CN109722653A - A kind of method that solwution method prepares witch culture tin oxide transparent conductive film - Google Patents
A kind of method that solwution method prepares witch culture tin oxide transparent conductive film Download PDFInfo
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- CN109722653A CN109722653A CN201910001788.0A CN201910001788A CN109722653A CN 109722653 A CN109722653 A CN 109722653A CN 201910001788 A CN201910001788 A CN 201910001788A CN 109722653 A CN109722653 A CN 109722653A
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Abstract
The invention belongs to transparent conductive film technical fields, disclose a kind of method that solwution method prepares witch culture tin oxide transparent conductive film.Tungsten powder and hydrogenperoxide steam generator are sufficiently reacted in ice-water bath, is diluted after filtering and impurity removing with distilled water, obtains tungstic acid；By SnCl2·2H2O is dissolved in anhydrous ethanol solvent, is stirred evenly, and stannous chloride solution is obtained；Tungstic acid and H are added dropwise into stannous chloride solution2O2Solution, it is that achromaticity and clarification is transparent that sonic oscillation, which is handled to solution, stands aging, obtains mixed liquor；The mixed liquor obtained by spin coating in the glass substrate cleaned up, annealing, obtains witch culture tin oxide transparent conductive film.The present invention is adulterated using wolframic acid and H is added2O2The stability and permeability for improving solution make in final cured film, and W is with the WO of+6 valences3Form exists, and improves the transmittance of film.
Description
Technical field
The invention belongs to transparent conductive film technical fields, and in particular to a kind of solwution method prepares witch culture tin oxide transparent
The method of conductive film.
Background technique
Transparent conductive film is widely used in field of photoelectric technology.The transparent conductive material of commercial applications has indium tin at present
Oxide (ITO), fluorine-doped tin oxide (FTO), Al-Doped ZnO (AZO) etc..Wherein ITO has excellent electric conductivity, height thoroughly
Penetrate rate, easily etching the advantages that and be used widely.With the fast development of relevant industries, transparent conductive material demand is increasingly mentioned
It rises, and the phosphide element in ITO is precious metal element, scarcity of resources, it is difficult to meet future development demand.Although the high electricity of FTO, AZO
It leads, but transmissivity is lower.Meanwhile the common preparation process such as ITO, FTO, AZO is vacuum sputtering, equipment cost is high.Cause
This, is badly in need of exploitation raw material resources and enriches, makes transparent conductive film at low cost, that electric conductivity is excellent.
SnO 2 thin film abundant raw material can be prepared by solwution method, and cost is relatively low.By suitably adulterate (such as W, F,
Sb etc.) electric conductivity and transmission performance of SnO 2 thin film can be significantly improved.Solwution method preparation is mixed W SnO 2 thin film and is often adopted
Use WCl6As dopant, the film of preparation although high conductance, but film transmission is low, cannot meet high-transmission rate very well
It is required that.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the purpose of the present invention is to provide a kind of solution legal systems
The method of standby witch culture tin oxide transparent conductive film.There is high electricity using the transparent conductive film that the method for the present invention is prepared
It leads, highly transmissive advantage.
The object of the invention is achieved through the following technical solutions:
A kind of method that solwution method prepares witch culture tin oxide transparent conductive film, including following preparation step:
(1) tungsten powder and hydrogenperoxide steam generator are sufficiently reacted in ice-water bath, after reaction solution is filtered to remove residual impurity
It is diluted with distilled water, obtains tungstic acid；
(2) by SnCl2·2H2O is dissolved in anhydrous ethanol solvent, is stirred evenly, and stannous chloride solution is obtained；
(3) tungstic acid and H are added dropwise into stannous chloride solution2O2Solution, sonic oscillation processing become until solution from muddiness
It is transparent for achromaticity and clarification, aging is stood, mixed liquor is obtained；
(4) in the glass substrate cleaned up spin-coating step (3) mixed liquor, annealing, obtain witch culture oxidation
Tin transparent conductive film.
Preferably, the concentration of tungstic acid described in step (1) is 0.8~1mol/L.
Preferably, the concentration of stannous chloride solution described in step (2) is 0.5~0.7mol/L.
Preferably, it is calculated in step (3) with Solute mass fraction, wolframic acid doping is the 2%~6% of total soluble matters quality.
Preferably, H described in step (3)2O2The additional amount of solution is the 5%~10% of mixed liquor total volume fraction.
Preferably, sonic oscillation described in step (3) processing time be 30~90min, stand aging time be 1~
3 days.
Preferably, the revolving speed of spin coating described in step (4) is 3000~5000rpm, and spin-coating time is 30~50s.
Preferably, described in step (4) annealing refer to first at a temperature of 120~150 DEG C pre-anneal treatment 10~
Then 20min makes annealing treatment 60~120min at a temperature of 500~600 DEG C.
Preferably, the number of repetition of spin coating and annealing is 2~4 times in step (4).
The principle of the present invention are as follows:
Using W6+Replace part Sn4+The concentration of carrier in film can be promoted afterwards, promote electric conductivity.In SnCl2It is molten
In liquid, wolframic acid is in SnCl after instilling wolframic acid2Reproducibility, the effect of the oxidisability of hydrogen peroxide is lower that series of chemical occurs,
The complexing of last and ethyl alcohol, forms colorless and transparent colloidal sol.H2O2Introducing effectively prevent W6+It is reduced, it is penetrating to increase solution
Property, it is eventually exhibited as improving the transmissivity of film.
Compared with prior art, the invention has the following advantages and beneficial effects:
The invention proposes using wolframic acid as dopant, traditional WCl can be replaced6Dopant.Simultaneously using wolframic acid doping
H is added2O2The stability and permeability for improving solution make in final cured film, and W is with the WO of+6 valences3Form exists, thin
Film conductivity preferably can improve the transmittance of film.
Detailed description of the invention
Fig. 1 is gained witch culture tin oxide transparent conductive film in embodiment 1 in the transmittance graph figure of visible light wave range.
Fig. 2 is gained witch culture tin oxide transparent conductive film in embodiment 2 in the transmittance graph figure of visible light wave range.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) it is sufficiently reacted in ice-water bath using 1.84g tungsten powder and 30% hydrogenperoxide steam generator of 8mL, is adopted after fully reacting
Residual impurity is filtered out with 0.22 μm of filter tip, 1mol/L tungstic acid is then obtained using distilled water titration.
(2) 1.35g SnCl is weighed2·2H2O after being dissolved in 11mL ethyl alcohol, is added dropwise the 1mol/L tungstic acid of 120 μ L, then delays
It is slow that 1mL 30%H is added dropwise2O2Solution, sonic oscillation 30min after sealing is until solution is clarified, and then solution left standstill aging 2 days, obtain
SnCl is adulterated to the 2wt.% wolframic acid that solution concentration is 0.5mol/L2Ethanol solution, solution picture are as shown in Figure 1.
(3) it is cleaned by ultrasonic the glass substrate of 1cm × 1cm, film is prepared using the solution spin coating of step (2) after drying, revolves
Revolving speed 3000rpm, spin-coating time 30s are applied, 120 DEG C of annealing 10min of Pre-annealing Temperature, are warming up to 500 DEG C of annealing after the completion of spin coating
90min。
(4) step (3) are repeated twice, 3 layers of plated film, obtain witch culture tin oxide transparent conductive film in total.Obtain film
It is as shown in Figure 1 in the transmittance graph (glass substrate is blank control) of visible light wave range.
Film rectangular resistance is tested using four probe conduction rate testers, test obtains 1 square resistance of embodiment and is
435.2 ± 20 Ω/sq use step instrument measurement film thickness for 270.6 ± 10nm, and it is 1.18 × 10 that resistivity, which is calculated,-4
Ω·m。
Embodiment 2
(1) it is sufficiently reacted in ice-water bath using 1.84g tungsten powder and 30% hydrogenperoxide steam generator of 8mL, is adopted after fully reacting
Residual impurity is filtered out with 0.22 μm of filter tip, 1mol/L tungstic acid is then obtained using distilled water titration.
(2) 1.89g SnCl is weighed2·2H2O after being dissolved in 11mL ethyl alcohol, is added dropwise the 1mol/L tungstic acid of 504 μ L, then delays
It is slow that 1mL 30%H is added dropwise2O2Solution, sonic oscillation 90min after sealing is until solution is clarified, and then solution left standstill aging 3 days, obtain
SnCl is adulterated to the 6wt.% wolframic acid that solution concentration is 0.7mol/L2Ethanol solution.
(3) it is cleaned by ultrasonic the glass substrate of 1cm × 1cm, film is prepared using the solution spin coating of step (2) after drying, revolves
Revolving speed 5000rpm, spin-coating time 50s are applied, 150 DEG C of annealing 20min of Pre-annealing Temperature, are warming up to 600 DEG C of annealing after the completion of spin coating
120min。
(4) step (3) are repeated twice, 3 layers of plated film, obtain witch culture tin oxide transparent conductive film in total.Obtain film
It is as shown in Figure 2 in the transmittance graph (glass substrate is blank control) of visible light wave range.
Film rectangular resistance is tested using four probe conduction rate testers, test obtains 2 square resistance of embodiment and is
105.2 ± 20 Ω/sq use step instrument measurement film thickness for 400.5 ± 10nm, and it is 4.21 × 10 that resistivity, which is calculated,-5
Ω·m。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of method that solwution method prepares witch culture tin oxide transparent conductive film, it is characterised in that including preparing step as follows
It is rapid:
(1) tungsten powder and hydrogenperoxide steam generator are sufficiently reacted in ice-water bath, reaction solution is filtered to remove to use after residual impurity and is steamed
Distilled water dilution, obtains tungstic acid；
(2) by SnCl2·2H2O is dissolved in anhydrous ethanol solvent, is stirred evenly, and stannous chloride solution is obtained；
(3) tungstic acid and H are added dropwise into stannous chloride solution2O2Solution, sonic oscillation processing become nothing from muddiness until solution
Color clear stands aging, obtains mixed liquor；
(4) in the glass substrate cleaned up spin-coating step (3) mixed liquor, annealing, it is saturating to obtain witch culture tin oxide
Bright conductive film.
2. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: the concentration of tungstic acid described in step (1) is 0.8~1mol/L.
3. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: the concentration of stannous chloride solution described in step (2) is 0.5~0.7mol/L.
4. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: step is calculated in (3) with Solute mass fraction, and wolframic acid doping is the 2%~6% of total soluble matters quality.
5. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
It is: H described in step (3)2O2The additional amount of solution is the 5%~10% of mixed liquor total volume fraction.
6. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: the time of the processing of sonic oscillation described in step (3) is 30~90min, and the time for standing aging is 1~3 day.
7. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: the revolving speed of spin coating described in step (4) is 3000~5000rpm, and spin-coating time is 30~50s.
8. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: annealing described in step (4) refers to first 10~20min of pre-anneal treatment at a temperature of 120~150 DEG C, then exists
60~120min is made annealing treatment at a temperature of 500~600 DEG C.
9. the method that a kind of solwution method according to claim 1 prepares witch culture tin oxide transparent conductive film, feature
Be: the number of repetition of spin coating and annealing is 2~4 times in step (4).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
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| CN101413099A (en) * | 2008-11-27 | 2009-04-22 | 复旦大学 | Polycrystal tungsten-doped tin oxide transparent conductive oxide film and preparation thereof |
| CN103449508A (en) * | 2013-07-31 | 2013-12-18 | 深圳大学 | Tungsten doped tin dioxide nano powder and preparation method thereof |
| CN103695874A (en) * | 2013-12-26 | 2014-04-02 | 武汉理工大学 | Preparation method of intelligent temperature control color changing vanadium oxide film |
| WO2014183265A1 (en) * | 2013-05-14 | 2014-11-20 | Essilor International (Compagnie Generale D'optique) | Fluorine-doped stannic oxide colloids and method for preparing same |
| CN105540650A (en) * | 2016-02-25 | 2016-05-04 | 攀枝花学院 | Tungsten-doped stannic oxide sol nanocrystalline and preparing method thereof |
| CN107614437A (en) * | 2015-05-19 | 2018-01-19 | 埃西勒国际通用光学公司 | The tin oxide colloidal suspension and methods for making them of witch culture |
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2019
- 2019-01-02 CN CN201910001788.0A patent/CN109722653B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101413099A (en) * | 2008-11-27 | 2009-04-22 | 复旦大学 | Polycrystal tungsten-doped tin oxide transparent conductive oxide film and preparation thereof |
| WO2014183265A1 (en) * | 2013-05-14 | 2014-11-20 | Essilor International (Compagnie Generale D'optique) | Fluorine-doped stannic oxide colloids and method for preparing same |
| CN103449508A (en) * | 2013-07-31 | 2013-12-18 | 深圳大学 | Tungsten doped tin dioxide nano powder and preparation method thereof |
| CN103695874A (en) * | 2013-12-26 | 2014-04-02 | 武汉理工大学 | Preparation method of intelligent temperature control color changing vanadium oxide film |
| CN107614437A (en) * | 2015-05-19 | 2018-01-19 | 埃西勒国际通用光学公司 | The tin oxide colloidal suspension and methods for making them of witch culture |
| CN105540650A (en) * | 2016-02-25 | 2016-05-04 | 攀枝花学院 | Tungsten-doped stannic oxide sol nanocrystalline and preparing method thereof |
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| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
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