CN109722653B - Method for preparing tungsten-doped tin oxide transparent conductive film by solution method - Google Patents
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Abstract
The invention belongs to the technical field of transparent conductive films, and discloses a method for preparing a tungsten-doped tin oxide transparent conductive film by a solution method. Mixing tungsten powder and hydrogen peroxide solution inFully reacting in ice-water bath, filtering to remove impurities, and diluting with distilled water to obtain a tungstic acid solution; SnCl2·2H2Dissolving O in an absolute ethyl alcohol solvent, and uniformly stirring to obtain a stannous chloride solution; adding tungstic acid solution and H dropwise into stannous chloride solution2O2Carrying out ultrasonic oscillation treatment on the solution until the solution is colorless, clear and transparent, standing and aging to obtain a mixed solution; and spin-coating the obtained mixed solution on a cleaned glass substrate, and annealing to obtain the tungsten-doped tin oxide transparent conductive film. The invention adopts tungstic acid to dope and adds H2O2The stability and permeability of the solution are improved, and the WO with the valence of +6 in the finally solidified film3The form exists, and the transmission of the film is improved.
Description
Technical Field
The invention belongs to the technical field of transparent conductive films, and particularly relates to a method for preparing a tungsten-doped tin oxide transparent conductive film by a solution method.
Background
The transparent conductive film is widely applied in the field of photoelectric technology. Currently, Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), and the like are commercially available transparent conductive materials. Among them, ITO has advantages of excellent conductivity, high transmittance, easy etching, etc., and is widely used. With the rapid development of related industries, the demand of transparent conductive materials is increasing day by day, and the indium element in the ITO is a noble metal element, so that the resource is deficient, and the future development demand is difficult to meet. FTO and AZO have high conductivity, but have low transmittance. Meanwhile, the common preparation processes of ITO, FTO, AZO and the like are vacuum sputtering, and the equipment cost is high. Therefore, it is urgently needed to develop a transparent conductive film with abundant raw material resources, low cost and excellent conductivity.
The tin oxide film has rich raw materials, can be prepared by a solution method, and has lower cost. The conductivity and transmission properties of tin oxide films can be significantly improved by suitable doping (e.g., W, F, Sb, etc.). WCl is often adopted in solution method for preparing W-doped tin oxide film6As a doping agent, the prepared film has high conductivity, but the film has low transmittance, so that the requirement of high transmittance cannot be well met.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a tungsten-doped tin oxide transparent conductive film by a solution method. The transparent conductive film prepared by the method has the advantages of high conductivity and high transmission.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a tungsten-doped tin oxide transparent conductive film by a solution method comprises the following preparation steps:
(1) fully reacting tungsten powder with a hydrogen peroxide solution in an ice-water bath, filtering the reaction solution to remove residual impurities, and diluting with distilled water to obtain a tungstic acid solution;
(2) SnCl2·2H2Dissolving O in an absolute ethyl alcohol solvent, and uniformly stirring to obtain a stannous chloride solution;
(3) adding tungstic acid solution and H dropwise into stannous chloride solution2O2Carrying out ultrasonic oscillation treatment on the solution until the solution is changed from turbid to colorless, clear and transparent, and standing and aging to obtain a mixed solution;
(4) and (4) spin-coating the mixed solution obtained in the step (3) on a cleaned glass substrate, and annealing to obtain the tungsten-doped tin oxide transparent conductive film.
Preferably, the concentration of the tungstic acid solution in the step (1) is 0.8-1 mol/L.
Preferably, the concentration of the stannous chloride solution in the step (2) is 0.5-0.7 mol/L.
Preferably, in the step (3), the doping amount of the tungstic acid is 2-6% of the total solute mass calculated by the mass fraction of the solute.
Preferably, said H in step (3)2O2The adding amount of the solution is 5 to 10 percent of the total volume fraction of the mixed solution.
Preferably, the ultrasonic oscillation treatment time in the step (3) is 30-90 min, and the standing and aging time is 1-3 days.
Preferably, the spin coating in the step (4) has a rotation speed of 3000-5000 rpm and a spin coating time of 30-50 s.
Preferably, the annealing treatment in the step (4) is pre-annealing treatment at 120-150 ℃ for 10-20 min, and then annealing treatment at 500-600 ℃ for 60-120 min.
Preferably, the number of repetitions of the spin coating and the annealing in the step (4) is 2 to 4.
The principle of the invention is as follows:
by the use of W6+Replacement part Sn4+And the concentration of current carriers in the film can be improved, and the conductivity can be improved. In SnCl2Dropping tungstic acid into SnCl2The oxidation of hydrogen peroxide and the reducibility of the alcohol are carried out to generate a series of chemical reactions, and finally the alcohol is complexed to form colorless transparent sol. H2O2Introduction of (2) effectively prevents W6+Is reduced, increases the permeability of the solution and finally shows that the transmissivity of the film is improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention provides a method for using tungstic acid as a doping agent to replace the traditional WCl6A dopant. Doping with tungstic acid and adding H2O2The stability and permeability of the solution are improved, and the WO with the valence of +6 in the finally solidified film3The film has better conductivity and improves the transmission property of the film.
Drawings
Fig. 1 is a graph showing transmittance of the tungsten-doped tin oxide transparent conductive film obtained in example 1 in the visible light band.
Fig. 2 is a graph showing the transmittance of the tungsten-doped tin oxide transparent conductive film obtained in example 2 in the visible light band.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) 1.84g of tungsten powder and 8mL of 30% hydrogen peroxide solution are adopted to fully react in ice-water bath, a filter tip with the diameter of 0.22 mu m is adopted to filter out residual impurities after the reaction is completed, and then distilled water is adopted to titrate to obtain 1mol/L tungstic acid solution.
(2) Weighing 1.35g SnCl2·2H2O, dissolving in 11mL of ethanol, dropwise adding 120 mu L of 1mol/L tungstic acid solution, and slowly dropwise adding 1mL of 30% H2O2Sealing the solution, carrying out ultrasonic oscillation for 30min until the solution is clear, standing and aging the solution for 2 days to obtain 2 wt.% of tungstic acid doped SnCl with the solution concentration of 0.5mol/L2Ethanol solution, the picture of the solution is shown in figure 1.
(3) Ultrasonically cleaning a 1cm multiplied by 1cm glass substrate, drying, preparing a film by spin-coating the solution obtained in the step (2), wherein the spin-coating speed is 3000rpm, the spin-coating time is 30s, annealing at the pre-annealing temperature of 120 ℃ for 10min after the spin-coating is finished, and annealing at the temperature of 500 ℃ for 90 min.
(4) And (4) repeating the step (3) twice, and coating 3 layers in total to obtain the tungsten-doped tin oxide transparent conductive film. The transmittance curve of the resulting film in the visible wavelength band (glass substrate is blank) is shown in FIG. 1.
The sheet resistance of the film in example 1 is 435.2 +/-20 omega/sq by testing with a four-probe conductivity tester, the thickness of the film is 270.6 +/-10 nm by measuring with a step tester, and the resistivity is 1.18 multiplied by 10 by calculation-4Ω·m。
Example 2
(1) 1.84g of tungsten powder and 8mL of 30% hydrogen peroxide solution are adopted to fully react in ice-water bath, a filter tip with the diameter of 0.22 mu m is adopted to filter out residual impurities after the reaction is completed, and then distilled water is adopted to titrate to obtain 1mol/L tungstic acid solution.
(2) Weighing 1.89g SnCl2·2H2O, dissolving in 11mL of ethanol, dropwise adding 504 mu L of 1mol/L tungstic acid solution, and slowly dropwise adding 1mL of 30% H2O2Sealing the solution, performing ultrasonic oscillation for 90min until the solution is clear, standing and aging the solution for 3 days to obtain 6 wt.% of tungstic acid doped SnCl with the solution concentration of 0.7mol/L2Ethanol solution.
(3) Ultrasonically cleaning a 1cm multiplied by 1cm glass substrate, drying, preparing a film by spin-coating the solution obtained in the step (2), wherein the spin-coating speed is 5000rpm, the spin-coating time is 50s, annealing at the pre-annealing temperature of 150 ℃ for 20min after the spin-coating is finished, and annealing at the temperature of 600 ℃ for 120 min.
(4) And (4) repeating the step (3) twice, and coating 3 layers in total to obtain the tungsten-doped tin oxide transparent conductive film. The transmittance curve of the resulting film in the visible wavelength band (glass substrate is blank) is shown in FIG. 2.
The sheet resistance of the film is tested by a four-probe conductivity tester, the sheet resistance of the film obtained in example 2 is 105.2 +/-20 omega/sq, the thickness of the film is measured by a step profiler to be 400.5 +/-10 nm, and the resistivity is calculated to be 4.21 multiplied by 10-5Ω·m。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing a tungsten-doped tin oxide transparent conductive film by a solution method is characterized by comprising the following preparation steps:
(1) fully reacting tungsten powder with a hydrogen peroxide solution in an ice-water bath, filtering the reaction solution to remove residual impurities, and diluting with distilled water to obtain a tungstic acid solution;
(2) SnCl2·2H2Dissolving O in an absolute ethyl alcohol solvent, and uniformly stirring to obtain a stannous chloride solution;
(3) adding tungstic acid solution and H dropwise into stannous chloride solution2O2Carrying out ultrasonic oscillation treatment on the solution until the solution is changed from turbid to colorless, clear and transparent, and standing and aging to obtain a mixed solution;
(4) spin-coating the mixed solution obtained in the step (3) on a cleaned glass substrate, and annealing to obtain a tungsten-doped tin oxide transparent conductive film;
the annealing treatment in the step (4) is pre-annealing treatment at 120-150 ℃ for 10-20 min, and then annealing treatment at 500-600 ℃ for 60-120 min.
2. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: the concentration of the tungstic acid solution in the step (1) is 0.8-1 mol/L.
3. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: the concentration of the stannous chloride solution in the step (2) is 0.5-0.7 mol/L.
4. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: in the step (3), the doping amount of the tungstic acid is 2-6% of the total solute by mass percent.
5. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: said H in step (3)2O2The adding amount of the solution is 5 to 10 percent of the total volume fraction of the mixed solution.
6. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: the ultrasonic oscillation treatment time in the step (3) is 30-90 min, and the standing and aging time is 1-3 days.
7. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: and (4) the spin coating in the step (4) is carried out at the rotating speed of 3000-5000 rpm for 30-50 s.
8. The method for preparing the tungsten-doped tin oxide transparent conductive film according to claim 1, which comprises the following steps: the repetition times of the spin coating and the annealing treatment in the step (4) is 2-4 times.
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