CN113245161B - Preparation method of ultra-black coating with high ultraviolet band absorption - Google Patents

Preparation method of ultra-black coating with high ultraviolet band absorption Download PDF

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CN113245161B
CN113245161B CN202110401091.XA CN202110401091A CN113245161B CN 113245161 B CN113245161 B CN 113245161B CN 202110401091 A CN202110401091 A CN 202110401091A CN 113245161 B CN113245161 B CN 113245161B
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ultra
black coating
spraying
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CN113245161A (en
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吴晓宏
熊启阳
卢松涛
李杨
秦伟
洪杨
康红军
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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
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    • 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
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • 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
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
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    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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]

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Abstract

The invention discloses a preparation method of an ultra-black coating with high ultraviolet band absorption, belonging to the field of stray light suppression of a space optical system. The invention solves the problem that the conventional spraying process for preparing the ultra-black coating generally has low ultraviolet band absorption rate. The method takes carbon black as a black coloring agent, constructs a controllable structure film layer with concentration gradient transition by regulating the mass fraction of the carbon black coloring agent in a multilayer spraying process, and deposits TiO on the surface of the ultra-black coating by adopting an atomic layer deposition technology2A film. The invention further improves the ultraviolet band absorption rate of the ultra-black material by utilizing the high conformality characteristic of the atomic layer deposition technology on the basis of not influencing the stray light inhibition structure on the surface of the ultra-black coating, and expands the application space of the ultra-black coating in the field of space optics.

Description

Preparation method of ultra-black coating with high ultraviolet band absorption
Technical Field
The invention belongs to the field of stray light suppression of a space optical system.
Background
Space optical loads such as optical cameras, detectors, and solar energy conversion devices adversely affect performance due to stray light incident from outside the space and unwanted reflections of incident light from interfaces. Which results in a reduction of the signal-to-noise ratio, sensitivity and reliability of the optical device. In order to improve the performance of the spatial optical load, it is necessary to eliminate the adverse effect of stray light on the spatial optical load. The super-black coating is the most common light absorption material, can effectively reduce the reflection interfering the imaging of the optical load within a certain range, and can greatly absorb the stray light on the surface of the material. Therefore, the development of the high light absorption super-black coating which can be applied to a space optical system has important significance for aerospace industry and space exploration. As the space environment has the characteristics of high vacuum, large temperature difference, multi-ultraviolet irradiation and the like, the high light absorption ultra-black coating with good weather resistance is generally used as a material for eliminating the stray light of the aerospace optical system. Most of common high light absorption super black coatings are prepared by adding carbon black, carbon nano tubes and the like serving as light absorbers into resin materials such as silicon resin, polyurethane and the like. However, the ultra-black coating prepared by the method usually shows low absorption rate in the ultraviolet-near infrared band, the absorption rate bottleneck of 0.97 is difficult to break through, and the absorption rate in the ultraviolet band usually is obviously reduced, so that the application space of the ultra-black coating in the space environment is limited.
Disclosure of Invention
The invention aims to solve the technical problem that the ultraviolet band absorption rate is low commonly existing in the conventional spraying process for preparing the ultra-black coating; and provides a preparation method of the ultra-black coating with high ultraviolet band absorption.
The method takes carbon black as a black coloring agent, constructs a controllable structure film layer with concentration gradient transition by regulating the mass fraction of the carbon black coloring agent in a multilayer spraying process, and deposits TiO on the surface of the ultra-black coating by adopting an atomic layer deposition technology2The film utilizes the high conformality characteristic of the atomic layer deposition technology to further improve the ultraviolet band absorption rate of the ultra-black material on the basis of not influencing the stray light inhibition structure on the surface of the ultra-black coating, and expands the application space of the ultra-black coating in the field of space optics.
In order to solve the technical problem, the invention discloses a preparation method of an ultra-black coating with high ultraviolet band absorption, which is realized by the following steps:
step one, mixing potassium silicate, water and an auxiliary agent, adding grinding beads, uniformly stirring and dispersing, uniformly dividing into any equal parts, respectively adding carbon black with different mass fractions, performing ultrasonic dispersion, continuously stirring, filtering by using filter cloth, and slowly stirring until suspension is stable and does not precipitate to obtain spraying liquids with different concentrations;
secondly, respectively loading the materials into spray guns, and then sequentially spraying and curing the materials on the ground substrate material according to the sequence of concentration from high to low to obtain a concentration gradient super-black coating on the substrate material;
step three, forming TiO on the ultra-black coating obtained in the step two through atomic layer deposition2And (3) forming a film, namely obtaining the ultra-black coating with high ultraviolet band absorption.
Further limiting, the mass fraction of the carbon black in the spraying liquid in the first step is more than or equal to 0.1 percent and is not less than 1 percent; the mass fraction of potassium silicate with the solid content of 37 percent is 30 percent; the mass fraction of the auxiliary agent is 0.2%.
Further defined, step one is that the carbon black has a particle size (40nm, 100 nm).
Further defined, the auxiliary agent in the first step is Tego810 (DigaTEGO Foamex-810 antifoaming agent), Tego747W (DigaTEGO Dispers 747W) or Tego280 (Digao TEGO Dispers 747W)
Figure BDA0003020383660000021
Wet 280)。
Further, the grinding beads used in the first step are zirconium beads with a diameter of 1mm, and the amount of the grinding beads is one third of the liquid volume.
Further limiting, in the second step, the caliber of the spray gun is 0.5mm, and the spraying air pressure is 0.25 MPa.
And further limiting, dividing the mixture into five equal parts in the first step, carrying out curing at 30 ℃ for 0.5h and 55 ℃ for 0.5h after the first spraying to the fourth spraying in the second step, and carrying out curing at 30 ℃ for 0.5h, 55 ℃ for 12h, 85 ℃ for 1h and 125 ℃ for 1h after the fifth spraying.
Further, the atomic layer deposition in the third step is to dispose the substrate material sprayed with the ultra-black coating in the reaction chamber and then process the substrate material by the following steps:
firstly, under the conditions that the temperature is 150-220 ℃ and the pressure is 0.1-0.2 torr, introducing a titanium precursor in a pulse mode for reaction, wherein the pulse time is 0.015-0.025 s, and then introducing nitrogen to purge reaction residues for 20-60 s;
secondly, under the same temperature and pressure conditions, introducing water or an ozone precursor in a pulse mode for reaction, wherein the pulse time is 0.015-0.025 s, and then introducing nitrogen to purge reaction residues for 20-60 s;
and step III, repeating the operation from the step I to the step II for 49 to 500 times.
More specifically, the titanium precursor in the step (i) is titanium tetraisopropoxide.
Further, the temperature in the step I is 180-220 ℃.
The invention adopts a multilayer spraying process to prepare the ultra-black coating, and adopts carbon black with different mass fractions as a colorant with adjustable concentration gradient in each layer of spraying process. And (3) spraying layer by layer, wherein the carbon black concentration is gradually reduced, so that an ultra-black film layer structure with the carbon black concentration gradually reduced from bottom to top is formed. The structure of the film layer is shown in the figure. The concentration gradient structure provides sufficient incident space for stray light, light can be reflected and scattered for multiple times on the inner surface of a single micropore to realize high-efficiency absorption, and a relatively ideal air filling medium is provided to play a role of gradient refractive index, so that the light reflection on the surface of the ultra-black coating is weakened, and the excellent stray light inhibition performance of the ultra-black coating in an ultraviolet-visible range is ensured.
On the basis of preparing the ultra-black coating with the gradient concentration gradient by layered spraying, the invention prepares a layer of three-dimensional coated TiO on the surface of the coating by the atomic layer deposition technology2A membrane as shown. TiO22The film can strengthen the absorptivity of super black coating ultraviolet band, and meanwhile, the AZO film through atomic layer deposition has the shape keeping ability, can guarantee to the maximum extent that super black coating stray light restraines the structure not influenced, further promotes ultraviolet band absorbing capacity when guaranteeing its stray light restraines ability.
Drawings
FIG. 1 is a schematic view of a concentration gradient structure of an ultra-black coating;
FIG. 2 is a schematic diagram of the conformality of an ALD deposited TiO2 thin film;
fig. 3 is a graph of light absorption of different coupons.
Detailed Description
Example 1: the preparation method of the ultra-black coating with high ultraviolet band absorption in the embodiment is realized by the following steps:
take 100g of spray solution as an example:
step one, mixing 30g of potassium silicate, 70mL of water and 0.2g of auxiliary agent Tego280, adding zirconium beads with the diameter of 1mm, wherein the using amount of the zirconium beads is one third of the volume of the liquid, uniformly stirring and dispersing, uniformly dividing into five equal parts, respectively adding high-performance carbon black with different mass fractions, performing ultrasonic dispersion for 3min, continuously stirring for 3h, filtering by using filter cloth, and slowly stirring (500rpm) until the suspension is stable and does not precipitate (consuming 0.5h) to obtain spraying liquids with different concentrations, wherein the mass fractions of the carbon black in the spraying liquid are respectively 0.5%, 0.4%, 0.3%, 0.2% and 0.1%;
secondly, respectively loading a spray gun, wherein the caliber of the spray gun is 0.5mm, the spraying air pressure is 0.25MPa, and then sequentially spraying and curing the ground substrate material according to the sequence of the concentration from high to low to obtain a concentration gradient ultra-black coating on the substrate material, wherein the spraying thickness of each layer is controlled to be 10 microns; wherein the curing is carried out for 0.5h at 30 ℃ and 0.5h at 55 ℃ after the first spraying to the fourth spraying, and the curing is carried out for 0.5h at 30 ℃, 12h at 55 ℃, 1h at 85 ℃ and 1h at 125 ℃ after the fifth spraying.
Step three, forming TiO on the ultra-black coating obtained in the step two through atomic layer deposition2A film is obtained, and the ultra-black coating with high ultraviolet band absorption is obtained;
wherein the particle size of the carbon black of the first step is 40 nm;
step three, the atomic layer deposition is to place the substrate material sprayed with the ultra-black coating into a reaction cavity and then process the substrate material according to the following steps:
firstly, under the conditions that the temperature is 220 ℃ and the pressure is 0.1torr, titanium tetraisopropoxide is introduced in a pulse mode for reaction, the pulse time is 0.02s, then nitrogen is introduced for purging reaction residues, and the purging time is 40 s;
introducing ultrapure water in a pulse mode for reaction under the same temperature and pressure condition, wherein the pulse time is 0.02s, and then introducing nitrogen with the mass purity of 99.999% to purge reaction residues for 40 s;
and step III, repeating the operation from the step I to the step II for 49 times.
Example 2: the preparation method of the ultra-black coating with high ultraviolet band absorption in the embodiment is realized by the following steps:
take 100g of spray solution as an example:
step one, mixing 30g of potassium silicate, 70mL of water and 0.2g of auxiliary agent Tego280, adding zirconium beads with the diameter of 1mm, wherein the using amount of the zirconium beads is one third of the volume of the liquid, uniformly stirring and dispersing, uniformly dividing into five equal parts, respectively adding high-performance carbon black with different mass fractions, ultrasonically dispersing for 5min, continuously stirring for 3h, filtering by using filter cloth, and slowly stirring (500rpm) until the suspension is stable and does not precipitate (consuming 0.5h) to obtain spraying liquids with different concentrations, wherein the mass fractions of the carbon black in the spraying liquid are respectively 1.0%, 0.8%, 0.6%, 0.4% and 0.2%;
secondly, respectively loading a spray gun, wherein the caliber of the spray gun is 0.5mm, the spraying air pressure is 0.25MPa, and then sequentially spraying and curing the ground substrate material according to the sequence of the concentration from high to low to obtain a concentration gradient ultra-black coating on the substrate material, wherein the spraying thickness of each layer is controlled to be 10 microns; wherein the curing is carried out for 0.5h at 30 ℃ and 0.5h at 55 ℃ after the first spraying to the fourth spraying, and the curing is carried out for 0.5h at 30 ℃, 12h at 55 ℃, 1h at 85 ℃ and 1h at 125 ℃ after the fifth spraying.
Step three, forming TiO on the ultra-black coating obtained in the step two through atomic layer deposition2A film is obtained, and the ultra-black coating with high ultraviolet band absorption is obtained;
wherein the particle size of the carbon black of the first step is 40 nm;
step three, the atomic layer deposition is to place the substrate material sprayed with the ultra-black coating into a reaction cavity and then process the substrate material according to the following steps:
firstly, under the conditions that the temperature is 220 ℃ and the pressure is 0.1torr, titanium tetraisopropoxide is introduced in a pulse mode for reaction, the pulse time is 0.02s, then nitrogen is introduced for purging reaction residues, and the purging time is 40 s;
introducing ultrapure water in a pulse mode for reaction under the same temperature and pressure condition, wherein the pulse time is 0.02s, and then introducing nitrogen with the mass purity of 99.999% to purge reaction residues for 40 s;
and step III, repeating the operation from the step I to the step II for 49 times.
Example 3: the preparation method of the ultra-black coating with high ultraviolet band absorption in the embodiment is realized by the following steps:
take 100g of spray solution as an example:
step one, mixing 30g of potassium silicate, 70mL of water and 0.2g of auxiliary agent Tego280, adding zirconium beads with the diameter of 1mm, wherein the using amount of the zirconium beads is one third of the volume of the liquid, uniformly stirring and dispersing, uniformly dividing into five equal parts, respectively adding high-performance carbon black with different mass fractions, performing ultrasonic dispersion for 4min, continuously stirring for 3h, filtering by using filter cloth, and slowly stirring (400rpm) until the suspension is stable and does not precipitate (consuming 0.5h) to obtain spraying liquids with different concentrations, wherein the mass fractions of the carbon black in the spraying liquid are respectively 0.5%, 0.4%, 0.3%, 0.2% and 0.1%;
secondly, respectively loading a spray gun, wherein the caliber of the spray gun is 0.5mm, the spraying air pressure is 0.25MPa, and then sequentially spraying and curing the ground substrate material according to the sequence of the concentration from high to low to obtain a concentration gradient ultra-black coating on the substrate material, wherein the spraying thickness of each layer is controlled to be 20 mu m; wherein the curing is carried out for 0.5h at 30 ℃ and 0.5h at 55 ℃ after the first spraying to the fourth spraying, and the curing is carried out for 0.5h at 30 ℃, 12h at 55 ℃, 1h at 85 ℃ and 1h at 125 ℃ after the fifth spraying.
Step three, forming TiO on the ultra-black coating obtained in the step two through atomic layer deposition2A film is obtained, and the ultra-black coating with high ultraviolet band absorption is obtained;
wherein, the particle diameter of the carbon black in the step one is 100 nm;
step three, the atomic layer deposition is to place the substrate material sprayed with the ultra-black coating into a reaction cavity and then process the substrate material according to the following steps:
firstly, under the conditions that the temperature is 220 ℃ and the pressure is 0.1torr, titanium tetraisopropoxide is introduced in a pulse mode for reaction, the pulse time is 0.02s, then nitrogen is introduced for purging reaction residues, and the purging time is 40 s;
introducing ultrapure water in a pulse mode for reaction under the same temperature and pressure condition, wherein the pulse time is 0.02s, and then introducing nitrogen with the mass purity of 99.999% to purge reaction residues for 40 s;
and step III, repeating the operation from the step I to the step II for 49 times.
Example 4: the preparation method of the ultra-black coating with high ultraviolet band absorption in the embodiment is realized by the following steps:
take 100g of spray solution as an example:
step one, mixing 30g of potassium silicate, 70mL of water and 0.2g of auxiliary agent Tego280, adding zirconium beads with the diameter of 1mm, wherein the amount of the zirconium beads is one third of the volume of the liquid, uniformly stirring and dispersing, uniformly dividing into five equal parts, respectively adding high-performance carbon black with different mass fractions, ultrasonically dispersing for 3min, continuously stirring for 3h, filtering by using filter cloth, and slowly stirring (500rpm) until the suspension is stable and does not precipitate (consuming 0.5h) to obtain spraying liquids with different concentrations, wherein the mass fractions of the carbon black in the spraying liquids are respectively 1.0%, 0.8%, 0.6%, 0.4% and 0.2%;
secondly, respectively loading a spray gun, wherein the caliber of the spray gun is 0.5mm, the spraying air pressure is 0.25MPa, and then sequentially spraying and curing the ground substrate material according to the sequence of the concentration from high to low to obtain a concentration gradient ultra-black coating on the substrate material, wherein the spraying thickness of each layer is controlled to be 20 mu m; wherein the curing is carried out for 0.5h at 30 ℃ and 0.5h at 55 ℃ after the first spraying to the fourth spraying, and the curing is carried out for 0.5h at 30 ℃, 12h at 55 ℃, 1h at 85 ℃ and 1h at 125 ℃ after the fifth spraying.
Step (ii) ofThirdly, forming TiO on the ultra-black coating obtained in the second step by atomic layer deposition2A film is obtained, and the ultra-black coating with high ultraviolet band absorption is obtained;
wherein, the particle diameter of the carbon black in the step one is 100 nm;
step three, the atomic layer deposition is to place the substrate material sprayed with the ultra-black coating into a reaction cavity and then process the substrate material according to the following steps:
firstly, under the conditions that the temperature is 220 ℃ and the pressure is 0.1torr, titanium tetraisopropoxide is introduced in a pulse mode for reaction, the pulse time is 0.02s, then nitrogen is introduced for purging reaction residues, and the purging time is 40 s;
introducing ultrapure water in a pulse mode for reaction under the same temperature and pressure condition, wherein the pulse time is 0.02s, and then introducing nitrogen with the mass purity of 99.999% to purge reaction residues for 40 s;
and step III, repeating the operation from the step I to the step II for 49 times.
The following experiments were used to verify the effect of the invention.
The ultra-black coating materials with different carbon black particle sizes and concentration gradient distributions prepared according to the above examples are prepared into sample pieces of 2 × 2cm, an ultraviolet-visible spectrophotometer is adopted to measure the absorptivity, the ultra-black coating material sample piece with the same thickness and the particle size of 40nm is used as a reference 1, the ultra-black coating material sample piece with the same thickness and the particle size of 100nm is used as a reference 2, the test is repeated for a plurality of times, and the measurement results are shown in fig. 3 and table 1:
TABLE 1 results of the light absorption test of different sample wafers in the 250nm band
Group of Absorption rate
Example 1 0.9547
Example 2 0.9721
Example 3 0.9435
Example 4 0.9455
Control group 1 0.9257
Control group 2 0.9239
As can be seen from FIG. 3 and Table 1, the method of the present invention improves the absorption capacity in the ultraviolet band.

Claims (10)

1. A preparation method of a super-black coating with high ultraviolet band absorption is characterized by comprising the following steps:
step one, mixing potassium silicate, water and an auxiliary agent, adding grinding beads, uniformly stirring and dispersing, uniformly dividing into any equal parts, then respectively adding carbon black with different mass fractions, performing ultrasonic dispersion for 3-5min, continuing stirring, filtering with filter cloth, and slowly stirring until suspension is stable and does not precipitate to obtain spraying liquids with different concentrations;
secondly, respectively loading the carbon black into a spray gun, and sequentially spraying and curing the ground substrate material layer by layer according to the sequence of the concentration from high to low to obtain a concentration gradient super-black coating with the carbon black concentration gradually reduced from bottom to top on the substrate material;
step three, forming TiO on the ultra-black coating obtained in the step two through atomic layer deposition2A film is obtained, and the ultra-black coating with high ultraviolet band absorption is obtained;
wherein the mass fractions of the carbon black in the spraying liquid are respectively 0.5%, 0.4%, 0.3%, 0.2% and 0.1%, or the mass fractions of the carbon black in the spraying liquid are respectively 1.0%, 0.8%, 0.6%, 0.4% and 0.2%.
2. The method according to claim 1, wherein the spraying liquid of step one has a mass fraction of potassium silicate of 37% solids content of 30%; the mass fraction of the auxiliary agent is 0.2%.
3. The method according to claim 1, wherein the carbon black of the first step has a particle size of 40 to 100 nm.
4. The method according to claim 3, wherein the auxiliary agent in step one is Tego810, Tego747w or Tego 280.
5. The method according to claim 1, wherein said grinding beads in the first step are zirconium beads having a diameter of 1mm, and the amount of the grinding beads is one third of the volume of the liquid.
6. The process according to claim 1, wherein in the second step, the bore of the spray gun is 0.5mm, and the spraying pressure is 0.25 MPa.
7. The method of claim 1, wherein the first step is divided into five equal parts, the second step is performed by spraying for the first to fourth times, then curing at 30 ℃ for 0.5h, then at 55 ℃ for 0.5h, and the fifth step is performed by spraying for the fifth time, then curing at 30 ℃ for 0.5h, at 55 ℃ for 12h, at 85 ℃ for 1h, and at 125 ℃ for 1 h.
8. The preparation method according to claim 1, wherein the atomic layer deposition in step three is carried out by disposing the substrate material sprayed with the ultra-black coating in the reaction chamber and then carrying out the following steps:
firstly, under the conditions that the temperature is 150-220 ℃ and the pressure is 0.1-0.2 torr, introducing a titanium precursor in a pulse mode for reaction, wherein the pulse time is 0.015-0.025 s, and then introducing nitrogen to purge reaction residues for 20-60 s;
secondly, under the same temperature and pressure conditions, introducing water or an ozone precursor in a pulse mode for reaction, wherein the pulse time is 0.015-0.025 s, and then introducing nitrogen to purge reaction residues for 20-60 s;
and step III, repeating the operation from the step I to the step II for 49 to 500 times.
9. The method according to claim 8, wherein the titanium precursor in step (i) is titanium tetraisopropoxide.
10. The method according to claim 8, wherein the temperature in step (i) is 180 to 220 ℃.
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