Method for preparing titanium dioxide and hybrid hydrophilic film thereof through low-temperature vapor deposition
Titanium dioxide and its hybrid film were prepared by low-temperature vapor-phase deposition method, which solved the transparency and self-cleaning performance problems caused by traditional methods, and achieved high transparency and self-cleaning effect of titanium dioxide film preparation.
Patent Information
- Application Number
- CN202510149590.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-11
- Publication Date
- 2025-07-04
AI Technical Summary
In the prior art, the preparation method of titanium dioxide thin film leads to poor light transmittance, and the thickness of the traditional sol-gel method is large, affecting the transparency and self-cleaning performance of the glass.
Titanium dioxide and its hybrid hydrophilic film were prepared by low-temperature vapor deposition method. It was deposited in a vacuum dryer by a mixed solution of tetrabutyl titanate and ammonium bicarbonate, and combined with muffle furnace annealing treatment, to form a dense titanium dioxide or hybrid film with a porous structure.
It has achieved high transparency titanium dioxide film preparation, with excellent water droplet super spreading performance and self-cleaning performance, which can effectively prevent mist formation and is suitable for large-scale production.
Smart Images
Figure CN120247424A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of semiconductor nanomaterial growth and glass empowerment, and particularly relates to a method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature chemical vapor deposition. Background Art
[0002] In the field of modern materials science, superhydrophilic self-cleaning glass, as a new material with unique properties, is gradually becoming a research hotspot. Titanium dioxide (TiO2) is well-known for its excellent optical, electrical, and chemical stability. When combined with a glass matrix, it exhibits a series of remarkable application prospects. This material not only has significant advantages in self-cleaning surface technology but also shows great potential in multiple fields such as biomedicine, environmental purification, and energy conversion. The preparation of hydrophilic titanium dioxide glass involves complex physico-chemical processes, including the synthesis, dispersion, and integration of titanium dioxide nanoparticles with the glass substrate. By precisely controlling these processes, the hydrophilicity and photocatalytic activity of the material can be regulated. Hydrophilicity endows the material surface with the property of rapid wetting, which not only helps reduce the adhesion of dust and dirt but also promotes the photocatalytic reaction, thereby achieving efficient self-cleaning and environmental purification functions. Wang and Fujishima et al. coated a uniform and transparent titanium dioxide nanofilm on the glass surface and found that the hydrophilicity of the film was significantly improved after ultraviolet irradiation. Sun et al. prepared nano-TiO2 sol by the sol-gel method and deposited hydrophilic TiO2 films on stainless steel plates through spin coating technology. The effects of pH value, complexing agent, and calcination temperature on the hydrophilicity of the films were studied. Claire Armstrong compared the morphology, electrical, and optical properties of titanium dioxide films deposited by spatial atomic layer deposition of titanium isopropoxide (TTIP) and titanium tetrachloride (TiCl4). Summary of the Invention
[0003] Aiming at the problems that titanium dioxide has a relatively large refractive index and the traditional sol-gel coating is relatively thick, resulting in poor light transmittance, the present invention provides a preparation technology for environmentally friendly, low-cost, and highly transparent gaseous titanium dioxide thin films and their hybrid films, and applies them to the surface hydrophilic self-cleaning of glass. The film presents a uniform rough granular structure on the glass surface, endowing the glass with excellent super-spreading performance, and the water droplet contact angle can be reduced to below 5° within one second. The preparation process of the present invention is simple, has high repeatability, low cost, and is green and environmentally friendly, suitable for large-scale production. After preparation, the transparency of the glass is hardly affected, and at the same time, excellent water droplet super-spreading characteristics can be exhibited without ultraviolet light irradiation on the film, which can effectively prevent the formation of fog on the glass surface and make the glass surface show good self-cleaning performance.
[0004] The present invention adopts the following technical solutions: A method for preparing titanium dioxide and its hybrid hydrophilic film by low-temperature chemical vapor deposition, comprising the following steps: First step, substrate cleaning; Second step, vapor-phase preparation of titanium dioxide film and its hybrid film; Third step, after the sample prepared in the second step is cooled, it is heated and annealed in a muffle furnace.
[0005] Furthermore, the substrate in the first step includes a glass substrate.
[0006] Furthermore, the glass substrate includes any one of ultra-white glass, quartz glass, soda-lime glass, and conductive glass.
[0007] Furthermore, the area of the glass substrate is 1-200 cm 2 .
[0008] Furthermore, the substrate cleaning step in the first step is as follows: after the substrate is cut, it is successively ultrasonically cleaned in acetone, absolute ethanol, and deionized water for 10-30 min each; the power of the ultrasonic cleaning is 50-150 W; A piranha solution is prepared by mixing concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:3. The dried substrate is placed in the piranha solution, heated to 90-180 °C, and heated for 1-6 h to deeply clean the substrate surface. After cooling to room temperature, the substrate is taken out, rinsed with deionized water more than 5 times, and dried.
[0009] Furthermore, the vapor-phase preparation step of the titanium dioxide film in the second step is as follows: Tetrabutyl titanate and ammonium bicarbonate particles are stirred and mixed to obtain a mixed solution, and the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1-5:1; The substrate and the mixed solution are evacuated in a vacuum dryer. After evacuation, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15-60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1-0.1:1; The vacuum dryer is placed in an oven for vapor deposition of the film. In the first step, it is heated at 20-50 °C for 2-12 h to form a dense titanium dioxide-based film at the bottom layer. In the second step, it is heated at 60-100 °C for 0.5-6 h to form a porous structure on the surface layer of the titanium dioxide nanometer film.
[0010] Furthermore, the titanium dioxide hybrid film in the second step includes a titanium dioxide and silica hybrid film or a titanium dioxide and zinc oxide hybrid film.
[0011] Furthermore, the vapor-phase preparation step of the titanium dioxide and silica hybrid film is as follows: Tetrabutyl titanate and ammonium bicarbonate particles are stirred and mixed to obtain a mixed solution of tetrabutyl titanate and ammonium bicarbonate, which is placed in beaker 1. Separately, an appropriate amount of tetraethyl orthosilicate solution is placed in beaker 2. The molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1 - 5:1, and the molar ratio of tetraethyl orthosilicate to tetrabutyl titanate is 1:1 - 1:10; The substrate, the mixed solution of tetrabutyl titanate and ammonium bicarbonate, and the tetraethyl orthosilicate solution are evacuated in a vacuum dryer. After evacuation, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15 - 60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1 - 0.1:1; The vacuum dryer is placed in an oven for vapor deposition of the film. In the first step, it is heated at 20 - 50 °C for 2 - 12 h to form a dense bottom layer of titanium dioxide - silica - based film, and in the second step, it is heated at 60 - 100 °C for 0.5 - 6 h to form a porous surface structure of the titanium dioxide - silica nanocomposite film.
[0012] Furthermore, the gas - phase preparation steps of the titanium dioxide and zinc oxide hybrid film are as follows: Growth of ZnO particle film Prepare a 0.001 - 0.01 mol / L zinc acetate ethanol solution, and use a dip coater to dip - coat and lift - coat the substrate. Each dipping time is 60 - 90 s, the interval is 60 - 120 s, and the lift - coating speed is 50 - 150 mm / min. Then, annealing crystallization is carried out, and the annealing temperature is 200 - 450 °C and the time is 30 - 60 min; Gas - phase preparation of titanium dioxide film layer Tetrabutyl titanate and ammonium bicarbonate particles are stirred and mixed to obtain a mixed solution, and the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1 - 5:1; The substrate with the ZnO particle film and the above - mentioned mixed solution are evacuated in a vacuum dryer. After evacuation, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15 - 60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1 - 0.1:1; The vacuum dryer is placed in an oven for vapor deposition of the film. In the first step, it is heated at 20 - 50 °C for 2 - 12 h to form a titanium dioxide - based film tightly combined with zinc oxide nanoparticles at the bottom layer, and in the second step, it is heated at 60 - 100 °C for 0.5 - 6 h to form a porous surface structure of the titanium dioxide - zinc oxide nanocomposite film.
[0013] Furthermore, the steps of heating and annealing in the muffle furnace in the third step are as follows: Heat from room temperature at a heating rate of 1 - 5 °C / min, stay at 100 - 200 °C for 10 - 120 min for drying, then heat to 350 - 600 °C at a rate of 1 - 10 °C / min for annealing for 0.5 - 4 h, and take it out after natural cooling.
[0014] The beneficial effects of the present invention are as follows: The preparation process of the present invention is simple, has high repeatability, low cost, is green and environmentally friendly, and is suitable for large-scale production. After the film is prepared, the transparency of the glass is hardly affected, and the glass surface has excellent anti-fogging and self-cleaning properties. This method is applicable to the surfaces of various glass substrates, is beneficial to the application on glass materials and devices, and can play an important role in the exterior walls of buildings, the front windshield of cars, the displays of electronic products, the lighting panels of solar panels, the surface treatment of medical devices, anti-fogging glasses and masks in the medical industry and other fields. Brief Description of the Drawings
[0015] Figure 1 It is a schematic diagram of the preparation of titanium dioxide thin film by the gas-phase reaction of ammonium bicarbonate and tetrabutyl titanate; Figure 2 It is an SEM image of the gas-phase titanium dioxide thin film grown on ultra-clear glass in Example 1; Figure 3 It is an SEM image of the titanium dioxide - silicon dioxide thin film grown on ultra-clear glass in Example 2; Figure 4 It is an SEM image of the titanium dioxide - zinc oxide hybrid thin film grown on ultra-clear glass in Example 3; Figure 5 It is an SEM image of the gas-phase titanium dioxide thin film grown on FTO conductive glass in Example 4; Figure 6 It is the contact angle of the water droplet spreading on the gas-phase titanium dioxide thin film grown on ultra-clear glass in Example 1 after 1 s; Figure 7 It is the contact angle of the water droplet spreading on the gas-phase titanium dioxide - silicon dioxide hybrid thin film grown on ultra-clear glass in Example 2 after 1 s; Figure 8 It is the contact angle of the water droplet spreading on the gas-phase titanium dioxide - zinc oxide hybrid thin film grown on ultra-clear glass in Example 3 after 1 s; Figure 9 It is the contact angle of the water droplet spreading on the gas-phase titanium dioxide thin film grown on FTO conductive glass in Example 4 after 1 s; Figure 10 It is an image of the change of the contact angle of the gas-phase titanium dioxide thin film grown on ultra-clear glass in Example 1 with time; Figure 11 It is an image of the change of the contact angle of the gas-phase titanium dioxide - silicon dioxide hybrid thin film grown on ultra-clear glass in Example 2 with time; Figure 12 Images showing the change in contact angle over time of the vapor-grown titanium dioxide-zinc oxide hybrid thin film on the ultra-clear glass of Example 3; Figure 13 Images showing the change in contact angle over time of the vapor-grown titanium dioxide thin film on the FTO conductive glass of Example 4; Figure 14 Anti-fogging test of the vapor-grown titanium dioxide thin film on the ultra-clear glass of Example 1. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide thin film; Figure 15 Anti-fogging test of the vapor-grown titanium dioxide-silica hybrid thin film on the ultra-clear glass of Example 2. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide-silica hybrid thin film; Figure 16 Anti-fogging test of the vapor-grown titanium dioxide-zinc oxide hybrid thin film on the ultra-clear glass of Example 3. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide-zinc oxide hybrid thin film; Figure 17 Anti-fogging test of the vapor-grown titanium dioxide thin film on the FTO conductive glass of Example 4. Here, on the left is the FTO conductive glass, and on the right is the FTO conductive glass with the grown titanium dioxide thin film; Figure 18 Transparency test of the vapor-grown titanium dioxide thin film on the ultra-clear glass of Example 1. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide thin film; Figure 19 Transparency test of the vapor-grown titanium dioxide-silica hybrid thin film on the ultra-clear glass of Example 2. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide-silica hybrid thin film; Figure 20 Transparency test of the vapor-grown titanium dioxide-zinc oxide hybrid thin film on the ultra-clear glass of Example 3. Here, on the left is the ultra-clear glass, and on the right is the ultra-clear glass with the grown titanium dioxide-zinc oxide hybrid thin film; Figure 21 Transparency test of the vapor-grown titanium dioxide thin film on the FTO conductive glass of Example 4. Here, on the left is the FTO conductive glass, and on the right is the FTO conductive glass with the grown titanium dioxide thin film; Figure 22 Transmittance curve of the vapor-grown titanium dioxide thin film on the ultra-clear glass of Example 1; Figure 23 Transmittance curve of the vapor-grown titanium dioxide-silica hybrid thin film on the ultra-clear glass of Example 2; Figure 24 Transmittance curve of the vapor-grown titanium dioxide-zinc oxide hybrid thin film on the ultra-clear glass of Example 3; Figure 25 Transmittance curve of the gas-phase titanium dioxide thin film grown on the FTO conductive glass in Example 4; Figure 26 Self-cleaning test diagram of ultra-clear glass; Figure 27 Self-cleaning test diagram of the gas-phase titanium dioxide thin film grown on the ultra-clear glass in Example 1; Figure 28 Self-cleaning test diagram of the gas-phase titanium dioxide-silica hybrid thin film grown on the ultra-clear glass in Example 2; Figure 29 Self-cleaning test diagram of the gas-phase titanium dioxide-zinc oxide hybrid thin film grown on the ultra-clear glass in Example 3; Figure 30 Self-cleaning test diagram of FTO conductive glass; Figure 31 Self-cleaning test diagram of the gas-phase titanium dioxide thin film grown on the FTO conductive glass in Example 4; Figure 32 XRD diagram of the surface of the FTO conductive glass on which the titanium dioxide thin film is grown. Detailed implementation manners
[0016] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the specific embodiments of the present invention are described in detail, but not limited thereto. Unless otherwise specified, the raw materials used in the embodiments are all ordinary commercially available products; the methods used are all common methods in the art unless otherwise specified.
[0017] Sample testing method of the present invention: (1) Microscopic morphology testing: The microscopic morphology of the sample is observed and analyzed by using a scanning electron microscope.
[0018] (2) Crystallinity analysis: The crystallinity of the thin film is analyzed by XRD.
[0019] (3) Wettability testing: By using a contact angle measuring instrument, the static contact angle of water droplets on the surface of the glass sample on which the titanium dioxide thin film or hybrid thin film is grown, as well as the image of the change of the contact angle with time, are tested to study its wettability.
[0020] (4) Anti-fogging testing: The blank glass and the glass with a film layer are simultaneously placed above hot water at 95 °C or higher and left standing for one minute. Then, with an A4 paper as the background, the atomization situation on the glass surface is observed to judge its anti-fogging ability.
[0021] (5)Transparency test: Print the letters SXNU on A4 paper. Place the blank control glass and the glass with a titanium dioxide film layer or a hybrid film layer on the paper in sequence to qualitatively evaluate the transparency of the two glasses. Use an angular resolution spectrometer to measure the transmittance of the blank glass and the glass with the film layer, and quantitatively analyze the transparency of the samples.
[0022] (6)Self-cleaning test of glass: Sprinkle a certain amount of copper powder on the blank control glass and the glass with a titanium dioxide thin film or a titanium dioxide hybrid thin film respectively. Rinse with deionized water and take pictures before and after rinsing to compare the self-cleaning performance of the samples.
[0023] Example 1 1. Substrate cleaning: Use a glass cutter to cut ultra-clear glass with dimensions of 2 cm × 1.75 cm. Place the ultra-clear glass in a cleaning basket, ultrasonically clean it with acetone for 20 min to remove surface grease and organic substances; ultrasonically clean it with absolute ethanol for 20 min to further clean the surface. Ultrasonically clean it with deionized water for 20 min to remove ionic impurities.
[0024] Prepare a piranha solution by mixing concentrated sulfuric acid and hydrogen peroxide in a ratio of 7:3. Place the ultra-clear glass in a beaker containing the piranha solution and heat it to 150 °C on a hot plate for 3 h to deeply clean the glass surface.
[0025] After cooling to room temperature, take out the ultra-clear glass, rinse it 5 times with deionized water, and dry it with nitrogen to ensure the surface is dry and clean.
[0026] 2. Preparation of titanium dioxide nano-film: Take 9 mL of tetrabutyl titanate and mix it with 8.3627 g of ammonium bicarbonate so that the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 1:4. Place the mixed solution in a beaker. Place the ultra-clear glass sample and the above mixed solution in a 2 L vacuum desiccator and evacuate it at a negative pressure of -0.06 MPa for 15 min to remove air bubbles in the solution. Place the vacuum desiccator in an oven for vapor deposition of the film. In the first step, heat it at 30 °C for 4 h, and in the second step, heat it at 60 °C for 2 h.
[0027] After taking out the sample, place it in a muffle furnace for annealing. The heating rate is 2 °C / min. Hold at 110 °C for 30 min, then heat up to 500 °C and hold for 2 h, and then cool naturally to room temperature and take out.
[0028] Thus, a titanium dioxide nano-film is prepared on the surface of the ultra-clear glass.
[0029] 3. Testing and characterization: (1)SEM images: Through Figure 2 A and Figure 2 B, it can be observed that a dense film of titanium dioxide is formed on the glass surface, and the film-forming property is good.
[0030] (2) Infiltration test: By Figure 6 and Figure 10 , it is found that the contact angle of the water droplet on the sample surface is 3.8° after spreading for 1 s, and it can be known that the sample has good super-spreading performance.
[0031] (3) Anti-fogging test: By Figure 14 comparison, it is found that a large number of small water droplets are generated on the surface of the ultra-clear glass in the blank control group, and the transparency becomes poor, while the surface of the ultra-clear glass with a titanium dioxide thin film grown is a water film and still has high transparency, showing good anti-fogging effect.
[0032] (4) Transparency test: As Figure 18 shown, it is found that there is no obvious difference in transparency between the ultra-clear glass in the blank control group and the ultra-clear glass with a titanium dioxide thin film grown. And by Figure 22 it is found that the transmittance of the ultra-clear glass with a titanium dioxide thin film grown is only about 2% lower than that of the original ultra-clear glass, and the curves almost coincide, indicating that the ultra-clear glass with a titanium dioxide thin film grown has good transparency.
[0033] (5) Self-cleaning test: As Figure 26 shown, it is found that after the ultra-clear glass in the blank control group is washed with deionized water, there is still copper powder residue, while Figure 27 after the ultra-clear glass with a titanium dioxide thin film grown is washed with deionized water, there is no copper powder residue, and it can be concluded that the ultra-clear glass with a titanium dioxide thin film grown has good self-cleaning performance.
[0034] Example 2 1. Substrate cleaning: Use a glass cutter to cut ultra-clear glass of 2 cm × 1.75 cm. Put the ultra-clear glass into a cleaning basket, ultrasonicate it with acetone for 20 min to remove the grease and organic substances on the surface; ultrasonicate it with absolute ethanol for 20 min to further clean the surface. Ultrasonicate it with deionized water for 20 min to remove ionic impurities.
[0035] Prepare piranha solution by mixing concentrated sulfuric acid and hydrogen peroxide in a ratio of 7:3. Put the ultra-clear glass into a beaker containing piranha solution, and heat it to 150 °C with a hot stage for 3 h to deeply clean the glass surface.
[0036] After cooling to room temperature, take out the ultra-clear glass, rinse it 5 times with deionized water, and dry it with nitrogen to ensure that the surface is dry and clean.
[0037] 2. Preparation of titanium dioxide-silicon dioxide hybrid film: Take 9 mL of tetrabutyl titanate and mix it with 8.3627 g of ammonium bicarbonate. Place the mixed solution in Beaker 1. Separately, take 1.18 mL of tetraethyl orthosilicate solution and place it in Beaker 2. The molar ratio of tetrabutyl titanate to ammonium bicarbonate is 1:4, and the molar ratio of tetraethyl orthosilicate to tetrabutyl titanate is 1:5. Place the ultra-white glass sample and the above solutions in a 2-L vacuum dryer, and evacuate for 15 min under a negative pressure of -0.06 MPa to remove the bubbles in the solution. Subsequently, place the dryer in an oven and heat it to carry out the vapor deposition reaction. In the first step, heat it to 30 °C and heat for 4 h. In the second step, heat it to 60 °C and heat for 2 h.
[0038] After taking out the sample, put it into a muffle furnace for annealing. The heating rate is 2 °C / min. Stay at 110 °C for 30 min, then heat up to 500 °C and stay for 2 h, and then cool it naturally to room temperature and take it out.
[0039] Thus, a titanium dioxide-silicon dioxide nanocomposite film was prepared on the surface of the ultra-white glass.
[0040] 3. Testing and characterization: (1) SEM image: Through Figure 3 A and Figure 3 B, it can be observed that a dense film of titanium dioxide has formed on the glass surface, and the film-forming property is good.
[0041] (2) Wettability test: Through Figure 7 and Figure 11 , it was found that the contact angle of the water droplet on the surface of the sample was 3.1° after spreading for 1 s, indicating that the sample has excellent super-spreading performance.
[0042] (3) Anti-fogging test: Through Figure 15 Comparison found that a large number of small water droplets formed on the surface of the ultra-white glass in the blank control group, and the transparency deteriorated. While the surface of the ultra-white glass with the titanium dioxide-silicon dioxide hybrid film was a water film and still had high transparency, showing good anti-fogging effect.
[0043] (4) Transparency test: As Figure 19 shown, no obvious difference in transparency was observed between the ultra-white glass in the blank control group and the ultra-white glass with the titanium dioxide-silicon dioxide hybrid film. And through Figure 23 it was found that the transmittance of the ultra-white glass with the titanium dioxide-silicon dioxide hybrid film only decreased by about 2% compared with the original ultra-white glass, and the curves almost coincided, indicating that the ultra-white glass with the titanium dioxide-silicon dioxide hybrid film has good transparency.
[0044] (5) Self-cleaning test: As Figure 26 shown, after the ultra-white glass in the blank control group was rinsed with deionized water, there was still copper powder residue, while Figure 28After the super-white glass with the grown titanium dioxide-silica hybrid film is washed with deionized water and no copper powder residue is left, it can be concluded that the super-white glass with the titanium dioxide-silica hybrid film has good self-cleaning performance.
[0045] Example 3 1. Substrate cleaning: Use a glass cutter to cut super-white glass with dimensions of 2 cm × 1.75 cm. Place the super-white glass in a cleaning basket, ultrasonically clean it with acetone for 20 min to remove grease and organic substances on the surface; ultrasonically clean it with absolute ethanol for 20 min to further clean the surface. Ultrasonically clean it with deionized water for 20 min to remove ionic impurities.
[0046] Prepare piranha solution by mixing concentrated sulfuric acid and hydrogen peroxide in a ratio of 7:3. Place the super-white glass in a beaker containing the piranha solution, and heat it to 150 °C on a hot stage for 3 h to deeply clean the glass surface.
[0047] After cooling to room temperature, take out the super-white glass, rinse it 5 times with deionized water, and dry it with nitrogen to ensure the surface is dry and clean.
[0048] 2. Preparation of titanium dioxide and zinc oxide hybrid film: (1) Growth of ZnO particle film Prepare an ethanol solution of zinc acetate with a concentration of 0.005 mol / L, and use a dip coater to dip and coat the glass sample. Perform 5 dips. The dipping time for each time is 60 s, the interval is 60 s, and the dipping speed is 100 mm / min. Then perform annealing crystallization, with an annealing temperature of 230 °C and a time of 30 min.
[0049] (2) Preparation of titanium dioxide nanometer film Take 9 mL of tetrabutyl titanate and mix it with 8.3627 g of ammonium bicarbonate so that the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 1:4, and place the mixed solution in a beaker. Place the super-white glass sample and the above mixed solution in a 2 L vacuum dryer, and evacuate it under a negative pressure of -0.06 MPa for 15 min to remove air bubbles in the solution. Subsequently, place the dryer in an oven and heat it to carry out a vapor deposition reaction. In the first step, heat it to 30 °C and heat for 4 h, and in the second step, heat it to 60 °C and heat for 2 h.
[0050] After taking out the sample, put it into a muffle furnace for annealing. The heating rate is 2 °C / min, stay at 110 °C for 30 min, then heat up to 500 °C, stay for 2 h, and take it out after natural cooling to room temperature.
[0051] Thus, a titanium dioxide-zinc oxide nanometer hybrid film is prepared on the surface of the super-white glass.
[0052] 3. Testing and characterization: (1) SEM image: ThroughFigure 4 A and Figure 4 B can observe that a dense film of titanium dioxide is formed on the glass surface, and the film-forming property is good.
[0053] (2)Wettability test: By Figure 8 and Figure 12 , it is found that the contact angle of the water droplet is 4.0° after spreading on the surface of Yangping for 1 s, and it can be known that the sample has good super-spreading performance.
[0054] (3)Anti-fogging test: By Figure 16 comparison, it is found that a large number of small water droplets are generated on the surface of the ultra-clear glass in the blank control group, and the transparency becomes poor, while the surface of the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film is a water film and still has high transparency, showing good anti-fogging effect.
[0055] (4)Transparency test: As Figure 20 shown, it is found that there is no obvious difference in transparency between the ultra-clear glass in the blank control group and the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film. And by Figure 24 it is found that the transmittance of the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film is only about 5% lower than that of the original ultra-clear glass, indicating that the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film has good transparency.
[0056] (5)Self-cleaning test: By Figure 26 shown, after the ultra-clear glass in the blank control group is flushed with deionized water, there is still copper powder residue, while Figure 29 after the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film is flushed with deionized water, there is no copper powder residue, and it can be concluded that the ultra-clear glass with a titanium dioxide-zinc oxide hybrid film has good self-cleaning performance.
[0057] Example 4 1. Substrate cleaning: Use a glass cutter to cut FTO conductive glass with a size of 2 cm×1.75 cm. Put the ultra-clear glass into the cleaning basket, and use acetone for ultrasonic cleaning for 20 min to remove the grease and organic substances on the surface; use absolute ethanol for ultrasonic cleaning for 20 min to further clean the surface. Use deionized water for ultrasonic cleaning for 20 min to remove ionic impurities.
[0058] Prepare piranha solution by mixing concentrated sulfuric acid and hydrogen peroxide in a ratio of 7:3. Put the FTO conductive glass into a beaker containing piranha solution, and heat it to 150 °C with a hot plate for 3 h to deeply clean the glass surface.
[0059] After cooling to room temperature, take out the FTO conductive glass, rinse it 5 times with deionized water, and dry it with nitrogen to ensure that the surface is dry and clean.
[0060] 2. Preparation of Titanium Dioxide Nanofilm: Take 9 mL of tetrabutyl titanate and mix it with 8.3627 g of ammonium bicarbonate so that the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 1:4. The mixed solution is placed in a beaker. Place the FTO conductive glass sample and the above mixed solution in a 2 L vacuum dryer, and evacuate for 15 min under a negative pressure of -0.06 MPa to remove the bubbles in the solution. Place the vacuum dryer in an oven for vapor deposition of the film. In the first step, heat to 30 °C and heat for 4 h. In the second step, heat to 60 °C and heat for 2 h.
[0061] After taking out the sample, put it into a muffle furnace for annealing. The heating rate is 2 °C / min. Stay at 110 °C for 30 min, then heat to 500 °C and stay for 2 h, and then cool naturally to room temperature and take it out.
[0062] Thus, a titanium dioxide nanofilm was prepared on the surface of the FTO conductive glass.
[0063] 3. Testing and Characterization: (1) SEM Image: Through Figure 5 A and Figure 5 B, it can be observed that a dense film of titanium dioxide is formed on the surface of the FTO glass, and it combines well with the original FTO film layer.
[0064] (2) Wettability Test: Through Figure 9 and Figure 13 , it is found that the contact angle of the water droplet is 3.2° after spreading on the surface of the FTO glass for 1 s, indicating that the sample has good super-spreading performance.
[0065] (3) Anti-fogging Test: Through Figure 17 Comparison reveals that a large number of small water droplets are formed on the surface of the FTO conductive glass in the blank control group, and the transparency deteriorates. While the surface of the FTO conductive glass with the titanium dioxide film grown is a water film and still has high transparency, showing good anti-fogging effect.
[0066] (4) Transparency Test: As Figure 21 shown, it is found that there is no obvious difference in transparency between the FTO conductive glass in the blank control group and the ultra-white glass with the titanium dioxide film grown on the FTO conductive glass. And through Figure 25 it is found that the transmittance of the FTO conductive glass with the titanium dioxide film grown is only about 1% lower than that of the original ultra-white glass, and the curves almost coincide, indicating that the FTO conductive glass with the titanium dioxide film grown has good transparency.
[0067] (5) Self-cleaning Test: Through Figure 30 shown, after the FTO conductive glass in the blank control group is flushed with deionized water, there is still copper powder residue, while Figure 31After the FTO conductive glass with the grown titanium dioxide thin film is rinsed with deionized water, there is no residual copper powder, indicating that the FTO conductive glass with the grown titanium dioxide thin film has excellent self-cleaning performance.
[0068] (6) Composition test: Conduct XRD test on the composition of the FTO glass with the grown titanium dioxide thin film. As Figure 32 shown, it is found that the main component of the thin film is TiO2.
[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention does not depart from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the protection scope of the claims of the present invention.
Claims
1. A method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature chemical vapor deposition, characterized in that: It includes the following steps: The first step is to clean the substrate; The second step is the gas-phase preparation of the titanium dioxide film and its hybrid film; In the third step, after the sample prepared in the second step is cooled, it is heated and annealed in a muffle furnace.
2. The method for preparing titanium dioxide and its hybrid hydrophilic film by low-temperature vapor deposition according to claim 1, characterized in that: The substrate described in the first step includes a glass substrate.
3. The method for preparing titanium dioxide and its hybrid hydrophilic film by low-temperature chemical vapor deposition according to claim 2, characterized in that: The glass substrate includes any one of ultra-white glass, quartz glass, soda-lime glass, and conductive glass.
4. A method for preparing titanium dioxide and its hybrid hydrophilic film by low-temperature vapor deposition according to claim 2, characterized in that: The area of the glass substrate is 1-200 cm 2 .
5. A method for preparing titanium dioxide and its hybrid hydrophilic film by low-temperature vapor deposition according to claim 1, characterized in that: The substrate cleaning step in the first step is as follows: After cutting the substrate, it is successively placed in acetone, absolute ethanol, and deionized water for ultrasonic cleaning for 10 - 30 min each; the power of the ultrasonic cleaning is 50 - 150 W; Prepare a piranha solution by mixing concentrated sulfuric acid and hydrogen peroxide in a volume ratio of 7:
3. Place the dried substrate in the piranha solution, heat it to 90 - 180 °C, heat for 1 - 6 h, deeply clean the surface of the substrate, take out the substrate after cooling to room temperature, rinse it with deionized water more than 5 times, and dry it.
6. A method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature vapor deposition according to claim 1, characterized in that: The gas-phase preparation step of the titanium dioxide film in the second step is as follows: Stir and mix tetrabutyl titanate and ammonium bicarbonate particles to obtain a mixed solution, and the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1 - 5:1; Vacuum the substrate and the mixed solution in a vacuum dryer. After vacuuming, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15 - 60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1 - 0.1:1; Place the vacuum dryer in an oven for gas-phase deposition of the film. In the first step, heat it at 20 - 50 °C for 2 - 12 h to form a dense titanium dioxide-based film at the bottom layer, and in the second step, heat it at 60 - 100 °C for 0.5 - 6 h to form a porous structure on the surface layer of the titanium dioxide nanometer film.
7. A method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature vapor deposition according to claim 1, characterized in that: The titanium dioxide hybrid film described in the second step includes a titanium dioxide and silica hybrid film or a titanium dioxide and zinc oxide hybrid film.
8. A method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature chemical vapor deposition according to claim 7, characterized in that: The gas-phase preparation step of the titanium dioxide and silica hybrid film is as follows: Stir and mix tetrabutyl titanate and ammonium bicarbonate particles to obtain a tetrabutyl titanate and ammonium bicarbonate mixed solution, and place it in beaker one. Separately take tetraethyl orthosilicate solution and place it in beaker two. The molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1 - 5:1, and the molar ratio of tetraethyl orthosilicate to tetrabutyl titanate is 1:1 - 1:10; Vacuum the substrate, the tetrabutyl titanate and ammonium bicarbonate mixed solution, and the tetraethyl orthosilicate solution in a vacuum dryer. After vacuuming, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15 - 60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1 - 0.1:1; Place the vacuum dryer in an oven for gas-phase deposition of the film. In the first step, heat it at 20 - 50 °C for 2 - 12 h to form a dense titanium dioxide-silica-based film at the bottom layer, and in the second step, heat it at 60 - 100 °C for 0.5 - 6 h to form a porous structure on the surface layer of the titanium dioxide-silica nanometer hybrid film.
9. A method for preparing titanium dioxide and its hybrid hydrophilic thin films by low-temperature chemical vapor deposition according to claim 7, characterized in that: The gas-phase preparation step of the titanium dioxide and zinc oxide hybrid film is as follows: ZnO particle film growth Prepare a zinc acetate ethanol solution with a concentration of 0.001 - 0.01 mol / L, and use a dip coater to dip and coat the substrate. The dipping time for each time is 60 - 90 s, the interval is 60 - 120 s, and the dipping speed is 50 - 150 mm / min. Then, perform annealing crystallization at an annealing temperature of 200 - 450 °C for 30 - 60 min; Gas-phase preparation of titanium dioxide film layer Stir and mix tetrabutyl titanate and ammonium bicarbonate particles to obtain a mixed solution, and the molar ratio of tetrabutyl titanate to ammonium bicarbonate is 0.0625:1 - 5:1; Put the substrate with zinc oxide particle film and the above mixed solution into a vacuum dryer to evacuate. After evacuation, the negative pressure in the dryer is -0.05 MPa to -0.09 MPa, and the duration is 15 - 60 min to remove the bubbles in the mixed solution; the volume ratio of tetrabutyl titanate to the space volume of the vacuum dryer is 0.0005:1 - 0.1:1; Put the vacuum dryer into an oven for gas-phase deposition of the film. In the first step, heat at 20 - 50 °C for 2 - 12 h to form a titanium dioxide-based film with a tightly bonded bottom layer to zinc oxide nanoparticles. In the second step, heat at 60 - 100 °C for 0.5 - 6 h to form a porous structure on the surface layer of the titanium dioxide-zinc oxide nanohybrid film.
10. A method for preparing titanium dioxide and its hybrid hydrophilic thin film by low-temperature chemical vapor deposition according to claim 1, characterized in that: The steps of heating and annealing in the muffle furnace in the third step are as follows: Heat from room temperature with a heating rate of 1 - 5 °C / min, stay at 100 - 200 °C for 10 - 120 min for drying, then heat to 350 - 600 °C at a rate of 1 - 10 °C / min for annealing for 0.5 - 4 h, and take it out after natural cooling.