CN113628808A - Preparation method of tin oxide-based composite conductive film - Google Patents
Preparation method of tin oxide-based composite conductive film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 36
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 239000010955 niobium Substances 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 47
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000002834 transmittance Methods 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 abstract 4
- 239000007921 spray Substances 0.000 abstract 2
- 229910008449 SnF 2 Inorganic materials 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/20—Electrodes
- H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Surface Treatment Of Glass (AREA)
- Non-Insulated Conductors (AREA)
Abstract
本发明公开了一种氧化锡基复合导电薄膜的制备方法。该复合导电薄膜的制备方法包括以下步骤：S1：以钛酸丁酯为钛源，无水乙醇为溶剂，乙酰丙酮为稳定剂，硝酸为抑制剂，按一定比例混合，得到TiO2:Sn前驱液；S2：以MBTC为锡源，SnF2为氟源，NbCl5为铌源，盐酸、甲醇为溶剂，按一定方法，得到NFTO前驱液；S3：将TiO2:Sn前驱液喷涂在加热好的玻璃基板上沉积成膜，将沉积好的TiO2:Sn薄膜分别在一定温度和时间热处理后，得到TiO2:Sn薄膜；S4：将NFTO前驱液喷涂在S3得到的石英玻璃基板上加热后沉积，保温一段时间后取出，自然冷却到室温，从而获得氧化锡基复合导电薄膜。本发明通过化学气相沉积法喷涂多层薄膜，最后获得透光性好，导电率高的复合导电薄膜，其制备方法方便，成本低。The invention discloses a preparation method of a tin oxide-based composite conductive film. The preparation method of the composite conductive film includes the following steps: S1: using butyl titanate as a titanium source, anhydrous ethanol as a solvent, acetylacetone as a stabilizer, and nitric acid as an inhibitor, and mixing them in a certain proportion to obtain a TiO 2 :Sn precursor S2: Using MBTC as tin source, SnF 2 as fluorine source, NbCl 5 as niobium source, hydrochloric acid and methanol as solvent, according to a certain method, obtain NFTO precursor solution; S3: spray TiO 2 :Sn precursor solution on the heated well The deposited TiO 2 :Sn thin film is deposited on the glass substrate of S3 to obtain a TiO 2 :Sn thin film after heat treatment at a certain temperature and time respectively; S4: After heating the NFTO precursor solution by spraying on the quartz glass substrate obtained from S3 Deposit, take out after holding for a period of time, and naturally cool to room temperature, thereby obtaining a tin oxide-based composite conductive film. The invention sprays the multi-layer film by chemical vapor deposition method, finally obtains the composite conductive film with good light transmittance and high conductivity, and the preparation method is convenient and the cost is low.
Description
Technical Field
The invention relates to the field of conductive film materials, in particular to a preparation method of a tin oxide-based composite conductive film.
Background
The transparent conductive film is a basic photoelectric material with high conductivity and high transparency in visible light wave band, is widely applied to the photoelectric display fields of displays, luminescent devices, solar cells, sensors, flexible touch screens and the like, and has wide commercial application prospect.
While SnO2The base transparent conductive film is used as a functional material and is widely applied in the fields of Low-E glass, thin-film solar cells and the like, and is very likely to become a substitute of an ITO film. However, ITO films are very flexible, are not easily bent, are toxic, require relatively complicated processes to maintain transparency and conductivity, have insignificant effects, and have low stability, and thus, it is necessary to develop alternative materials.
Through the search of the prior art, most of the technologies are that the flexible transparent conductive film is prepared by coating or spraying ink prepared from various conductive substances on a flexible substrate.
Disclosure of Invention
The invention provides a preparation method of a tin oxide-based composite conductive film, which effectively solves the key problem of poor conductivity of an oxide transparent conductive film and modifies SnO2Thin film and TiO doped with rutile structure2The tin oxide-based composite conductive film is obtained by depositing the base film by a vapor deposition method and treating the base film at a certain temperature, so that the conductivity of the film can be improved, and the composite transparent conductive film with good light transmittance and high conductivity can be obtained.
In order to achieve the above object, the present invention provides a method for preparing a tin oxide-based composite conductive film, comprising the steps of:
S1 TiO2preparing Sn precursor solution: butyl titanate is used as a titanium source, absolute ethyl alcohol is used as a solvent, acetylacetone is used as a stabilizer, and nitric acid is used as an inhibitor. Adding butyl titanate into 40-60ml of absolute ethyl alcohol, and preparing a solution A by magnetic stirring at the rotating speed of 400-; respectively mixing acetylacetone and concentrated nitric acid in proportion, adding into the solution A, and mixing to obtain solution B; dissolving MBTC into 10-30ml of absolute ethanol according to the Sn/Ti ratio of 0-15at.%, adding into the solution B, magnetically stirring for more than 2 hours, and aging for 12-24 hours for later use;
preparation of S2 NFTO precursor solution: using MBTC as a tin source, SnF2Being a fluorine source, NbCl5Mixing 10-20g of MBTC and 4-10ml of concentrated hydrochloric acid by taking methanol as a solvent as a niobium source, and placing the mixture in 50-100 ml of methanol solution to magnetically stir for 5-10min to prepare solution C; SnF with F/Sn of 20-30 at%2Dissolving in 5-15ml deionized water to obtain solution D; 1-5at.% of Nb/Sn to convert NbCl5Dissolving in 30-40ml methanol to obtain solution E; respectively adding the solution D and the solution E into the solution C, magnetically stirring for 2-4h to prepare an NFTO precursor solution, and aging the NFTO precursor solution for 18-24 h for later use;
S3 TiO2preparing and heat treating the Sn film: and ultrasonically cleaning the quartz glass sheet in acetone, deionized water and absolute ethyl alcohol for 3 min, and then placing the quartz glass sheet in a forced air drying oven for drying for later use. Placing the dried quartz glass sheet in a tube furnace, heating to 500-600 ℃, preserving heat for 6 min, and then obtaining TiO 12Spraying Sn precursor solution onto heated glass substrate to deposit film, and depositing TiO2The Sn film is thermally treated for 2 hours at the temperature of 500-700 ℃;
preparation of S4 tin oxide-based composite film: and (4) spraying the NFTO precursor liquid obtained in the step (S2) on the quartz glass substrate obtained in the step (S3), heating, depositing, keeping the temperature for 1-4 min, taking out, and naturally cooling to room temperature to obtain the tin oxide-based composite conductive film.
Preferably, the mass solubility of the butyl titanate in the step S1 is 2 to 4%.
Preferably, the dosage ratio of the acetylacetone to the concentrated nitric acid in the S1 is 2: 1.
Preferably, the ratio of the amount of the MBTC to the amount of the concentrated hydrochloric acid in the S2 is 2: 1.
Preferably, the heating temperature in step S4 is 500-600 ℃.
Compared with the prior art, the invention has the advantages that: the invention takes the butyl titanate as the titanium source to prepare the TiO in the absolute ethyl alcohol solution2Sn precursor solution and SnF with MBTC as tin source2Being a fluorine source, NbCl5Preparing NFTO precursor solution for a niobium source, and performing multilayer overlapping compounding by a vapor deposition method process to finally obtain a tin oxide-based composite conductive film; the method fully utilizes the influence of the doped conductive elements on the optical and electrical properties of the conductive film, and the prepared composite conductive film has the characteristics of good uniformity and thickness controllability, good light transmittance, high conductivity and the like.
Detailed Description
Technical solutions in the embodiments of the present invention will be described in detail below, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example one
A preparation method of a tin oxide-based composite conductive film comprises the following steps:
S1 TiO2preparing Sn precursor solution: butyl titanate is used as a titanium source, absolute ethyl alcohol is used as a solvent, acetylacetone is used as a stabilizer, and nitric acid is used as an inhibitor. Adding butyl titanate into 40ml of absolute ethyl alcohol, and preparing a solution A by magnetic stirring at a rotating speed of 400 r/min; respectively mixing acetylacetone and concentrated nitric acid in proportion, adding into the solution A, and mixing to obtain solution B; dissolving MBTC into 10ml of absolute ethyl alcohol according to the Sn/Ti ratio of 5at.%, adding the solution into the solution B, magnetically stirring for more than 2 hours, and aging for 12 hours for later use;
preparation of S2 NFTO precursor solution: using MBTC as a tin source, SnF2Being a fluorine source, NbCl5Is a niobium source, methanol is used as a solvent, 10g of MBTC is mixed with 4ml of concentrated hydrochloric acid, and the mixture is placed in 50ml of methanol solution to be magnetically stirred for 5min, preparing a solution C; SnF with F/Sn of 20 at%2Dissolving in 5ml deionized water to obtain solution D; 1at.% Nb/Sn NbCl5Dissolving in 30ml methanol to obtain solution E; respectively adding the solution D and the solution E into the solution C, magnetically stirring for 2h to prepare an NFTO precursor solution, and aging the NFTO precursor solution for 18 h for later use;
S3 TiO2preparing and heat treating the Sn film: and ultrasonically cleaning the quartz glass sheet in acetone, deionized water and absolute ethyl alcohol for 3 min, and then placing the quartz glass sheet in a forced air drying oven for drying for later use. Heating the dried quartz glass sheet in a tube furnace to 500 ℃ and preserving heat for 6 min, and then carrying out TiO 12Spraying Sn precursor solution onto heated glass substrate to deposit film, and depositing TiO2The Sn film is thermally treated for 2 hours at the temperature of 500 ℃;
preparation of S4 tin oxide-based composite film: and (4) spraying the NFTO precursor liquid obtained in the step (S2) on the quartz glass substrate obtained in the step (S3), heating, depositing, keeping the temperature for 1min, taking out, and naturally cooling to room temperature to obtain the tin oxide-based composite conductive film.
Example two
A preparation method of a tin oxide-based composite conductive film comprises the following steps:
S1 TiO2preparing Sn precursor solution: butyl titanate is used as a titanium source, absolute ethyl alcohol is used as a solvent, acetylacetone is used as a stabilizer, and nitric acid is used as an inhibitor. Adding butyl titanate into 50ml of absolute ethyl alcohol, and preparing a solution A by magnetic stirring at a rotating speed of 500 r/min; respectively mixing acetylacetone and concentrated nitric acid in proportion, adding into the solution A, and mixing to obtain solution B; dissolving MBTC into 20ml of absolute ethyl alcohol according to the Sn/Ti ratio of 10at.%, adding the solution into the solution B, magnetically stirring for more than 2 hours, and aging for 18 hours for later use;
preparation of S2 NFTO precursor solution: using MBTC as a tin source, SnF2Being a fluorine source, NbCl5Mixing 15g of MBTC and 4-10ml of concentrated hydrochloric acid as a solvent, and magnetically stirring in 75ml of methanol solution for 7.5min to obtain solution C; SnF at 25at.% F/Sn2Dissolving in 10ml deionized water to obtain solution D; 2at.% Nb/Sn NbCl5Dissolving in 35ml methanol to obtain solution E(ii) a Respectively adding the solution D and the solution E into the solution C, magnetically stirring for 3 hours to prepare an NFTO precursor solution, and aging the NFTO precursor solution for 20 hours for later use;
S3 TiO2preparing and heat treating the Sn film: and ultrasonically cleaning the quartz glass sheet in acetone, deionized water and absolute ethyl alcohol for 3 min, and then placing the quartz glass sheet in a forced air drying oven for drying for later use. Heating the dried quartz glass sheet in a tube furnace to 550 ℃, preserving heat for 6 min, and then carrying out TiO 12Spraying Sn precursor solution onto heated glass substrate to deposit film, and depositing TiO2The Sn film is thermally treated for 2 hours at the temperature of 600 ℃;
preparation of S4 tin oxide-based composite film: and (4) spraying the NFTO precursor liquid obtained in the step (S2) on the quartz glass substrate obtained in the step (S3), heating, depositing, keeping the temperature for 2.5min, taking out, and naturally cooling to room temperature to obtain the tin oxide-based composite conductive film.
EXAMPLE III
A preparation method of a tin oxide-based composite conductive film comprises the following steps:
S1 TiO2preparing Sn precursor solution: butyl titanate is used as a titanium source, absolute ethyl alcohol is used as a solvent, acetylacetone is used as a stabilizer, and nitric acid is used as an inhibitor. Adding butyl titanate into 60ml of absolute ethyl alcohol, and stirring by magnetic force at the rotating speed of 600r/min to prepare solution A; respectively mixing acetylacetone and concentrated nitric acid in proportion, adding into the solution A, and mixing to obtain solution B; dissolving MBTC into 30ml of absolute ethyl alcohol according to the Sn/Ti ratio of 15at.%, adding the solution into the solution B, magnetically stirring for more than 2 hours, and aging for 24 hours for later use;
preparation of S2 NFTO precursor solution: using MBTC as a tin source, SnF2Being a fluorine source, NbCl5Mixing 20g of MBTC and 10ml of concentrated hydrochloric acid as a solvent, and magnetically stirring in 100ml of methanol solution for 10min to obtain solution C; SnF at 30at.% F/Sn2Dissolving in 15ml deionized water to obtain solution D; NbCl with Nb/Sn of 5 at%5Dissolving in 40ml methanol to obtain solution E; respectively adding the solution D and the solution E into the solution C, magnetically stirring for 4 hours to prepare an NFTO precursor solution, and aging the NFTO precursor solution for 24 hours for later use;
S3 TiO2preparing and heat treating the Sn film: and ultrasonically cleaning the quartz glass sheet in acetone, deionized water and absolute ethyl alcohol for 3 min, and then placing the quartz glass sheet in a forced air drying oven for drying for later use. Heating the dried quartz glass sheet in a tube furnace to 600 ℃ and preserving heat for 6 min, and then carrying out TiO 1 on the obtained product2Spraying Sn precursor solution onto heated glass substrate to deposit film, and depositing TiO2The Sn film is thermally treated for 2 hours at the temperature of 700 ℃;
preparation of S4 tin oxide-based composite film: and (4) spraying the NFTO precursor liquid obtained in the step (S2) on the quartz glass substrate obtained in the step (S3), heating, depositing, keeping the temperature for 4min, taking out, and naturally cooling to room temperature to obtain the tin oxide-based composite conductive film.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the tin oxide-based composite conductive film is characterized by comprising the following steps of:
S1 TiO2preparing Sn precursor solution: butyl titanate is taken as a titanium source, absolute ethyl alcohol is taken as a solvent, acetylacetone is taken as a stabilizer, and nitric acid is taken as an inhibitor; adding butyl titanate into 40-60ml of absolute ethyl alcohol, and preparing a solution A by magnetic stirring at the rotating speed of 400-; respectively mixing acetylacetone and concentrated nitric acid in proportion, adding into the solution A, and mixing to obtain solution B; dissolving MBTC into 10-30ml of absolute ethanol according to the Sn/Ti ratio of 0-15at.%, adding into the solution B, magnetically stirring for more than 2 hours, and aging for 12-24 hours for later use;
preparation of S2 NFTO precursor solution: using MBTC as a tin source, SnF2Being a fluorine source, NbCl5Mixing 10-20g of MBTC and 4-10ml of concentrated hydrochloric acid by taking methanol as a solvent as a niobium source, and placing the mixture in 50-100 ml of methanol solution to magnetically stir for 5-10min to prepare solution C; SnF with F/Sn of 20-30 at%2Dissolving in 5-15ml deionized water to obtain solution D; 1-5at.% of Nb/Sn to convert NbCl5Dissolved inPreparing solution E from 30-40ml of methanol; respectively adding the solution D and the solution E into the solution C, magnetically stirring for 2-4h to prepare an NFTO precursor solution, and aging the NFTO precursor solution for 18-24 h for later use;
S3 TiO2preparing and heat treating the Sn film: ultrasonically cleaning a quartz glass sheet in acetone, deionized water and absolute ethyl alcohol for 3 min respectively, and then placing the quartz glass sheet in a forced air drying oven for drying for later use;
placing the dried quartz glass sheet in a tube furnace, heating to 500-600 ℃, preserving heat for 6 min, and then obtaining TiO 12Spraying Sn precursor solution onto heated glass substrate to deposit film, and depositing TiO2The Sn film is thermally treated for 2 hours at the temperature of 500-700 ℃;
preparation of S4 tin oxide-based composite film: and (4) spraying the NFTO precursor liquid obtained in the step (S2) on the quartz glass substrate obtained in the step (S3), heating, depositing, keeping the temperature for 1-4 min, taking out, and naturally cooling to room temperature to obtain the tin oxide-based composite conductive film.
2. The method for preparing a tin oxide-based composite conductive film according to claim 1, characterized in that: the mass solubility of the butyl titanate in the step S1 is 2-4%.
3. The method of claim 1, wherein the amount ratio of acetylacetone to concentrated nitric acid in S1 is 2: 1.
4. The method of claim 1, wherein the ratio of the amount of MBTC to the amount of concentrated hydrochloric acid in S2 is 2: 1.
5. The method as claimed in claim 1, wherein the heating temperature in step S4 is 500-600 ℃.
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| CN108751741A (en) * | 2018-07-11 | 2018-11-06 | 燕山大学 | A kind of low emissivity glass and preparation method thereof with buffer layer and codope |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108751741A (en) * | 2018-07-11 | 2018-11-06 | 燕山大学 | A kind of low emissivity glass and preparation method thereof with buffer layer and codope |
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Application publication date: 20211109 |