Anti-reflection hydrophobic wear-resistant composite film and preparation method thereof
By alternately depositing aluminum oxide/titanium oxide layers on a glass substrate and combining hot water treatment and low surface energy modification, the problem of insufficient film wear resistance was solved, and a composite film with high transmittance, hydrophobicity and wear resistance was achieved, which is suitable for optical lenses, solar cells and architectural glass.
Patent Information
- Application Number
- CN202510817592.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-18
- Publication Date
- 2025-09-19
AI Technical Summary
While existing films achieve anti-reflection and hydrophobic properties, they lack wear resistance, resulting in a short lifespan.
An atomic layer deposition system is used to alternately deposit aluminum oxide/titanium oxide layers on the surface of a glass substrate, combined with high-temperature hot water treatment and low surface energy modification to form an anti-reflective, hydrophobic, and wear-resistant composite film.
It achieves high transmittance and hydrophobicity, while significantly improving the wear resistance of the film and extending its service life.
Smart Images
Figure CN120664789A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of new materials, and in particular to a permeability-enhancing, hydrophobic, and wear-resistant composite film and a preparation method thereof. Background Art
[0002] Anti-reflection films can minimize the loss of light beams on the surface or interface of components. This characteristic has led to their widespread application in optical lenses, displays, sensors, laser technology, optoelectronics technology, optical communication technology, optical display technology, and optical storage technology. The thickness of this film is directly related to the wavelength of the target anti-reflection band. To achieve anti-reflection in the visible light range, the thickness of the film should be between 100-200nm. Hydrophobic films are also widely used in fields such as anti-fouling and water-resistant buildings, buoyancy enhancement, corrosion resistance, and microfluidic control. This is due to the self-cleaning, stain-resistant, waterproof, and anti-icing properties of hydrophobic films.
[0003] Generally speaking, a film only needs to have either antireflection or hydrophobic properties to meet usage requirements. However, the rapid development of solar cells in recent years has put forward new requirements for films: they must possess both antireflection and hydrophobic properties. This requirement brings with it a new problem: films with both antireflection and hydrophobic properties have a short lifespan. This is because achieving hydrophobicity requires a hydrophobic surface microstructure, and achieving antireflection properties in the visible light range results in a film thickness of less than 200nm. This surface microstructure reduces the wear resistance of the film, thereby affecting its lifespan. This phenomenon becomes more pronounced when the film scale reaches the nanometer level, resulting in a sharp decline in wear resistance. Summary of the Invention
[0004] In view of the above situation, the present invention provides a transmissive, hydrophobic, and wear-resistant composite film and a preparation method thereof, so as to increase the life of the film while achieving transmissive and hydrophobic properties.
[0005] One aspect of the present invention provides a method for preparing a transmissive, hydrophobic, and wear-resistant composite film, comprising:
[0006] Step S1, atomic layer deposition system coating;
[0007] Step S2, hot water treatment;
[0008] Step S3, low surface energy modification;
[0009] Wherein, step S1 specifically includes:
[0010] Step S1.1, substrate pretreatment: Cut the glass slide into glass of a predetermined size. Then, ultrasonically clean the glass in ethanol, acetone, distilled water, and ethanol, respectively. Finally, blow dry the cleaned glass and activate it in a UV-ozone cleaning machine.
[0011] Step S1.2, coating: Place the glass into the reaction chamber of the atomic layer deposition system. Use a mechanical pump to evacuate the ALD system to a pressure of 40 Pa. Subsequently, introduce argon gas until the chamber pressure reaches 60 Pa. The oxygen source, aluminum source, and titanium source used in the atomic layer deposition system are deionized water, trimethylaluminum, and titanium tetraisopropoxide, respectively.
[0012] Step S1.3: Stop the deposition process. After reaching the preset number of cycles, close the raw material tanks for the oxygen, aluminum, and titanium sources. Use a mechanical pump to evacuate the residual gas in the cavity, then introduce argon gas to atmospheric pressure. Remove the sample to obtain a thin film of glass.
[0013] Step S2 specifically includes: placing the glass film obtained in step S1.3 into a polytetrafluoroethylene glass rack, and placing the glass rack into hot water, so that the glass is completely immersed in the hot water;
[0014] Step S3 specifically includes:
[0015] Step S3.1, fixing: Use high-temperature tape to adhere the glass treated in step S2 to the top of the culture dish lid. Wrap the culture dish with aluminum foil. Then, drip tridecafluorooctyltriethoxysilane into the culture dish. Wrap the outermost layer of the culture dish with plastic wrap.
[0016] Step S3.2, modification, placing the culture dish wrapped in plastic wrap in an oven for heating;
[0017] Step S3.3, stop the modification, and after the heating is finished, remove the plastic wrap and open the lid and keep warm for a preset time to remove the unreacted tridecafluorooctyltriethoxysilane in the culture dish, and finally obtain an anti-reflective, hydrophobic, and wear-resistant composite film.
[0018] Preferably, step S1.1 is specifically as follows:
[0019] For substrate pretreatment, the glass slides were cut into glass of preset size, and then the glass was ultrasonically cleaned in ethanol, acetone, distilled water and ethanol in sequence for 30 minutes using a cleaning machine with a cleaning power of 100W and a cleaning temperature of room temperature. Finally, the cleaned glass pieces were blown dry and placed in a UV ozone cleaning machine for irradiation activation for 30 minutes.
[0020] Preferably, step S1.2 is specifically as follows:
[0021] Coating, the glass is placed in the reaction chamber of the atomic layer deposition system, and the ALD system is evacuated to a pressure of 40Pa using a mechanical pump. Subsequently, argon gas is introduced until the pressure in the chamber is 60Pa. The oxygen source, aluminum source and titanium source used in the atomic layer deposition system are deionized water, trimethylaluminum and titanium tetraisopropoxide, respectively. The temperature of the raw material tanks of the oxygen source and the aluminum source is maintained at room temperature, the temperature of the raw material tank of the titanium source is 80°C, the reaction chamber temperature is set to 150°C, the feed pipe temperature is set to 150°C, and the tail gas pipe is set to 80°C; the purge gas and the carrier gas are both argon with a purity of 99.999% and a flow rate of 50sccm. The cycle process includes 1 aluminum oxide cycle and 2 titanium oxide cycles, wherein the oxygen source pulse time is 0.1s, the exposure time is 8s, and the purge time is 25s, the aluminum source pulse time is 0.02s, the exposure time is 8s, and the purge time is 25s, the titanium source pulse time is 0.05s, the exposure time is 8s, and the purge time is 25s, and the number of cycles is 133 times.
[0022] Preferably, step S2 is specifically as follows:
[0023] Place the glass with the film obtained in step S1.3 into a polytetrafluoroethylene glass rack, and place the glass rack with the glass into hot water. The glass needs to be completely immersed in the hot water. The water used is deionized water with a temperature of at least 95°C and the soaking time is at least 10 hours.
[0024] Preferably, step S3.2 is specifically as follows:
[0025] Modification: The culture dish wrapped in plastic wrap was placed in an oven and heated at 130 °C for 2 h.
[0026] Preferably, step S3.3 is specifically as follows:
[0027] After the modification and heating are stopped, the plastic wrap is removed and the lid is opened and kept warm for another 1 hour to remove the unreacted tridecafluorooctyltriethoxysilane in the culture dish, and finally an anti-reflective, hydrophobic and wear-resistant composite film is obtained.
[0028] Another aspect of the present invention provides an anti-reflective, hydrophobic, and wear-resistant composite film, which is prepared by the above method.
[0029] The present invention utilizes an atomic layer deposition system to alternately deposit aluminum oxide / titanium oxide layers on the surface of a glass substrate to obtain a composite film. High-purity argon is used as a protective gas and a power gas. The film is then subjected to a long-term high-temperature hot water treatment, with the treatment temperature being at least 95°C and the treatment time being at least 10 hours. The glass with the composite film, which has been soaked in hot water, is then subjected to a vapor deposition method to perform low-surface energy modification. The composite film obtained by the present invention has good uniformity and density, and because the film is bonded to the substrate through a chemical bond, the bonding strength is good and the film is not easy to fall off. While maintaining a high maximum transmittance (>94%) and hydrophobicity (water contact angle>130°), the composite film significantly improves wear resistance (basically no loss of performance after 20 cycles of wear), and is suitable for optical lenses, solar cells, architectural glass and other fields. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is a surface scanning electron microscope image of the composite film prepared in Example 1;
[0031] Figure 2 This is a comparison chart of the transmittance of the composite film and the worn composite film prepared in Example 1, the aluminum oxide film and the worn aluminum oxide film prepared in Comparative Example 1, the titanium oxide film and the worn titanium oxide film prepared in Comparative Example 2, and ordinary glass;
[0032] Figure 3 These are the water contact angle diagrams of the composite film prepared in Example 1, the worn composite film, the aluminum oxide film prepared in Comparative Example 1, the worn aluminum oxide film, the titanium oxide film prepared in Comparative Example 2, and the worn titanium oxide film, and ordinary glass. DETAILED DESCRIPTION
[0033] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to various embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.
[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.
[0035] Embodiment 1 of the present invention provides a method for preparing a transmissive, hydrophobic, and wear-resistant composite film, comprising:
[0036] Step S1, atomic layer deposition system coating;
[0037] Step S2, hot water treatment;
[0038] Step S3: low surface energy modification.
[0039] Wherein, step S1 specifically includes:
[0040] Step S1.1: Substrate pretreatment: Cut the glass slide into glass pieces measuring 25 mm × 25 mm × 10 mm. Then, ultrasonically clean the glass in ethanol (analytical grade), acetone (analytical grade), distilled water, and ethanol (analytical grade) for 30 minutes, in that order. The cleaning power was set to 100 W at room temperature. Cleaning with ethanol and acetone effectively removed impurities and grease from the sample surface. Acetone is slightly toxic, so it should be cleaned with pure water. Finally, the cleaned glass slide was blown dry and activated in a UV-ozone cleaning machine for 30 minutes.
[0041] Step S1.2, coating, place the glass in the reaction chamber of the ALD (atomic layer deposition system), use a mechanical pump to evacuate the ALD system to a pressure of 40Pa, then introduce argon gas to a chamber pressure of 60Pa. The ALD process for synthesizing oxides is essentially a chemical synthesis. The metal in the oxide comes from a gaseous metal organic salt compound, and the oxygen in the oxide comes from gaseous water. These two gaseous substances occupy the reaction chamber for a period of time respectively, so that their substances are combined with the substrate surface. In this process, the hydroxyl groups on the substrate surface first combine with the metal ions, and then the metal ions combine with the oxygen ions, and these combinations will form covalent bonds. The oxygen source, aluminum source and titanium source used are deionized water, trimethylaluminum (TMA) and titanium tetraisopropoxide, respectively. The temperature of the raw material tanks of the oxygen source and aluminum source is maintained at room temperature, the temperature of the raw material tank of the titanium source is 80°C, the reaction chamber temperature is set to 150°C, the feed pipe temperature is set to 150°C (the reaction chamber temperature is consistent with the feed pipe temperature), and the tail gas pipe is set to 80°C; high-purity argon (Ar, 99.999%) is used as the purge gas and the carrier gas, with a flow rate of 50sccm. The cycle process includes 1 aluminum oxide cycle and 2 titanium oxide cycles, in which the oxygen source pulse time is 0.1s, the exposure time is 8s, and the purge time is 25s; the aluminum source pulse time is 0.02s, the exposure time is 8s, and the purge time is 25s; the titanium source pulse time is 0.05s, the exposure time is 8s, and the purge time is 25s. The number of cycles is 133 times;
[0042] Step S1.3, stop the deposition. After reaching the preset number of cycles, close the raw material tanks of the oxygen source, aluminum source and titanium source, use a mechanical pump to evacuate the residual gas in the cavity, and then introduce argon gas into the machine to atmospheric pressure. Take out the sample to obtain glass coated with a thin film with a thickness of 35nm.
[0043] Step S2 specifically includes placing the glass with the film obtained in step S1.3 into a Teflon glass rack. This rack allows the glass to stand upright, maximizing the area of the film exposed to the hot water. The rack containing the glass is placed in hot water, ensuring that the glass is completely immersed. Deionized water should be used, at a temperature of at least 95°C, and the immersion time should be at least 10 hours.
[0044] Step S3 specifically includes:
[0045] Step S3.1: Secure the glass treated in step S2 to the top of the culture dish using high-temperature tape. Tape the four corners of the glass. Wrap the culture dish with aluminum foil. Then, add 25 μL of tridecafluorooctyltriethoxysilane (POTS) to the dish. The surface of the glass with the film should face the POTS. Wrap the outermost layer of the dish with plastic wrap to prevent the POTS from evaporating.
[0046] Step S3.2, modification: Place the culture dish wrapped in plastic wrap in an oven and heat it at 130°C for 2 hours;
[0047] Step S3.3, stop the modification, and after the heating is finished, remove the plastic wrap and open the lid and keep warm for another 1 hour to remove the unreacted POTS in the culture dish, and finally obtain an anti-reflective, hydrophobic, and wear-resistant composite film.
[0048] Comparative Example 1
[0049] The only difference from Example 1 is that during the coating process of step S1 , titanium oxide is not added and the number of cycles is 300, that is, the film is a single-component film containing only aluminum oxide.
[0050] Comparative Example 2
[0051] The only difference from Example 1 is that during the coating process of step S1 , aluminum oxide is not added and the number of cycles is 300, that is, the film is a single-component film containing only titanium oxide.
[0052] Test Example 1
[0053] The surface scanning electron microscope image of the composite film prepared in Test Example 1 is as follows: Figure 1 shown.
[0054] The transmittance comparison chart of the composite film prepared in Example 1, the worn composite film, the aluminum oxide film prepared in Comparative Example 1, the worn aluminum oxide film, the titanium oxide film prepared in Comparative Example 2, the worn titanium oxide film, and ordinary glass is shown in the following figure. Figure 2The abrasion method is to use a brush dipped in water to scrub the glass surface, scrubbing 10 times as one cycle, and perform 20 cycles.
[0055] The contact angles of the composite film and the worn composite film prepared in Example 1, the aluminum oxide film and the worn aluminum oxide film prepared in Comparative Example 1, and the titanium oxide film and the worn titanium oxide film prepared in Comparative Example 2 with ordinary glass were tested. The results are as follows: Figure 3 The abrasion method is to use a brush dipped in water to scrub the glass surface, scrubbing 10 times as one cycle, and perform 20 cycles.
[0056] from Figure 2 and Figure 3 It can be seen that the maximum transmittance of the composite film prepared in Example 1 is 94.58% and the water contact angle is 132°, and the maximum transmittance of the worn composite film is 94.32% and the water contact angle is 131°. This shows that the composite film prepared in Example 1 can maintain a high maximum transmittance (>94%) and hydrophobicity (water contact angle>130°) before and after wear, and significantly improves the wear resistance (there is basically no loss in performance after 20 cycles of wear).
[0057] The aluminum oxide film prepared in Comparative Example 1 had a maximum transmittance of 97.34% and a water contact angle of 152°. The abraded aluminum oxide film had a maximum transmittance of 89.37% and a water contact angle of 56°. This indicates that without the addition of titanium oxide, while aluminum oxide exhibits excellent anti-reflection and hydrophobic properties, it exhibits extremely poor wear resistance. Compared to Comparative Example 1, the covalent bonds formed during the ALD process in this embodiment provide the film's fundamental wear resistance, while the addition of titanium oxide protects the aluminum oxide's structure. Ultimately, the anti-reflection and hydrophobic composite film of the present invention possesses even better wear resistance.
[0058] The titanium oxide film prepared in Comparative Example 2 had a maximum transmittance of 88.15% and a water contact angle of 45°. This indicates that the absence of aluminum oxide renders the surface structure ineffective in enhancing transmittance and renders it hydrophilic. The worn titanium oxide film had a maximum transmittance of 87.64% and a water contact angle of 41°, demonstrating its wear resistance. While titanium oxide itself exhibits excellent wear resistance, its structure and refractive index make it lack both anti-reflection and hydrophobic properties.
[0059] In summary, an atomic layer deposition system is used to alternately deposit aluminum oxide / titanium oxide layers on the surface of a glass substrate to obtain a composite film. High-purity argon is used as a protective gas and a power gas. The film is then subjected to a long-term high-temperature hot water treatment, with a treatment temperature of at least 95°C and a treatment time of at least 10 hours. The glass with the composite film that has been soaked in hot water is then subjected to low surface energy modification using an evaporation method. The composite film obtained by the present invention has good uniformity and density, and because the bonding between the film and the substrate is achieved through chemical bonds, the bonding force is good and the film is not easy to fall off. While maintaining a high maximum transmittance (>94%) and hydrophobicity (water contact angle>130°), the composite film significantly improves wear resistance (basically no loss of performance after 20 cycles of wear), and can be applied to optical lenses, solar cells, architectural glass and other fields.
[0060] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.
Claims
1. A method for preparing a transparent, hydrophobic, and wear-resistant composite film, characterized in that: include: Step S1, atomic layer deposition system coating; Step S2, hot water treatment; Step S3, low surface energy modification; Wherein, step S1 specifically includes: Step S1.1, substrate pretreatment: Cut the glass slide into glass of a predetermined size. Then, ultrasonically clean the glass in ethanol, acetone, distilled water, and ethanol, respectively. Finally, blow dry the cleaned glass and activate it in a UV-ozone cleaning machine. Step S1.2, coating: Place the glass into the reaction chamber of the atomic layer deposition system. Use a mechanical pump to evacuate the ALD system to a pressure of 40 Pa. Subsequently, introduce argon gas until the chamber pressure reaches 60 Pa. The oxygen source, aluminum source, and titanium source used in the atomic layer deposition system are deionized water, trimethylaluminum, and titanium tetraisopropoxide, respectively. Step S1.3: Stop the deposition process. After reaching the preset number of cycles, close the raw material tanks for the oxygen, aluminum, and titanium sources. Use a mechanical pump to evacuate the residual gas in the cavity, then introduce argon gas to atmospheric pressure. Remove the sample to obtain a thin film of glass. Step S2 specifically includes: placing the glass film obtained in step S1.3 into a polytetrafluoroethylene glass rack, and placing the glass rack into hot water, so that the glass is completely immersed in the hot water; Step S3 specifically includes: Step S3.1, fixing: Use high-temperature tape to adhere the glass treated in step S2 to the top of the culture dish lid. Wrap the culture dish with aluminum foil. Then, drip tridecafluorooctyltriethoxysilane into the culture dish. Wrap the outermost layer of the culture dish with plastic wrap. Step S3.2, modification, placing the culture dish wrapped in plastic wrap in an oven for heating; Step S3.3, stop the modification, and after the heating is finished, remove the plastic wrap and open the lid and keep warm for a preset time to remove the unreacted tridecafluorooctyltriethoxysilane in the culture dish, and finally obtain an anti-reflective, hydrophobic, and wear-resistant composite film.
2. The method for preparing the anti-reflective, hydrophobic, and wear-resistant composite film according to claim 1, wherein: Step S1.1 is specifically as follows: For substrate pretreatment, the glass slides were cut into glass of preset size, and then the glass was ultrasonically cleaned in ethanol, acetone, distilled water and ethanol in sequence for 30 minutes using a cleaning machine with a cleaning power of 100W and a cleaning temperature of room temperature. Finally, the cleaned glass pieces were blown dry and placed in a UV ozone cleaning machine for irradiation activation for 30 minutes.
3. The method for preparing the anti-reflective, hydrophobic, and wear-resistant composite film according to claim 1, wherein: Step S1.2 is specifically as follows: Coating, the glass is placed in the reaction chamber of the atomic layer deposition system, and the ALD system is evacuated to a pressure of 40Pa using a mechanical pump. Subsequently, argon gas is introduced until the pressure in the chamber is 60Pa. The oxygen source, aluminum source and titanium source used in the atomic layer deposition system are deionized water, trimethylaluminum and titanium tetraisopropoxide, respectively. The temperature of the raw material tanks of the oxygen source and the aluminum source is maintained at room temperature, the temperature of the raw material tank of the titanium source is 80°C, the reaction chamber temperature is set to 150°C, the feed pipe temperature is set to 150°C, and the tail gas pipe is set to 80°C; the purge gas and the carrier gas are both argon with a purity of 99.999% and a flow rate of 50sccm. The cycle process includes 1 aluminum oxide cycle and 2 titanium oxide cycles, wherein the oxygen source pulse time is 0.1s, the exposure time is 8s, and the purge time is 25s, the aluminum source pulse time is 0.02s, the exposure time is 8s, and the purge time is 25s, the titanium source pulse time is 0.05s, the exposure time is 8s, and the purge time is 25s, and the number of cycles is 133 times.
4. The method for preparing the anti-reflective, hydrophobic, and wear-resistant composite film according to claim 1, wherein: Step S2 is specifically as follows: Place the glass with the film obtained in step S1.3 into a polytetrafluoroethylene glass rack, and place the glass rack with the glass into hot water. The glass needs to be completely immersed in the hot water. The water used is deionized water with a temperature of at least 95°C and the soaking time is at least 10 hours.
5. The method for preparing the anti-reflective, hydrophobic, and wear-resistant composite film according to claim 1, wherein: Step S3.2 is specifically as follows: Modification: The culture dish wrapped in plastic wrap was placed in an oven and heated at 130 °C for 2 h.
6. The method for preparing the anti-reflective, hydrophobic, and wear-resistant composite film according to claim 1, wherein: Step S3.3 is specifically as follows: After the modification and heating are stopped, the plastic wrap is removed and the lid is opened and kept warm for another 1 hour to remove the unreacted tridecafluorooctyltriethoxysilane in the culture dish, and finally an anti-reflective, hydrophobic and wear-resistant composite film is obtained.
7. A transparent, hydrophobic, and wear-resistant composite film, characterized in that: The anti-reflective, hydrophobic, and wear-resistant composite film is prepared by the preparation method according to any one of claims 1 to 6.