof |
| CN113864906A (en) * | 2021-09-16 | 2021-12-31 | 杭州华风智慧科技有限公司 | Dehumidifier |
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| CN1383161A (en) * | 2002-05-31 | 2002-12-04 | 南京大学 | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method |
| CN1948221A (en) * | 2006-09-26 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method |
| CN101224904A (en) * | 2008-01-25 | 2008-07-23 | 华中科技大学 | Method for preparing Fe doped ZnO room-temperature diluted magnetic semiconductor material |
| KR20100007605A (en) * | 2008-07-14 | 2010-01-22 | 주식회사 엘지화학 | Conductive laminate and manufacturing method thereof |
| CN102503162A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Preparation method for Ag-Al co-doped p type ZnO film |
| CN104005011A (en) * | 2014-05-06 | 2014-08-27 | 昆明理工大学 | Preparation method for Cu-Al co-doped p-type ZnO film |
| CN104047053A (en) * | 2014-06-12 | 2014-09-17 | 济南大学 | Magnetic doped zinc oxide microstructure and preparation method thereof |
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2016
- 2016-01-21 CN CN201610040004.1A patent/CN105603400A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1383161A (en) * | 2002-05-31 | 2002-12-04 | 南京大学 | Diluted magnetic ZnO-base semiconductor prepared by sol-gel method |
| CN1948221A (en) * | 2006-09-26 | 2007-04-18 | 中国科学院上海硅酸盐研究所 | Method of preparing high temperature ferromagnetism ZnO:(Co,Al) nano-material using sol-gel method |
| CN101224904A (en) * | 2008-01-25 | 2008-07-23 | 华中科技大学 | Method for preparing Fe doped ZnO room-temperature diluted magnetic semiconductor material |
| KR20100007605A (en) * | 2008-07-14 | 2010-01-22 | 주식회사 엘지화학 | Conductive laminate and manufacturing method thereof |
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| CN104005011A (en) * | 2014-05-06 | 2014-08-27 | 昆明理工大学 | Preparation method for Cu-Al co-doped p-type ZnO film |
| CN104047053A (en) * | 2014-06-12 | 2014-09-17 | 济南大学 | Magnetic doped zinc oxide microstructure and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106229037A (en) * | 2016-08-10 | 2016-12-14 | 深圳市国华光电科技有限公司 | A kind of flexible composite transparent conductive film and preparation method thereof |
| CN106229037B (en) * | 2016-08-10 | 2018-03-09 | 深圳市国华光电科技有限公司 | A kind of flexible composite transparent conductive film and preparation method thereof |
| CN113864906A (en) * | 2021-09-16 | 2021-12-31 | 杭州华风智慧科技有限公司 | Dehumidifier |
| CN113864906B (en) * | 2021-09-16 | 2023-10-27 | 丁天柱 | Dehumidifier |
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