CN113877785B - High-permeability hydrophobic dustproof thin film and preparation method thereof - Google Patents

High-permeability hydrophobic dustproof thin film and preparation method thereof Download PDF

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CN113877785B
CN113877785B CN202111061544.5A CN202111061544A CN113877785B CN 113877785 B CN113877785 B CN 113877785B CN 202111061544 A CN202111061544 A CN 202111061544A CN 113877785 B CN113877785 B CN 113877785B
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film
hydrophobic
layer
deposition
coating
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CN113877785A (en
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卢松涛
李杨
吴晓宏
郭宝
李晓春
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Shenzhen Renfa Aerospace Technology Co ltd
Harbin Institute of Technology
Chongqing Research Institute of Harbin Institute of Technology
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Shenzhen Renfa Aerospace Technology Co ltd
Harbin Institute of Technology
Chongqing Research Institute of Harbin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/22—Silica

Abstract

The invention discloses a high-permeability hydrophobic dustproof thin film and a preparation method thereof, and belongs to the technical field of functional material preparation. The invention solves the technical problems of high preparation cost, complex process and poor film binding force of the existing hydrophobic self-cleaning film. According to the invention, an atomic layer deposition system is utilized to prepare a layer of ZnO film on the surface of a glass substrate, then organic silicon resin and hydrophobic nano silicon dioxide are combined and spin-coated on the surface of a test piece, and the film with a good dust removal effect is obtained. The maximum light transmittance of the hydrophobic self-cleaning film prepared by the method reaches 98.12%, and the hydrophobic angle is 127 degrees. In addition, the coating also has the advantages of friction resistance, strong adhesive force, long service life and the like.

Description

High-permeability hydrophobic dustproof thin film and preparation method thereof
Technical Field
The invention relates to a high-permeability hydrophobic dustproof film and a preparation method thereof, belonging to the technical field of functional material preparation.
Background
The special environment of the moon ensures that the moon dust is easy to adhere to the surface of an optical device, reduces the output power, is easy to overheat and lose efficacy, and brings great harm to the moon exploration project. The main sources of lunar dust are weathering of the lunar surface and collision of the microfluidics. The lunar dust deposited on the surface of the lunar exploration equipment is difficult to naturally remove due to strong adhesion, and finally the lunar exploration equipment is failed or even fails.
At present, the protection mode of the lunar dust is mainly divided into active protection and passive protection. The active protection is mainly to clean the protected surface or prevent the accumulation of lunar dust on the surface of the device by using external force, and the common methods are a mechanical method and an electric dust removal method. Mechanical methods include air jet, ultrasound, gel, viscose, etc. besides the dust removal brush, all of which require the participation of astronauts or robots, wasting resources and time. However, the electric dust removal method requires an additional device and a control circuit, increases the structural complexity of the lunar exploration equipment, and brings about potential safety hazards. Unlike the active protection technology, the passive technology can reduce the adsorption of lunar dust on the surface of the optical device without the aid of external force. The devices are typically surface modified prior to use to reduce the forces between the dust and the surface to be protected for protection purposes.
As a passive dust removal technology, the hydrophobic self-cleaning film depends on a micro-nano structure and low surface energy, and can take away a large amount of dust in the presence of water, but in a lunar environment, the dust removal effect of most hydrophobic self-cleaning films is not ideal, and the low-surface-energy substance mainly containing fluorocarbon has high cost, complex preparation process and poor film binding force. Therefore, from the viewpoint of improving the transparency and the bonding force of the film, it is necessary to provide a highly transparent hydrophobic dustproof film and a preparation method thereof.
Disclosure of Invention
The invention provides a high-permeability hydrophobic dustproof thin film and a preparation method thereof, aiming at solving the technical problems in the prior art.
The technical scheme of the invention is as follows:
a high-permeability hydrophobic dustproof thin film takes a zinc oxide coating as a lower layer film and takes a hydrophobic nano silicon dioxide thin film as an upper layer film; the lower layer film is a single-layer zinc oxide coating, and the thickness of the lower layer film is 15-45 nm; the upper layer film is a single-layer hydrophobic nano silicon dioxide film, and the thickness is 100-300 nm.
Further limit, the particle size of the hydrophobic nano silicon dioxide is 10-30 nm.
The preparation method of the high-permeability hydrophobic dustproof film comprises the following steps:
step 1, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate;
step 2, preparing a lower film layer: performing atomic layer deposition treatment on the pretreated substrate, depositing a ZnO film layer on the surface of the substrate,
step 3, preparing an upper film layer: and (3) spin-coating a hydrophobic nano silicon dioxide-containing coating on the surface of the lower film layer, and carrying out post-treatment on the coating by heating the coating on a heating table at the temperature of 80 ℃ for 5min to obtain the high-permeability hydrophobic dustproof film.
Further, the specific operation of ultrasonic cleaning in step 1 is called as: firstly, absolute ethyl alcohol is used for cleaning for 15min, and the cleaning frequency is 1 time; then cleaning with acetone for 20min for 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 2 times; then washing for 15min by using deionized water, wherein the washing frequency is 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 1 time; finally drying for 1h at 70 ℃.
Further, the specific operation of the deposition process of the atomic layer in step 2 is referred to as:
(1) placing the substrate processed in the step 1 in a deposition cavity of an atomic layer deposition instrument, and pumping the vacuum cavity to 4-6 multiplied by 10 -3 Torr, then introducing nitrogen to the pressure of the cavity at 0.1-0.2Torr, and keeping the temperature of the cavity at 100 ℃ and 200 ℃;
(2) and carrying out atomic layer periodic deposition growth on the surface of the substrate, and repeatedly executing 150-250 growth deposition periods to obtain the substrate plated with the ZnO film layer.
More specifically, the process of each growth deposition cycle is as follows:
firstly, injecting a zinc source into a deposition cavity of the atomic layer deposition instrument in a pulse mode, wherein the pulse time t is 1 0.01-0.03 s;
② cutting off the air intake valve and the exhaust valveReaction, reaction time t 2 Is 5-8 s;
thirdly, opening an air inlet valve and an air outlet valve, and purging by using nitrogen for purging time t 3 Is 30-50 s;
fourthly, injecting a water source into the deposition cavity in a pulse mode, wherein the temperature of the water source is room temperature, and the pulse time t 4 0.01-0.03 s;
fifthly, the air inlet valve and the exhaust valve are cut off for reaction for a reaction time t 5 5-8s, forming ZnO;
sixthly, opening an air inlet valve and an air outlet valve, purging by using nitrogen, and purging for time t 6 For 40s, one deposition growth cycle was completed.
More particularly, the zinc source is diethyl zinc.
Further limiting, the spin coating conditions in step 3 are as follows: the rotating speed is 3000r/min, the acceleration is 1000r/min, and the time is 30 s.
Further limiting, the post-treatment conditions in step 3 are as follows: heating at 80 deg.C for 5 min.
Further limiting, the preparation process of the coating is as follows:
fully dispersing 0.5g of hydrophobic nano-silica particles into 50mL of ethanol solution to obtain a silica dispersion liquid;
adding 10mL of organic silicon resin into 40mL of ethanol solution for full dissolution to obtain organic silicon resin solution;
and thirdly, adding 5mL of organic silicon resin solution into the silicon dioxide dispersion liquid obtained in the step I, and fully stirring to obtain the coating.
Further limiting, the dispersion effect of the nano silicon dioxide is enhanced by adopting the dispersion balls.
The invention has the following beneficial effects: according to the invention, firstly, an atomic layer deposition system is utilized to prepare a layer of ZnO film on the surface of a glass substrate, then, organic silicon resin and hydrophobic nano silicon dioxide are combined and spin-coated on the surface of a test piece, and the film with a good dust removal effect is obtained. The invention also has the following advantages:
(1) compared with the prior art, the invention can achieve the hydrophobic effect without fluorine modification by using the hydrophobic silicon dioxide;
(2) the film obtained by the invention has the highest light transmittance of 98.12 percent and the hydrophobic angle of 127 degrees, and has the advantages of friction resistance, strong adhesive force, long service life and the like;
(3) the preparation method provided by the invention has the advantages of simple process, easily available raw materials and low cost.
Drawings
FIG. 1 shows the transmittance at 400-800nm of the glass with the hydrophobic dustproof film prepared in example 1;
FIG. 2 is an optical photograph of a drop of water on a glass substrate;
FIG. 3 is an optical photograph of a glass having a hydrophobic dustproof thin film prepared in example 1, to which water droplets are dropped;
FIG. 4 is a contact angle optical photograph of a water drop on a glass substrate;
FIG. 5 is a contact angle optical photograph of a glass water droplet having a hydrophobic dustproof thin film obtained in example 1;
FIG. 6 is an optical picture (glass substrate on the side close to the angle ruler) of spraying basalt powder on a glass substrate and the glass with the hydrophobic dustproof thin film prepared in example 1;
FIG. 7 is an optical photograph showing the dropping of basalt powder from the glass substrate at an inclination angle of 50 ℃ and the glass with the hydrophobic dustproof thin film obtained in example 1 (the glass substrate is on the side close to the angle ruler);
FIG. 8 is an optical photograph of a surface state of a glass substrate after dropping of basalt powder and the glass with the hydrophobic dustproof thin film manufactured in example 1 (the right side is a glass substrate);
FIG. 9 is a schematic view showing the bonding force and abrasion resistance test procedure of the hydrophobic dustproof thin film prepared in example 1;
FIG. 10 is an optical photograph of the water contact angle of the hydrophobic dustproof film obtained in example 1 after rubbing the film for 1 time;
FIG. 11 is an optical photograph of the water contact angle of the hydrophobic dustproof film obtained in example 1 after rubbing the film 3 times;
FIG. 12 is an optical photograph of the water contact angle of the hydrophobic dustproof film obtained in example 1 after rubbing the film 10 times;
FIG. 13 is an optical photograph showing the contact angle of a water drop of the thin film obtained in comparative example 1;
FIG. 14 is a photograph showing the water contact angle of the film obtained in comparative example 1 after rubbing the film 10 times;
FIG. 15 is an optical photograph of the water contact angle of the edge area of the film obtained in comparative example 1 after rubbing the film 10 times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
first, pre-treatment of substrate
Carrying out ultrasonic cleaning on a glass substrate:
firstly, absolute ethyl alcohol is used for cleaning for 15min, and the cleaning frequency is 1 time; then cleaning with acetone for 20min for 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 2 times; then washing for 15min by using deionized water, wherein the washing frequency is 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 1 time; finally drying for 1h at 70 ℃.
Secondly, preparation of coating
Preparing a lower film layer:
carrying out atomic layer deposition treatment on the pretreated glass substrate, and depositing a ZnO film layer on the surface of the glass substrate, wherein the operation is called as:
(1) placing the substrate processed in the step 1 in a deposition cavity of an atomic layer deposition instrument, and pumping the vacuum cavity to 5 x 10 -3 Torr, then introducing nitrogen until the pressure of the cavity is 0.15Torr, and keeping the temperature of the cavity at 150 ℃;
(2) carrying out atomic layer periodic deposition growth on the surface of the substrate, and repeatedly executing 180 growth deposition periods to obtain the glass substrate plated with the ZnO film layer with the thickness of 30 nm;
the process of each growth and deposition cycle is as follows:
firstly, injecting a zinc source into a deposition cavity of the atomic layer deposition instrument in a pulse mode, wherein the pulse time t is 1 Is 0.03 s;
② cutting off the air inlet valve and the exhaust valve to react for t 2 Is 6 s;
thirdly, opening an air inlet valve and an air outlet valve, and purging by using nitrogen for purging time t 3 Is 40 s;
fourthly, injecting a water source into the deposition cavity in a pulse mode, wherein the temperature of the water source is room temperature, and the pulse time t 4 Is 0.03 s;
cutting off the air inlet valve and the exhaust valve for reaction for a reaction time t 5 Is 6s, ZnO is formed;
sixthly, opening an air inlet valve and an air outlet valve, purging by using nitrogen, and purging for time t 6 For 40s, one deposition growth cycle was completed.
(II) preparing an upper film layer:
(1) preparing the coating: 0.5g of hydrophobic nano-silica particles was dispersed in 50mL of ethanol solution under vigorous stirring, and dispersion balls were used to ensure sufficient dispersion of the nanoparticles. 10mL of silicone resin was added to 40mL of ethanol solution for sufficient dissolution. Adding 5mL of organic silicon resin solution into the silicon dioxide dispersion liquid, and fully stirring to obtain the coating;
(2) and spin-coating the coating on the substrate plated with the ZnO film layer by using a spin coater, wherein the spin-coating speed is 3000r/min, the acceleration is 1000r/min, the time is 30s, the coating thickness is 150nm, and the glass with the hydrophobic dustproof film is obtained through post-treatment after the coating is finished.
Thirdly, performing performance characterization on the obtained glass with the hydrophobic dustproof film:
(1) and (3) transmittance test:
the glass with the hydrophobic dustproof thin film obtained in example 1 is tested by using an ultraviolet-visible spectrophotometer, and the result is shown in fig. 1, the average light transmittance at the wavelength of 400-800nm is 96.77% (the glass substrate is 100%), the highest light transmittance is 98.12%, and the test result shows that the hydrophobic dustproof thin film prepared by the method has high light transmittance and almost no change in surface transparency. This is because the dispersion effect of the nano-silica is enhanced by the dispersion balls, and the light transmittance of the test piece is improved.
(2) Hydrophobicity test:
the glass substrate and the glass with the hydrophobic dustproof thin film obtained in example 1 were respectively dropped with water drops, and the optical photographs are shown in fig. 2 and fig. 3, and it can be seen from comparison of fig. 2 and fig. 3 that the hydrophobic dustproof thin film prepared in this example has a good hydrophobic effect, and the measurement results of the contact angle tester are shown in fig. 4 and fig. 5, where the hydrophobic angle of the glass substrate is 27 °, and the hydrophobic angle of the glass with the hydrophobic dustproof thin film obtained in example 1 is increased to 127 °, further illustrating that the hydrophobic dustproof thin film prepared in this example has a good hydrophobic effect.
(3) And (3) testing the dust removal performance:
a layer of basalt powder having a weight of about 0.2g was scattered on the glass substrate and the glass surface having the hydrophobic dustproof thin film obtained in example 1 to simulate the moondust, and was placed on a goniometer, as shown in fig. 6, in which the glass substrate was located on the side close to the goniometer and the glass having the hydrophobic dustproof thin film was located on the side far from the goniometer, and the basalt powder was completely dropped on the glass surface having the hydrophobic dustproof thin film at an inclination angle of about 50 ° without dropping the basalt powder on the glass substrate surface, as shown in fig. 7. The surface states of the glass substrate after the dust removal test and the glass with the hydrophobic dustproof thin film prepared in example 1 are shown in fig. 8, in which the side close to the angle ruler is the glass substrate, and the side far from the angle ruler is the glass with the hydrophobic dustproof thin film, as can be seen from fig. 8, the surface states of the glass with the hydrophobic dustproof thin film after dust removal are almost the same as those of the original test piece.
(4) Testing the film binding force and wear resistance:
the test method is as shown in fig. 9, a 100g weight is added on the glass on the back of the film layer, an adhesive tape is adhered on the glass surface for sample wafer dragging, then the film layer is downwards faced, the glass is dragged for 20cm on 240-mesh sand paper, finally the binding force and the wear resistance test of the coating are evaluated through the water contact angle before and after the film layer dragging is tested, in order to reduce the experimental error, the water contact angle is tested for 5 times in different areas of the sample wafer, and the middle value is taken as the evaluation standard. After 1 rubbing, the water contact angle is as shown in fig. 10, the water contact angle of the coating is reduced from 127 ° to 125 °, and the hydrophobicity of the surface is not changed significantly; after 3 times of rubbing, the water contact angle is as shown in fig. 11, the water contact angle is reduced to 123 degrees, and high hydrophobicity can be still ensured; after 10 times of rubbing, the water contact angle is reduced to 113 degrees as shown in fig. 12, and the surface has fine scratches, which result in the reduction of the hydrophobicity of the coating.
Comparative example 1:
the difference between this comparative example and example 1 is that an upper film layer was directly formed on a pretreated glass substrate to obtain a film containing no lower film layer. The hydrophobicity test was performed on the surface of the film obtained in this comparative example, and the test result is shown in fig. 13, where the water contact angle was 123 °, and it can be seen from a comparison between fig. 5 and fig. 13 that the presence or absence of the upper film layer did not affect the water contact angle of the film.
After 10 times of friction experiments, the water contact angle of the film obtained in comparative example 1 is shown in fig. 14, the water contact angle is reduced from 127 degrees to 89 degrees, the coating is almost completely failed due to severe abrasion of abrasive paper in the edge area, the water contact angle is only 56 degrees as shown in fig. 15, and the ALD is shown as an intermediate layer, so that the glass is given certain roughness, mechanical interlocking is generated with the upper silicon coating, the bonding force of the coating is enhanced, and the coating is not easy to fall off in an abrasion test.
Any modifications, equivalents, improvements and the like made within the principle are intended to be included within the scope of the present invention.

Claims (5)

1. A preparation method of a high-permeability hydrophobic dustproof film is characterized in that,
the film takes a zinc oxide coating as a lower layer film and takes a hydrophobic nano silicon dioxide film as an upper layer film; the lower layer film is a single-layer zinc oxide coating, and the thickness of the lower layer film is 15-45 nm; the upper layer film is a single-layer hydrophobic nano silicon dioxide film, and the thickness is 100-300 nm;
the method comprises the following steps:
step 1, pretreatment of a substrate: carrying out ultrasonic cleaning on the substrate;
step 2, preparing a lower film layer: performing atomic layer deposition treatment on the pretreated substrate, depositing a ZnO film layer on the surface of the substrate,
the specific operation process of the deposition treatment of the atomic layer in the step 2 is as follows:
(1) placing the substrate processed in the step 1 in a deposition cavity of an atomic layer deposition instrument, and pumping the vacuum cavity to 4-6 multiplied by 10 -3 Torr, then introducing nitrogen to the cavity at 0.15Torr, and keeping the temperature of the cavity at 100 ℃ and 200 ℃;
(2) carrying out atomic layer periodic deposition growth on the surface of the substrate, and repeatedly executing 150-250 growth deposition periods to obtain the substrate plated with the ZnO film layer;
the process of each growth and deposition cycle comprises the following steps:
firstly, injecting a zinc source into a deposition cavity of the atomic layer deposition instrument in a pulse mode, wherein the pulse time t is 1 0.01-0.03 s;
② cutting off the air inlet valve and the exhaust valve to react for t 2 Is 5-8 s;
thirdly, opening an air inlet valve and an air outlet valve, and purging by using nitrogen for purging time t 3 Is 30-50 s;
fourthly, injecting a water source into the deposition cavity in a pulse mode, wherein the temperature of the water source is room temperature, and the pulse time t 4 0.01-0.03 s;
fifthly, the air inlet valve and the exhaust valve are cut off for reaction for a reaction time t 5 Forming ZnO within 5-8 s;
sixthly, opening an air inlet valve and an air outlet valve, purging by using nitrogen, and purging for time t 6 Completing a deposition growth period of 40 s;
step 3, preparing an upper film layer: coating a hydrophobic nano silicon dioxide-containing coating on the surface of the lower film layer in a spin coating manner, and carrying out post-treatment on the coating by heating the coating on a heating table at the temperature of 80 ℃ for 5min to obtain a high-permeability hydrophobic dustproof film;
the preparation process of the coating comprises the following steps:
fully dispersing 0.5g of hydrophobic nano-silica particles into 50mL of ethanol solution to obtain a silica dispersion liquid;
adding 10mL of organic silicon resin into 40mL of ethanol solution for full dissolution to obtain organic silicon resin solution;
and thirdly, adding 5mL of organic silicon resin solution into the silicon dioxide dispersion liquid obtained in the step I, and fully stirring to obtain the coating.
2. The method for preparing the high-permeability hydrophobic dustproof film according to claim 1, wherein the particle size of the hydrophobic nano silica is 10-30 nm.
3. The method for preparing the high-permeability hydrophobic dustproof film according to the claim 1, wherein the specific operation of the ultrasonic cleaning in the step 1 is called as: firstly, absolute ethyl alcohol is used for cleaning for 15min, and the cleaning frequency is 1 time; then cleaning with acetone for 20min for 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 2 times; then washing for 15min by using deionized water, wherein the washing frequency is 1 time; then using absolute ethyl alcohol to clean for 15min, wherein the cleaning frequency is 1 time; finally drying for 1h at 70 ℃.
4. The method of claim 1, wherein the zinc source is diethyl zinc.
5. The method for preparing the highly permeable hydrophobic dustproof thin film according to claim 1, wherein the spin coating conditions in the step 3 are as follows: the rotating speed is 3000r/min, the acceleration is 1000r/min, and the time is 30 s.
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