CN109761506B - Method for preparing compact tin oxide film by room temperature ultrasonic oscillation - Google Patents
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- CN109761506B CN109761506B CN201910166334.9A CN201910166334A CN109761506B CN 109761506 B CN109761506 B CN 109761506B CN 201910166334 A CN201910166334 A CN 201910166334A CN 109761506 B CN109761506 B CN 109761506B
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Abstract
The invention relates to a method for preparing a compact tin oxide film by room-temperature ultrasonic oscillation. The method comprises the following steps: adding tin salt into a solvent, carrying out reflux reaction, standing and aging, spin-coating the obtained tin oxide sol on a pretreated conductive substrate, and finally carrying out ultrasonic oscillation. The tin oxide film with good crystallinity, uniformity, compactness and excellent conductivity is obtained by the method, plays a role in low-temperature sintering, and is particularly suitable for forming a film on the surface of a high-molecular substrate.
Description
Technical Field
The invention belongs to the field of tin oxide film preparation, and particularly relates to a method for preparing a compact tin oxide film by room-temperature ultrasonic oscillation.
Background
Tin oxide is an important electronic, ceramic and chemical material. In the field of electrical and electronic engineering, the tin oxide film has the characteristics of transparent conductivity, good thermodynamic, chemical and mechanical stability and no biotoxicity, can be used as a transparent electrode material, and is widely applied to solar cells, thin film resistors and flat panel displays.
The current methods for preparing tin oxide films are mainly sol-gel, chemical bath deposition and atomic layer deposition. The sol-gel method is the most commonly used method for preparing tin oxide films, and a heat treatment of more than 180 ℃ is usually required in the preparation process to promote the crystallization of tin oxide. The heat treatment process consumes a large amount of energy and is not suitable for producing a tetragonal crystalline tin oxide film on a high molecular substrate having poor heat resistance, such as PET-ITO or PEN-ITO, because 180 c is much higher than the glass transition temperature of PET or PEN, above which PET or PEN is thermally deformed. The method for pretreating tin oxide sol by using chemical bath improves the compactness of the film, but the method also needs high-temperature heat treatment and is not suitable for preparing high-quality tin oxide films on high-molecular substrates. The method for depositing the atomic layer realizes the low-temperature preparation of the tin oxide film, but the prepared tin oxide film has low crystallinity, and meanwhile, the method has the advantages of complex process, high cost and strong dependence on equipment.
CN2003101070713 discloses a method for preparing a tin dioxide nanocrystalline film, which comprises the steps of firstly putting a cleaned substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide to hydroxylate the surface of the substrate; secondly, the substrate is soaked in X (CH)2)nSi(OCH3)3Or X (CH)2)nSiCl3Or HS (CH)2)mForming an organic molecule self-assembly monolayer film on the surface of the substrate in the Y solution; then soaking the substrate by using saturated potassium hydrogen persulfate solution to functionalize the organic molecule self-assembly layer on the surface of the substrate; finally immersing the substrate in SnCl4Hydrochloric acid solution or SnF2The boric acid solution to prepare the tin dioxide nano crystalline film. The liquid phase deposition method can prepare oxidation at a low temperature of 80 DEG CTin nanocrystalline films, but this method takes up to 2 days to produce.
CN2016108770441 discloses a method for preparing a doped tin oxide transparent conductive film, which reduces the sheet resistance of the tin oxide conductive film through a multi-element doping synergistic effect to obtain a multi-element doped tin oxide conductive film with high transparency and low sheet resistance, but the preparation process still requires high-temperature sintering at 400 ℃, and is not suitable for polymer-based flexible thin-film solar cells.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a compact tin oxide film by room-temperature ultrasonic oscillation so as to overcome the defect that the tin oxide film is long in preparation time or the thermal deformation of polymer substrates such as PET (polyethylene terephthalate) and the like is caused by high-temperature heat treatment in the prior art.
The invention discloses a method for preparing a compact tin oxide film by room-temperature ultrasonic oscillation, which comprises the following steps:
(1) adding tin salt into a solvent to obtain a tin oxide precursor solution with the concentration of 1-1.5M, performing reflux reaction, performing hydrolysis or alcoholysis reaction on the precursor and the solvent to obtain unstable tin oxide sol, and standing and aging to obtain stable tin oxide sol;
(2) and (2) coating the stable tin oxide sol obtained in the step (1) on a pretreated conductive substrate in a spinning manner, and performing ultrasonic oscillation on the obtained tin oxide film at room temperature to obtain the compact tin oxide film.
The tin salt in the step (1) comprises SnCl2·2H2O、SnC2O4、SnCl4·5H2O or (CH)3CH2CH2CH2)2SnO。
The solvent in the step (1) comprises isopropanol, ammonia water, a sodium carbonate aqueous solution, triethanolamine or ethanol.
In the step (1), the reflux reaction temperature is 50-100 ℃, and the reflux reaction time is 0.5-2.0 h.
And (2) in the step (1), the standing and aging temperature is room temperature, and the standing and aging time is more than 6 hours.
The conductive substrate in the step (2) comprises FTO glass, ITO glass, AZO glass or a polymer substrate conductive film.
The polymer substrate conductive film comprises ITO-PET or ITO-PEN.
The conductive substrate pretreatment in the step (2) comprises the following steps: and (3) ultrasonically cleaning the conductive substrate for 15-25 min by sequentially adopting a glass cleaning agent, acetone and ethanol, and then drying in an oven at the temperature of 60-80 ℃ for 30-60 min.
The rotating speed of the spin in the step (2) is 1500-3000 r/min.
In the step (2), the ultrasonic oscillation power is 5-20W, and the ultrasonic oscillation time is 1-10 min.
The compact tin oxide film in the step (2) has strong crystallinity, uniform compactness and high conductivity.
In the step (2), the concentration of chloride ions in the dense tin oxide film is lower than 4.15 at%, the sheet resistance of the film is 48.46 omega. □, and the microstructure is dense.
The precursor is mainly selected from inorganic substances containing tin, the raw materials are uniformly mixed in a liquid phase, and the inorganic substances containing tin are hydrolyzed to generate Sn (OH)2. Sn (OH) during standing and aging2The hydroxyl in the catalyst is dehydrated and condensed to generate amorphous SnO. In the process of heating or ultrasonic oscillation, the residual-OH continues to be broken, the residual solvent is volatilized, and SnO is oxidized to generate tetragonal crystalline SnO2. The main reaction formula involved in the invention is as follows:
SnCl2+H2O→Sn(OH)2+2HCl (1)
Sn(OH)2→SnO+H2O (2)
in the formula (1), stannous chloride is slowly hydrolyzed into stannous hydroxide sol under the action of isopropanol solution and water vapor in air, the stannous hydroxide sol can be dehydrated and decomposed into stannous oxide gel according to the formula (2), and finally stannic oxide crystals are generated under the condition of heating or ultrasonic oscillation according to the formula (3).
The invention roughly estimates the energy required in the sintering process of the tin oxide film, and is mainly used for the cracking of-OH and the drying of the film. The energy required to break the-OH bond was 460KJ/mol, and the tin oxide sol used was at a concentration of 1mol/mL, assuming that one dose was 1mL, the energy required was calculated to be 460 KJ. While the mechanical energy provided by ultrasonic oscillation under the conditions of 10W and 40kHz is 680KJ/s, and it is estimated that the complete-OH fracture in the film can be completed within 1 s. However, it was found experimentally that the completion of the sintering of the tin oxide film additionally requires energy for the drying process of the film, requiring a suitable extension of the time of the ultrasonic oscillation.
Advantageous effects
The invention adopts the ultrasonic oscillation tin oxide sol film to prepare the compact tin oxide film, in particular to prepare crystalline SnO on a high molecular substrate2The tin oxide nanocrystalline film is obtained by utilizing the cavitation of ultrasonic waves through providing energy for the local part of the tin oxide film by oscillation, and the tin oxide film with good crystallinity, uniformity, compactness and excellent conductivity is prepared at room temperature. Compared with the traditional thermal sintering method, the ultrasonic oscillation method realizes low-temperature sintering, effectively saves energy, can prepare a compact tin oxide film on a polymer substrate which is not high in temperature resistance, and is expected to be used for preparing inorganic materials which are easily decomposed by heating, such as Prussian blue and the like.
Drawings
FIG. 1 is a diagram of an apparatus for preparing a dense tin oxide film according to the present invention;
FIG. 2 is a scanning electron microscope photograph of a tin oxide nanocrystal film of example 1;
FIG. 3 is an X-ray powder diffraction pattern of the tin oxide nanocrystal film of example 1;
FIG. 4 is an I-V plot of a tin oxide nanocrystalline film of example 1;
FIG. 5 is an X-ray powder diffraction pattern of a tin oxide nanocrystalline film of example 2;
FIG. 6 is an I-V plot of a tin oxide nanocrystal film of example 2;
FIG. 7 is an X-ray powder diffraction pattern of a tin oxide nanocrystalline film of example 3;
FIG. 8 is an I-V plot of a tin oxide nanocrystal film of example 3;
FIG. 9 is an X-ray powder diffraction pattern of a tin oxide thin film in comparative example 1;
FIG. 10 is an I-V plot of a tin oxide nanocrystalline film of comparative example 1;
FIG. 11 is an X-ray powder diffraction pattern of a tin oxide thin film in comparative example 2;
FIG. 12 is an I-V graph of a tin oxide film in comparative example 2.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Adding 1.128g of stannous chloride dihydrate (purchased from Sigma-Aldrich company) into 50ml of anhydrous isopropanol (purchased from Chinese medicine) solution to prepare 1M of stannic oxide precursor solution, refluxing for 1h at 70 ℃ to obtain stannic oxide sol, and standing and aging the stannic oxide sol for 8h at room temperature to obtain stable stannic oxide sol;
(2) ultrasonically cleaning PET (purchased from Hunan City science and technology Co., Ltd.) sputtered with ITO with a glass cleaning agent, acetone and ethanol for 20min in sequence, and drying in an oven at 70 ℃ for 45 min; spin-coating the 1M tin oxide sol on the pretreated conductive substrate at 3000 r/min to obtain a tin oxide sol film;
(3) and ultrasonically oscillating the tin oxide sol film at room temperature of 10W for 3min to obtain a uniform and compact tin oxide film.
The tin oxide film obtained in this example was observed by a scanning electron microscope, and as a result, a uniform and dense tin oxide film was obtained as shown in fig. 2.
As a result of observing the tin oxide film obtained in this example by an X-ray diffractometer, as shown in fig. 3, the tin oxide film having good crystallinity was obtained, and the (101) crystal plane at 37.7 ° had the strongest diffraction peak.
The I-V curve of the tin oxide film obtained in this example was obtained from the givensis table, and the results are shown in fig. 4, according to the formula: the conductivity is film thickness/(area-slope), and the area and film thickness are fixed at 16mm2And 30nm, wherein the slope value is 131.28, and the conductivity of the tin oxide film is 0.246S/m according to the formula, so that the tin oxide film has excellent conductivity.
Example 2
The preparation process was the same as in steps (1) and (2) of example 1, to obtain a tin oxide sol film. And ultrasonically oscillating the prepared sol film at 10W for 2min to obtain the tin oxide film.
The tin oxide film obtained in this example was observed by an X-ray diffractometer, and as a result, as shown in fig. 5, a crystalline tin oxide film was obtained, and a sample in which the diffraction peak corresponding to the (101) crystal plane at a 2 θ angle of 37.7 ° was weaker than that of 10W oscillation for 3 minutes was obtained.
The I-V curve of the tin oxide film obtained in this example was obtained from the givensis source table, and the results are shown in fig. 6, according to the formula: the conductivity is film thickness/(area-slope), and the area and film thickness are fixed at 16mm2And 30nm, wherein the slope value is 72.37, and the conductivity of the tin oxide film is 0.136S/m and the conductivity is weaker than that of the tin oxide film prepared by 10W oscillation for 3min according to the formula.
Example 3
The preparation process was the same as in steps (1) and (2) of example 1, to obtain a tin oxide sol film. And ultrasonically oscillating the prepared sol film at 15W for 1min to obtain the tin oxide film.
As a result of observing the tin oxide film obtained in this example by an X-ray diffractometer, as shown in fig. 7, a crystalline tin oxide film was obtained, and the diffraction peak corresponding to the (101) crystal plane at a 2 θ angle of 37.7 ° was slightly weaker than that of the sample oscillated at 10W for 3 minutes and stronger than that of the sample oscillated at 10W for 2 minutes.
The I-V curve of the tin oxide film obtained in this example was obtained from the givensis table, and the results are shown in fig. 8, according to the formula: the conductivity is film thickness/(area-slope), and the area and film thickness are fixed at 16mm2And 30nm, slope in the graphThe value is 114.01, and the conductivity of the tin oxide film is calculated according to the formula to be 0.214S/m, and the conductivity is weaker than that of the tin oxide film prepared by 10W oscillation for 3 minutes.
Comparative example 1
And annealing the tin oxide sol film at 185 ℃ for 3h to obtain the tin oxide film. The preparation method of the tin oxide sol film is the same as that of the example 1.
The tin oxide film obtained in the present comparative example was observed by an X-ray diffractometer, and as a result, as shown in fig. 9, the crystallinity of the tin oxide film obtained was closer to that of the sample in which the diffraction peak corresponding to the (101) crystal plane at a 2 θ angle of 37.7 ° was weaker than that of the sample in which the 10W oscillation was carried out for 3 minutes, and that of the sample in which the 15W oscillation was carried out for 1 minute.
The I-V curve of the tin oxide film obtained in this comparative example was obtained from the givensis source table, and the results are shown in fig. 10, according to the formula: the conductivity is film thickness/(area-slope), and the area and film thickness are fixed at 16mm2And 30nm, wherein the slope value is 102.05, and the conductivity of the tin oxide film is 0.191S/m according to the formula calculation, and the conductivity is slightly inferior to that of the tin oxide film treated by ultrasonic oscillation.
Comparative example 2
A tin oxide sol film was prepared as in example 1, without treatment, as a comparative reference.
The tin oxide film obtained in the present comparative example was observed by an X-ray diffractometer, and as a result, an uncrystallized tin oxide film was obtained as shown in fig. 11.
The I-V curve of the tin oxide film obtained in this comparative example was obtained from the givensis source table, and the results are shown in fig. 12, according to the formula: the conductivity is film thickness/(area-slope), and the area and film thickness are fixed at 16mm2And 30nm, wherein the slope value is 19.72, the conductivity of the tin oxide film is 0.037S/m according to the formula, and the conductivity is obviously weaker than that of the tin oxide film subjected to ultrasonic oscillation or heating treatment.
Comparing the test results of the examples and the comparative examples, it can be seen that the optimal conditions for preparing the tin oxide film by ultrasonic oscillation are that 10W is oscillated for 3 minutes, and the peak sample is more crystalline than the peak sample oscillated for 2 minutes at 10W, and it is presumed that the sample treated for 2 minutes may not react completely; the conductivity was higher than that of the sample oscillated at 15W for 1 minute, and it was suspected that the 15W power destroyed the dense structure on the surface of the tin oxide film. Comparing the tin oxide film treated for 3 minutes under the oscillation power of 10W with the tin oxide film prepared by heating and non-heating, the tin oxide film prepared by the ultrasonic oscillation of 10W for 3 minutes is found to have better crystallinity, more uniform and compact film surface and more excellent conductivity. The ultrasonic oscillation method can effectively replace heating treatment and has the function of room temperature sintering.
Claims (8)
1. A method for preparing a compact tin oxide film by room temperature ultrasonic oscillation comprises the following steps:
(1) adding tin salt into a solvent to obtain a tin oxide precursor solution with the concentration of 1-1.5M, performing reflux reaction to obtain unstable stannous hydroxide sol, and standing and aging to obtain stable stannous oxide gel;
(2) and (2) rotationally coating the stable stannous oxide gel obtained in the step (1) on a pretreated conductive substrate, and performing ultrasonic oscillation oxidation on the obtained stannous oxide film at room temperature to obtain a compact stannic oxide film.
2. The method of claim 1, wherein the tin salt in step (1) comprises SnCl2×2H2O or SnC2O4(ii) a The solvent comprises isopropanol, ammonia water, sodium carbonate aqueous solution, triethanolamine or ethanol.
3. The method according to claim 1, wherein the reflux reaction temperature in the step (1) is 50-100 ℃, and the reflux reaction time is 0.5-2.0 h.
4. The method according to claim 1, wherein the standing and aging temperature in step (1) is room temperature, and the standing and aging time is 6 hours or more.
5. The method according to claim 1, wherein the conductive substrate in step (2) comprises FTO glass, ITO glass, AZO glass or polymer substrate conductive film.
6. The method of claim 5, wherein the polymer-based conductive film comprises ITO-PET or ITO-PEN.
7. The method of claim 1, wherein the conductive substrate pretreatment of step (2) comprises: and (3) ultrasonically cleaning the conductive substrate for 15-25 min by sequentially adopting a glass cleaning agent, acetone and ethanol, and then drying in an oven at the temperature of 60-80 ℃ for 30-60 min.
8. The method as claimed in claim 1, wherein the spin rate in the step (2) is 1500-3000 rpm; the ultrasonic oscillation power is 5-20W, and the ultrasonic oscillation time is 1-10 min.
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Non-Patent Citations (5)
| Title |
|---|
| Grain engineering by ultrasonic substrate vibration post-treatment of wet perovskite films for annealing-free, high performance, and stable perovskite solar cells;Hao Xiong等;《Nanoscale》;20180329;第10卷;第8526-8535页 * |
| In fluences of ultrasonic vibration on morphology and photoelectric properties of F-doped SnO2 thin fi lms during laser annealing;Bao-jia Li等;《Applied Surface Science》;20180726;第940–948页 * |
| Toward scale-up of perovskite solar cells：Annealing-free perpvskite layer by low-cost ultrasonic substrate vibration of wet films;Mohammad-Reza等;《Materials Today Communications》;20180106;第14卷;第151-159页 * |
| Ultrasonic vibration imposed on nanoparticle-based ZnO film improves the performance of the ensuing perovskite solar cell;Yihe Miao等;《Materials Research Express》;20180228;第1-18页 * |
| 柔性太阳电池发展研究;王辉等;《中国工程科学》;20180615(第03期);第66-73页 * |
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