CN111979532A - F, Sb double-element co-doped SnO2Method for producing thin film - Google Patents
F, Sb double-element co-doped SnO2Method for producing thin film Download PDFInfo
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 28
- 239000010409 thin film Substances 0.000 title description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 45
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000004140 cleaning Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 8
- 210000004884 grey matter Anatomy 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 53
- 239000000463 material Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- QLKSCXOGMDNMRI-UHFFFAOYSA-N [Sn].[F+][O-] Chemical compound [Sn].[F+][O-] QLKSCXOGMDNMRI-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000004969 ion scattering spectroscopy Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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Abstract
The invention discloses F, Sb co-doped SnO2The preparation method of the film comprises the following steps: (1) stannic chloride pentahydrate as SnO2The precursor of (1) takes hydrofluoric acid and antimony trichloride as F, Sb element doping sources respectively, and adopts a sol-gel method to prepare the needed sol; (2) cleaning the silicon wafer substrate to obtain the surface of the silicon wafer substrate meeting the requirements; (3) spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel, cooling and cleaning the gray matter to obtain SnO2And (3) preparing a film. The invention adopts F, Sb elements with low price, wide raw material source and easy realization of industrial production; the film is prepared by adopting a sol-gel method, so that the preparation process is simplified, the time and the labor intensity are saved, and the operability is improved; the method of combining low-temperature preheating treatment and high-temperature heat treatment is adopted to improve the stability of the film and the binding capacity of the film and the substrate, and the method is used for preparing double-element co-doped SnO2The film provides a new idea.
Description
Technical Field
The invention belongs to the technical field of thin film material preparation, and particularly relates to F, Sb double-element co-doped SnO2A method for preparing a film.
Background
Is transparentThe study of conductive oxide thin films is now one of the hot topics in the field of material research. It is a film which has a high transparency in the visible range and at the same time has excellent conductive properties. Currently, indium tin oxide (In) is the most widely used commercially2O3: sn, ITO) material, due to scarcity of indium resources and high price, researchers are forced to search for and develop new cheap TCO materials with excellent performance. SnO2The transparent conductive film is a wide-bandgap n-type semiconductor solid film, is generally polycrystalline, has a tetragonal rutile structure, has a forbidden bandwidth of 3.6-4.2 eV, is low in production cost, and has excellent electrical and optical properties. The film can be well adhered to the surfaces of glass and ceramics and can be combined with a substrate through chemical bonds.
Based on SnO2The transparent conductive oxide film material has attracted extensive attention in both experimental and theoretical research, for example, tin antimony oxide and tin fluorine oxide have been manufactured and industrially produced, but the conductivity of the transparent conductive oxide film material is still different from that of indium tin oxide. Therefore, there is still a continuing need to explore new SnO-based catalysts2The transparent conductive film material can meet the living and production requirements of people.
Disclosure of Invention
The invention aims to provide F, Sb double-element co-doped SnO2The method for preparing the thin film can obtain the thin film material with high light transmission and good conductivity.
The technical scheme of the invention is as follows: f, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
(1) sol preparation: firstly, preparing 20-30 ml of tin tetrachloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 25-45 min; mixing antimony trichloride, hydrofluoric acid and acetylacetone with the volume of 20-30 ml, and stirring for 25-45 min; then mixing the two mixed solutions, adding a stabilizer, and stirring for 1.5-2.5 hours to prepare 40-60 ml of sol;
(2) cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5-10 min in sequence to obtain the silicon wafer substrate surface meeting the requirements;
(3)SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel, cooling and cleaning the gray matter to obtain SnO2And (3) preparing a film.
Further, the mass ratio of the tin tetrachloride pentahydrate to the absolute ethyl alcohol is (1-3): (5-6); the mass ratio of the antimony trichloride to the hydrofluoric acid to the acetylacetone is (1-2): (1-2): (45-50).
Further, the mass fraction of the hydrofluoric acid is 5%.
Further, mixing the stannic chloride pentahydrate and absolute ethyl alcohol, stirring at normal temperature, mixing antimony trichloride, hydrofluoric acid and acetylacetone, carrying out water-bath heating magnetic stirring, mixing the two mixed solutions, and adding a stabilizer to carry out water-bath heating magnetic stirring; the water bath heating and magnetic stirring are used for maintaining the temperature condition required for preparing the sol so as to ensure that the liquid reaches the experimental requirement after being mixed.
Further, the stabilizer comprises polyethylene glycol and collodion; polyethylene glycol has better solubilization and dispersion effects, and the polyethylene glycol is selected as a stabilizer, so that the prepared sol is more uniform, and the concentration and the viscosity of the sol meet the experimental requirements; collodion, as a cosolvent, may also perform a similar function.
Further, in the step (3), drying is carried out when each layer of sol is coated, wherein the temperature is 120-180 ℃, and the time is 10-20 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 400-800 ℃, and the time is 1-2 h.
The invention has the beneficial effects that:
1. f, Sb is adopted as two elements which have low price, wide raw material source and easy realization of industrial production; preparing the double-doped SnO2: (F + Sb) film with SnO2F film, SnO2: the Sb film has better photoelectric property compared with the Sb film.
2. The film is prepared by adopting a sol-gel method, so that the preparation process is simplified, the time and the labor intensity are saved, and the operability is improved.
3. The method of combining low-temperature preheating treatment and high-temperature heat treatment is adopted to improve the stability of the film and the bonding capability of the film and the substrate, and the method is used for preparing double-element co-doped SnO2The film provides a new idea.
Drawings
FIG. 1 shows SnO with F, Sb doping amounts of 5% and 10%, respectively, in examples 1-5 of the present invention2XRD patterns of the film at different annealing temperatures.
FIG. 2 shows SnO with F, Sb doping amounts of 5% and 10%, respectively, in examples 1-5 of the present invention2The resistivity, carrier concentration and Hall mobility of the film are changed along with the annealing temperature.
FIG. 3 shows SnO with F, Sb doping amounts of 5% and 10%, respectively, in examples 1-5 of the present invention2The ultraviolet and visible light transmittance curves of the film at different annealing temperatures.
Detailed Description
The present invention will be further described with reference to the following examples and accompanying drawings, but the present invention is not limited to the scope of protection and application.
Example 1
F, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
1. sol preparation: firstly, preparing 25ml of stannic chloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 30 min; 25ml of antimony trichloride, 5% hydrofluoric acid and acetylacetone are mixed and stirred for 30 min; then mixing the two mixed solutions, adding a stabilizer (polyethylene glycol and collodion) and stirring for 2 hours to prepare 50ml of sol;
2. cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5min in sequence to obtain a silicon wafer substrate surface meeting the requirements;
3.SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel; wherein each layer of sol is coatedDrying at 150 deg.C for 15 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 600 ℃, the annealing time is 1h, the gray matter is cleaned after cooling, and the SnO is prepared2And (3) preparing a film.
Example 2
F, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
1. sol preparation: firstly, preparing 25ml of stannic chloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 30 min; 25ml of antimony trichloride, 5% hydrofluoric acid and acetylacetone are mixed and stirred for 30 min; then mixing the two mixed solutions, adding a stabilizer (polyethylene glycol and collodion) and stirring for 2 hours to prepare 50ml of sol;
2. cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5min in sequence to obtain a silicon wafer substrate surface meeting the requirements;
3.SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel; wherein, each layer of sol is dried at 150 ℃ for 15 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 550 ℃, the annealing time is 1h, cooling and then cleaning the gray matter to prepare SnO2And (3) preparing a film.
Example 3
F, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
1. sol preparation: firstly, preparing 25ml of stannic chloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 30 min; 25ml of antimony trichloride, 5% hydrofluoric acid and acetylacetone are mixed and stirred for 30 min; then mixing the two mixed solutions, adding a stabilizer (polyethylene glycol and collodion) and stirring for 2 hours to prepare 50ml of sol;
2. cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5min in sequence to obtain a silicon wafer substrate surface meeting the requirements;
3.SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel; wherein, each layer of sol is dried at 150 ℃ for 15 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 500 ℃, the annealing time is 1h, cooling and then cleaning the gray matter to prepare SnO2And (3) preparing a film.
Example 4
F, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
1. sol preparation: firstly, preparing 25ml of stannic chloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 30 min; 25ml of antimony trichloride, 5% hydrofluoric acid and acetylacetone are mixed and stirred for 30 min; then mixing the two mixed solutions, adding a stabilizer (polyethylene glycol and collodion) and stirring for 2 hours to prepare 50ml of sol;
2. cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5min in sequence to obtain a silicon wafer substrate surface meeting the requirements;
3.SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel; wherein, each layer of sol is dried at 150 ℃ for 15 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 450 ℃, the annealing time is 1h, the gray matter is cleaned after cooling, and the SnO is prepared2And (3) preparing a film.
Example 5
F, Sb double-element co-doped SnO2The preparation method of the film comprises the following steps:
1. sol preparation: firstly, preparing 25ml of stannic chloride pentahydrate and absolute ethyl alcohol, mixing and stirring for 30 min; 25ml of antimony trichloride, 5% hydrofluoric acid and acetylacetone are mixed and stirred for 30 min; then mixing the two mixed solutions, adding a stabilizer (polyethylene glycol and collodion) and stirring for 2 hours to prepare 50ml of sol;
2. cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5min in sequence to obtain a silicon wafer substrate surface meeting the requirements;
3.SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel; wherein, each layer of sol is dried at 150 ℃ for 15 min; carrying out annealing heat treatment after drying treatment; annealing at 400 deg.C for 1 hr, cooling, and cleaning to obtain SnO2And (3) preparing a film.
SnO with F, Sb doping amounts of 5% and 10% in examples 1-5 of the present invention, respectively2A film; the doping amount is 5% F/Sn and 10% Sb/Sn, respectively, and refers to the mass ratio of elements in the thin film, and the doping amount is obtained by performing comparative studies on parameter changes such as doping concentration of element F, Sb, the type and amount of a stabilizer, mixing and stirring time, temperature of low-temperature preheating treatment, temperature of high-temperature heat treatment and the like by using an orthogonal test method, and finding out an optimal preparation process. In the optimal process case, namely: F. sb doping amounts of 5% and 10%, the number of coating layers of 5, and annealing temperature of 550 ℃ respectively to obtain SnO2The lowest resistivity of the film is 2.255 multiplied by 10-3Omega cm, the average transmittance of the film in the visible light region was 80.12%, and the overall performance of the film was the best. The following description is made with reference to the accompanying drawings.
As shown in fig. 1, it can be seen from the graph that, from 400 ℃ to 600 ℃, the intensity of the (110) diffraction peak increases and then decreases with increasing temperature, and the diffraction intensity reaches a maximum value when the temperature increases to 550 ℃, i.e., the best crystallization effect is obtained at 550 ℃. While the diffraction peak intensity of the (110) crystal face is obviously greater than that of other crystal faces, because SnO2The film is mainly grown along the preferential growth of the (110) crystal face, and the result shows that the proper annealing temperature is effective to improve SnO2(F + Sb) film organization structure and performance.
SnO as shown in FIG. 22The resistivity of the film decreased first and then increased with increasing temperature and was a minimum of 2.255 х 10 at an annealing temperature of 550 deg.C-3Omega cm, which is the largest at a temperature of 400 ℃ and which changes in a zigzag shape. The carrier concentration of the film is high and is 0.6109 multiplied by 1019～8.668×1019The range varies, increasing in value and decreasing in value. And the Hall mobility is changed within the range of 2.529-15.39, and the change trend is increased firstly and then reduced. This indicates to some extent that Sb usually replaces the position of Sn in the form of a substitutional ion, while F atoms occupy the position of O ions in the form of a substitutional ion, but when the temperature is raised to some extent, partial lattice distortion is caused due to the effects of ionized impurities caused by Sb and oxygen vacancies caused by F, so that the resistivity of the thin film is increased and then decreased, similarly to the results of XRD analysis.
SnO at a temperature of 550 DEG C2The (F + Sb) thin film has the smallest resistivity, the largest carrier concentration and the Hall mobility. This shows that the increase of the hall mobility and the carrier concentration of the thin film depends on the optimization of the crystallization quality of the thin film, because the better the crystallization quality, the larger the grain size, the smaller the grain boundary, and the smaller the carrier scattering of the thin film by the grain boundary, which is beneficial to increasing the hall mobility. Furthermore, the crystallinity of the thin film is good to a certain extent, and thus, the defects in the thin film can be reduced to reduce the binding force of the defects to free electrons, resulting in an increase in carrier concentration. Dopant ion scattering and grain boundary scattering are the primary scattering mechanisms that affect the mobility of the film carriers. The defect energy level introduced by doping F, Sb double elements can increase the carrier concentration and improve the conductivity of the film.
As shown in FIG. 3, it is possible to see the interference fringes having deep valleys and high peaks, indicating that the surface of the prepared film is smooth and dense, the film formation quality is good, and the average transmittance observed in the visible light region is more than 80%. However, SnO at different annealing temperatures2The (F + Sb) thin film has a slight difference in light absorption. The transmittance map shows that the average light transmittance is sharply increased within a visible light range of 270-320 nm. For the transparent conductive film, the average transmittance in the visible light region (380-800 nm) has a high requirement, generally more than 80%, so as to be applied to photoelectric devices. At 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.CSnO produced at temperature2Average transmittance (T) of (F + Sb) filmavg) Respectively 81.45%, 88.28%, 85.04%, 80.12% and 81.09%, and the obtained average transmittance is high, the optical performance is good, and the optical film can be practically applied to optoelectronic devices.
The working principle of the invention is as follows: by sol-gel method, with tin tetrachloride pentahydrate (SnCl)4·5H2O) as SnO2The precursor of (a) is prepared from hydrofluoric acid (HF) and antimony trichloride (SbCl)3) Respectively used as fluorine (F) and antimony (Sb) element doping sources, and F, Sb co-doped SnO is prepared on a glass silicon wafer substrate2The transparent conductive film adopts a Hall test system, an X-ray diffractometer and an ultraviolet visible spectrophotometer to characterize the tissue structure and the photoelectric property of the film. The method adopts an orthogonal test method to compare and research the parameter changes of element F, Sb doping concentration, the type and dosage of a stabilizer, the mixing and stirring time, the low-temperature preheating treatment temperature, the high-temperature heat treatment temperature and the like, and finds out the optimal preparation process parameters through a great deal of creative work.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or simple substitutions which are not thought of through the inventive work should be included in the scope of the present invention.
Claims (6)
1. F, Sb double-element co-doped SnO2The preparation method of the film is characterized by comprising the following steps:
(1) sol preparation: firstly, preparing 20-30 ml of tin tetrachloride pentahydrate and absolute ethyl alcohol, mixing, and stirring for 25-45 min; mixing antimony trichloride, hydrofluoric acid and acetylacetone with the volume of 20-30 ml, and stirring for 25-45 min; then mixing the two mixed solutions, adding a stabilizer, and stirring for 1.5-2.5 hours to prepare 40-60 ml of sol;
(2) cleaning a silicon wafer substrate: ultrasonically cleaning the silicon wafer substrate with deionized water, hydrofluoric acid, acetone and absolute ethyl alcohol for 5-10 min in sequence to obtain the silicon wafer substrate surface meeting the requirements;
(3)SnO2preparing a film: spin-coating sol on a silicon wafer substrate by using a spin coater, and obtaining gel through a gelling process; drying and heat treating the gel, cooling and cleaning the gray matter to obtain SnO2And (3) preparing a film.
2. F, Sb Bi-element co-doped SnO according to claim 12The preparation method of the film is characterized by comprising the following steps: the mass ratio of the tin tetrachloride pentahydrate to the absolute ethyl alcohol is (1-3): (5-6); the mass ratio of the antimony trichloride to the hydrofluoric acid to the acetylacetone is (1-2): (1-2): (45-50).
3. F, Sb Bi-element co-doped SnO according to claim 22The preparation method of the film is characterized by comprising the following steps: the mass fraction of the hydrofluoric acid is 5%.
4. F, Sb Bi-element co-doped SnO according to claim 32The preparation method of the film is characterized by comprising the following steps: mixing the stannic chloride pentahydrate and absolute ethyl alcohol, stirring at normal temperature, mixing the antimony trichloride, the hydrofluoric acid and the acetylacetone, heating in water bath, magnetically stirring, mixing the two mixed solutions, adding the stabilizer, heating in water bath, and magnetically stirring.
5. F, Sb Bi-element co-doped SnO according to claim 1 or 42The preparation method of the film is characterized by comprising the following steps: the stabilizer comprises polyethylene glycol and collodion.
6. F, Sb Bi-element co-doped SnO according to claim 12The preparation method of the film is characterized by comprising the following steps: in the step (3), drying is carried out when each layer of sol is coated, wherein the temperature is 120-180 ℃, and the time is 10-20 min; carrying out annealing heat treatment after drying treatment; the annealing temperature is 400-800 ℃, and the time is 1-2 h.
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