CN113066900A - Preparation method of low-cost ZnO transparent conductive film - Google Patents
Preparation method of low-cost ZnO transparent conductive film Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 80
- 239000011701 zinc Substances 0.000 claims abstract description 38
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000012159 carrier gas Substances 0.000 claims abstract description 17
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000004246 zinc acetate Substances 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 13
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000000889 atomisation Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims abstract description 5
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 5
- 239000010980 sapphire Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 34
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 13
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 11
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 abstract description 15
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 235000019441 ethanol Nutrition 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 54
- 238000010438 heat treatment Methods 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000004151 rapid thermal annealing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
- B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
- B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a preparation method of a low-cost ZnO transparent conductive film, which comprises the steps of respectively taking zinc acetate, ammonium fluoride, aluminum nitrate and gallium chloride as a zinc source, a fluorine source, an aluminum source, a gallium source and a chlorine source, taking water or absolute ethyl alcohol and an aqueous solution as solvents, preparing a solution with a certain concentration, and propelling the solution to an ultrasonic atomization generator by a peristaltic pump according to a certain flow rate; the invention uses high-pressure air or high-pressure nitrogen as high-pressure carrier gas to convey the mixed solution atomized by an atomization generator to a heated substrate, the substrate is glass, sapphire or quartz, the substrate temperature is 350-550 ℃, the invention uses salts which are easily soluble in water or alcohols and the like as raw materials under the non-vacuum condition, and utilizes the low-cost ultrasonic spraying technology to prepare the ZnO transparent conductive film which has strong conductive capability, high ultraviolet-visible-near infrared region transmittance, low cost, stable performance and easy large-area production.
Description
Technical Field
The invention belongs to the technical field of transparent conductive oxide films, and particularly relates to a preparation method of a low-cost ZnO transparent conductive film.
Background
In recent years, with the development of flat panel display and solar cell technologies, transparent conductive thin films have been widely used as electrode materials. The ZnO (ZnO) film has attracted extensive attention by the characteristics of wide optical band gap, high visible light transmittance, low cost, strong radiation resistance, strong conductive ability after doping and the like, and becomes a substitute for the current common Sn-doped In2O3(ITO) a candidate material for the transparent conductive film.
However, physical deposition technologies such as magnetron sputtering, pulsed laser deposition, electron beam evaporation, atomic layer deposition and the like are mostly adopted in the ZnO transparent conductive film with better performance, the technologies all need to be prepared in a vacuum environment, and the preparation equipment and experimental materials, namely target materials or metal organic sources, are expensive, so that the production cost is reduced on the basis of keeping the excellent photoelectric characteristics of the ZnO film by combining the advantages of no toxicity, low price, rich reserves and the like of the ZnO transparent conductive film, and the preparation method is particularly important for expanding the application range of the ZnO transparent conductive film and reducing the production cost of devices.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a low-cost ZnO transparent conductive film, so as to solve the problems mentioned in the background art.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a low-cost ZnO transparent conductive film comprises the following steps:
s1, zinc acetate Zn (CHCOO)2As zinc source, ammonium fluoride NH4F as a source of fluorine for doping, aluminum nitrate Al (NO)3)3As a source of doped aluminum, gallium chloride GaCl3Respectively as a doped chlorine source and a doped gallium source, mixing water and absolute ethyl alcohol to be used as a solvent, preparing zinc acetate into a zinc source solution, preparing a fluorine source solution from a fluorine source, preparing an aluminum source solution from an aluminum source, and respectively preparing a gallium source solution and a gallium source solution from a gallium source and a chlorine sourceA chlorine source solution;
s2, mixing the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution prepared in the step S1 according to a certain mass ratio, and adding glacial acetic acid after mixing to prepare a mixed solution;
s3, propelling the mixed solution prepared in the S2 to an ultrasonic atomization nozzle by a peristaltic pump;
and S4, conveying the mixed solution passing through the ultrasonic atomization nozzle to the surface of the clean substrate by using high-pressure carrier gas to finish the preparation of the ZnO transparent conductive film.
Preferably, in S1, the mixing volume ratio of water and absolute ethyl alcohol is 0: 1-5: 1 volume mixing ratio;
the concentration of the prepared zinc source solution is less than 92g/L, the concentration of the prepared fluorine source solution is less than 0.37g/L, the concentration of the prepared aluminum source solution is less than 2.13g/L, and the concentrations of the prepared gallium source solution and the prepared chlorine source solution are less than 0.18 g/L.
Preferably, in S2, the zinc source solution and the fluorine source solution, the aluminum source solution, and the gallium source solution are mixed in accordance with the ratio of Zn: f: al: ga 100%: 0-0.55%: 0.58%: 0.96% by mass.
Preferably, in S2, the zinc source solution and the fluorine source solution, the aluminum source solution, and the gallium source solution are mixed in accordance with the ratio of Zn: f: al: ga 100%: 0.20%: 0-0.29%: 0.96% by mass.
Preferably, in S2, the zinc source solution and the fluorine source solution, the aluminum source solution, and the gallium source solution are mixed in accordance with the ratio of Zn: f: al: ga 100%: 0.20%: 0.58%: 0 to 1.69% by mass.
Preferably, in S2, the zinc source solution, the fluorine source solution, the aluminum source solution, and the gallium source solution are mixed in proportion, and then glacial acetic acid with a volume ratio of 0 to 30% is added.
Preferably, in S3, the speed of the peristaltic pump for propelling the mixed solution is 1-10 ml/min, and the power of the ultrasonic atomization nozzle is 0.1-4W.
Preferably, in S4, the high-pressure carrier gas is high-pressure air, high-pressure nitrogen or high-pressure argon, and the pressure of the high-pressure carrier gas is less than 0.3 MPa.
Preferably, in S4, the substrate is glass, sapphire, or quartz.
Preferably, in S4, the substrate is subjected to a heating process during preparation, and the heating temperature is 350-550 ℃.
Compared with the prior art, the invention has the following advantages:
the invention utilizes a solution method which is easy to regulate and control the doping proportion and has low cost, utilizes four elements of F, Cl, Al and Ga to codope and prepare a ZnO (FCAGZO) transparent conductive film, utilizes doped anions F and Cl to simultaneously regulate valence bands to realize the effect of donor doping based on that each doping element has a certain ideal solid solution doping proportion in ZnO crystal lattices, utilizes doped cations Al and Ga to simultaneously regulate conduction bands to realize the effect of donor doping, and realizes the preparation of the ZnO transparent conductive film which has strong conductive capability, high ultraviolet-visible-near infrared region transmission, low cost, stable performance and easy large-area production by improving the carrier mobility of the film on the basis of not sacrificing the carrier concentration of the ZnO transparent conductive film Salts of acetic acid or alcohols, zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3Gallium chloride GaCl3The ZnO transparent conductive film is subjected to post-annealing treatment, so that the photoelectric property of the ZnO transparent conductive film is further improved.
Drawings
FIG. 1 is a SEM topography for example 3 of the present invention;
FIG. 2 is an X-ray diffraction chart of example 4 of the present invention;
FIG. 3 is a three-dimensional topography of an AFM in accordance with example 5 of the present invention;
fig. 4 is an optical transmission diagram of embodiment 6 of the present invention.
Fig. 5 is an absorptance profile of example 7 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1, the present invention provides a technical solution: a preparation method of a low-cost ZnO transparent conductive film comprises the following steps:
s1, zinc acetate Zn (CHCOO)2As zinc source, ammonium fluoride NH4F as a source of fluorine for doping, aluminum nitrate Al (NO)3)3As a source of doped aluminum, gallium chloride GaCl3Respectively serving as a doped chlorine source and a doped gallium source, and mixing water and absolute ethyl alcohol according to a volume ratio of 0: 1-5: 1 as a solvent after being mixed in a volume mixing ratio, preparing zinc acetate into a zinc source solution, preparing a fluorine source solution from a fluorine source, preparing an aluminum source solution from an aluminum source, and respectively preparing a gallium source solution and a chlorine source solution from a gallium source and a chlorine source, wherein the concentration of the prepared zinc source solution is less than 92g/L, the concentration of the prepared fluorine source solution is less than 0.37g/L, the concentration of the prepared aluminum source solution is less than 2.13g/L, and the concentrations of the prepared gallium source solution and the prepared chlorine source solution are less than 0.18 g/L;
s2, mixing the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution prepared in the step S1 according to a certain mass ratio, and adding glacial acetic acid with the volume ratio of 0-30% after mixing to prepare a mixed solution;
s3, propelling the mixed solution prepared in the S2 to an ultrasonic atomizing nozzle at a speed of 1-10 ml/min by using a peristaltic pump, wherein the power of the ultrasonic atomizing nozzle is 0.1-4W;
s4, conveying the mixed solution passing through the ultrasonic atomization nozzle to the surface of the clean substrate by using high-pressure carrier gas to finish the preparation of the ZnO conductive film, wherein the high-pressure carrier gas is high-pressure air or high-pressure N2,The pressure of the high-pressure carrier gas is lower than 0.3MPa, the substrate is one of glass, sapphire, quartz or stainless steel,the substrate is heated during preparation, and the heating temperature is 350-550 ℃.
And finally, carrying out rapid thermal annealing treatment on the prepared conductive film, namely the ZnO conductive film, at 750 ℃ in a high-pressure nitrogen atmosphere.
Wherein the chemical reaction equation of the zinc acetate, the ammonium fluoride, the aluminum nitrate and the gallium chloride in the mixed solution is as follows:
example 2, the mass ratios of 1: 0.20%: 0.58%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As solute, mixed solution of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as solvent;
firstly, placing the cleaned glass substrate on a heating table;
then adjusting the temperature of the heating table to 380 ℃, spraying the ZnO transparent conductive film with the thickness of 471.3nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing spray head is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, performing rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere to obtain the ZnO transparent conductive film:
the test result shows that: the mobility of the ZnO transparent conductive film is 18.8cm2Vs, carrier concentration 1.82 × 1020cm-3Resistivity of 1.82X 10-3Omega cm, square resistance 38.7 omega/sq.
Example 3, the following mass ratios were used, respectively 1: 0.35%: 0.58%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As a solute, a mixture of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as a solvent.
Firstly, placing the cleaned glass substrate on a heating table;
then adjusting the temperature of the heating table to 400 ℃, spraying the ZnO transparent conductive film with the thickness of 831.2nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, performing rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere, wherein the SEM topography of the ZnO transparent conductive film is specifically shown in figure 1.
The test shows that the mobility of the ZnO transparent conductive film is 24.8cm2Vs, carrier concentration 2.48 × 1020cm-3Resistivity of 1.01X 10-3Omega cm, 400-1600nm average transmittance of 80.7%.
Example 4, the following compositions were used in a mass ratio of 1: 0.20%: 0.29%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As solute, mixed solution of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as solvent;
firstly, placing the cleaned sapphire substrate on a heating table;
then adjusting the temperature of the heating table to 400 ℃, spraying the ZnO transparent conductive film with the film thickness of 802.0nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, carrying out rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere, wherein an X-ray diffraction pattern of the ZnO transparent conductive film is shown in figure 2.
The test shows that the mobility of the ZnO transparent conductive film is 19.6cm2Vs, carrier concentration 2.73 × 1020cm-3Resistivity of 1.17X 10-3Omega cm, 400-1600nm average transmittance of 82.6%.
Example 5, mass ratios were 1: 0.20%: 0.58%: 1.20% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As a solute, a mixture of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as a solvent. The method comprises the following steps:
firstly, placing the cleaned quartz substrate on a heating table;
then adjusting the temperature of the heating table to 400 ℃, spraying the ZnO transparent conductive film with the thickness of 767.0nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, performing rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere, wherein an AFM (atomic force microscopy) three-dimensional topography of the ZnO transparent conductive film is shown in FIG. 3:
the test shows that the mobility of the ZnO transparent conductive film is 20.7cm2Vs, carrier concentration 2.31 × 1020cm-3Resistivity of 1.31X 10-3Omega-cm, 400-1600nm average transmittance of 83.1%.
Example 6, the following compositions were used in a mass ratio of 1: 0.20%: 0.58%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As solute, mixed solution of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as solvent;
firstly, placing the cleaned glass substrate on a heating table;
then adjusting the temperature of the heating table to 400 ℃, spraying the ZnO transparent conductive film with the thickness of 516.0nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, carrying out rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere, wherein the optical transmission diagram of the ZnO transparent conductive film is shown in figure 4:
the test result shows that: the mobility of the ZnO transparent conductive film is 19.4cm2Vs, carrier concentration 2.19 × 1020cm-3Resistivity of 1.47X 10-3Omega cm, 400-1600nm average transmittance of 86.7%.
Example 7, using a mass ratio of 1: 0.20%: 0.58%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As solute, mixed solution of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as solvent;
firstly, placing the cleaned glass substrate on a heating table;
then adjusting the temperature of the heating table to 440 ℃, spraying the ZnO transparent conductive film with the thickness of 756.1nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, performing rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere, wherein the absorption rate chart of the ZnO transparent conductive film is shown in figure 5:
the test result shows that: the ZnO transparent conductive filmThe mobility of the film was 16.5cm2Vs, carrier concentration 2.52 × 1020cm-3Resistivity of 1.78X 10-3Omega cm, square resistance 22.7 omega/sq.
Example 8, the following compositions were used in a mass ratio of 1: 0.20%: 0.58%: 0.96% Zinc acetate Zn (CHCOO)2Ammonium fluoride NH4F. Aluminum nitrate Al (NO)3)3And gallium chloride GaCl3As solute, mixed solution of 135ml of deionized water, 45ml of absolute ethyl alcohol and 20ml of acetic acid is used as solvent;
firstly, placing the cleaned glass substrate on a heating table;
then adjusting the temperature of the heating table to 480 ℃, spraying the ZnO transparent conductive film with the thickness of 670.5nm on the glass substrate, wherein the spraying height is 45mm, the speed of a peristaltic pump is 2ml/min, the power of an ultrasonic atomizing nozzle is 1.2 watts, and the pressure of high-pressure carrier gas is 0.1 Mpa;
and finally, performing rapid thermal annealing treatment on the prepared ZnO transparent conductive film at 750 ℃ under a high-purity nitrogen atmosphere to obtain the ZnO transparent conductive film:
the test result shows that: the mobility of the ZnO transparent conductive film is 13.3cm2Vs, carrier concentration 2.55 × 1020cm-3Resistivity of 1.84X 10-3Omega cm, square resistance 27.4 omega/sq.
The test results of the comprehensive examples 2 to 8 show that the ZnO transparent conductive film prepared in the application improves the mobility of the prepared ZnO transparent conductive film, improves the conductive capability and expands the transmittance of the film in a near infrared region on the basis of maintaining the concentration of carriers unchanged;
meanwhile, the ultraviolet-visible-near infrared light transmission rate is high, and the performance is stable.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a low-cost ZnO transparent conductive film is characterized by comprising the following steps:
s1, zinc acetate Zn (CHCOO)2As zinc source, ammonium fluoride NH4F as a source of fluorine for doping, aluminum nitrate Al (NO)3)3As a source of doped aluminum, gallium chloride GaCl3Respectively serving as a doped chlorine source and a doped gallium source, mixing water and absolute ethyl alcohol to serve as a solvent, preparing zinc acetate into a zinc source solution, preparing a fluorine source solution from a fluorine source, preparing an aluminum source solution from an aluminum source, and respectively preparing a gallium source solution and a chlorine source solution from the gallium source and the chlorine source;
s2, mixing the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution prepared in the step S1 according to a certain mass ratio, and adding glacial acetic acid after mixing to prepare a mixed solution;
s3, propelling the mixed solution prepared in the S2 to an ultrasonic atomization nozzle by a peristaltic pump;
and S4, conveying the mixed solution passing through the ultrasonic atomization nozzle to the surface of the clean substrate by using high-pressure carrier gas to finish the preparation of the ZnO transparent conductive film.
2. The method for preparing a low-cost ZnO transparent conductive film according to claim 1, wherein in S1, the mixing volume ratio of water and absolute ethyl alcohol is 0: 1-5: 1 volume mixing ratio;
the concentration of the prepared zinc source solution is less than 92g/L, the concentration of the prepared fluorine source solution is less than 0.37g/L, the concentration of the prepared aluminum source solution is less than 2.13g/L, and the concentrations of the prepared gallium source solution and the prepared chlorine source solution are less than 0.18 g/L.
3. The method of claim 1, wherein in S2, the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution are mixed in the ratio of Zn: f: al: ga 100%: 0-0.55%: 0.58%: 0.96% by mass.
4. The method of claim 1, wherein in S2, the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution are mixed in the ratio of Zn: f: al: ga 100%: 0.20%: 0-0.29%: 0.96% by mass.
5. The method of claim 1, wherein in S2, the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution are mixed in the ratio of Zn: f: al: ga 100%: 0.20%: 0.58%: 0 to 1.69% by mass.
6. The method according to claim 1, wherein in S2, glacial acetic acid with a volume ratio of 0-30% is added after the zinc source solution, the fluorine source solution, the aluminum source solution and the gallium source solution are mixed in proportion.
7. The method for preparing a low-cost ZnO transparent conductive film according to claim 1, wherein in S3, the speed of the peristaltic pump for propelling the mixed solution is 1-10 ml/min, and the power of the ultrasonic atomizing nozzle is 0.1-4W.
8. The method of claim 1, wherein in S4, the high pressure carrier gas is high pressure air, high pressure nitrogen or high pressure argon, and the pressure of the high pressure carrier gas is lower than 0.3 MPa.
9. The method of claim 1, wherein in S4, the substrate is glass, sapphire or quartz.
10. The method as claimed in claim 1, wherein in S4, the substrate is heated at 350-550 ℃ during the preparation process.
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