CN113045214A - Anti-reflection film with ceramic hole array structure and preparation method thereof - Google Patents

Anti-reflection film with ceramic hole array structure and preparation method thereof Download PDF

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CN113045214A
CN113045214A CN202110281101.0A CN202110281101A CN113045214A CN 113045214 A CN113045214 A CN 113045214A CN 202110281101 A CN202110281101 A CN 202110281101A CN 113045214 A CN113045214 A CN 113045214A
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ceramic
substrate
hole array
sputtering
array structure
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CN113045214B (en
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高俊华
汪湾
曹鸿涛
胡海搏
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C03C2218/328—Partly or completely removing a coating
    • C03C2218/33—Partly or completely removing a coating by etching

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a reflection reducing film with a ceramic hole array structure, which comprises a substrate and a reflection reducing film; the substrate is a transparent substrate, and one or more layers of antireflection films are formed from the substrate to the outside in a one-way or two-way mode; the anti-reflection film structure is a ceramic hole array structure; the thickness of the ceramic pore array structure is 50-300nm, and the ceramic pore array structure comprises a ceramic mother phase and an air pore array layer standing on the ceramic mother phase; the diameter of the holes of the air hole array layer is not less than 2nm, and the average distance between the holes is 1.5-30 nm. The anti-reflection film disclosed by the invention has high transmittance and low haze under wide-spectrum and large-angle light irradiation. The invention also discloses a preparation method of the anti-reflection film with the ceramic hole array structure, and the preparation method is simple and efficient.

Description

Anti-reflection film with ceramic hole array structure and preparation method thereof
Technical Field
The invention belongs to the technical field of optical films, and particularly relates to an antireflection film with a ceramic hole array structure and a preparation method thereof.
Background
The glass substrate is used as an important component of a plurality of photoelectric devices, and has important significance in smart phones, tablet computers, backlight displays, Light Emitting Diodes (LEDs) and solar cells. The glass substrate can protect the device from the influence of the surrounding environment on the one hand, and can enable light to effectively enter or penetrate out of the photoelectric device by utilizing the higher light transmittance of the glass substrate on the other hand, so that the high-performance requirement of the device is met. High transmittance glass substrates are a prerequisite for optoelectronic devices to achieve high performance, however, achieving high transmittance simultaneously over a relatively wide range of wavelengths and angles remains a challenge.
In addition, some application scenarios also put demands on the scattering performance of transmitted light while achieving high transmission. Haze is a parameter that quantifies light scattering, and is generally expressed as the ratio of the luminous flux in the visible range that passes through an object at an angle of more than 2.5 ° from the incident light direction to the total transmitted luminous flux, with greater scattering of light leading to higher haze. The haze of a transparent material is mainly caused by diffuse reflection of light inside or on the surface of the material, and is related to the size and number of scattering micro-regions of the material. The glass substrate with high transmittance and low haze can be applied to the fields of smart phones, tablet computers, glass windows and the like, and is used for increasing the definition of touch screens, display devices and glass windows.
The transmission performance and the haze of the glass substrate can be regulated and controlled through two ways, one way is to directly etch transparent glass by using an etching method, change the surface appearance of the glass and realize the gradual change of the refractive index from air to a glass substrate, so that the reflection loss of light at the interface between the air and the glass is reduced, the transmittance is improved, and the haze of the material is regulated and controlled by changing the rough appearance size of the surface. For example, in the patent of the invention of chinese application No. CN201811215036.6, the anti-glare glass with a haze value of less than 3.5% is obtained by directly etching the glass by a chemical method, but the patent does not give a specific value of the transmittance of the prepared anti-glare glass, and the haze performance has an optimization space. The Chinese patent application with the application number of CN202010805925.9 discloses a preparation method of a high-haze glass substrate. The glass is processed by means of reactive plasma etching and chemical etching, and the surface appearance size of the glass substrate is controlled to be between 0.3 and 2 mu m by changing etching conditions. The controllable haze value is changed from 0.8% to 98.5% while the transmittance higher than 90% is obtained. In the two patents, the rough surface is generated by directly etching the glass, so that the good transmission performance is obtained, but the stability of the glass is greatly reduced, and the wide-spectrum transmission characteristic and the antireflection performance under a large angle are not researched.
The other method is to prepare an anti-reflection film on the surface of the glass substrate, so that the problem of structural stability caused by a direct etching method can be effectively improved. It is common to achieve antireflection with a high and low refractive index stack structure. Common preparation methods of the anti-reflection film layer include a sol-gel method, magnetron sputtering, a vapor deposition method and the like. The Chinese patent application with the application number of CN202010732939.2 discloses an anti-reflection and anti-reflection composite film for a glass substrate and a preparation method thereof. Preparing 7 layers of antireflection films on one side of a glass substrate by an ion source assisted magnetron sputtering method, wherein a first tungsten-doped VO is arranged from the surface of a glass substrate to the outside in sequence2Thin film layer (45-55 nm), Si3N4A thin film layer (100-120 nm) and a second tungsten-doped VO2Thin film layer (45-55 nm), Si3N4A thin film layer (100-120 nm) and a third tungsten-doped VO2Thin film layer (45-55 nm), Si3N4A thin film layer (100 to 120nm) and SiO2A thin film layer (200-260 nm). The transmittance of the coated glass in a visible light range is improved by about 10 percent, and the transmittance curve is relatively gentle. However, the design of the multilayer film system structure is too complicated, the invention only focuses on the transmission characteristic of the antireflection film structure, the haze characteristic is not researched, and in addition, the wide spectrum and the high angle characteristic are not reflected in the antireflection structure.
In conclusion, the direct etching method is simple, but a micron-sized rough surface is generated, and the stability of the structure is affected. Although the anti-reflection film prepared on the glass surface can effectively avoid the generation of a rough surface, the high transmittance with a wide spectrum is required to be stacked by film layers with high and low refractive indexes with different thicknesses, and the preparation process is complicated and is angle-sensitive. It remains a challenge to achieve the broad spectrum, high transmission at large angles, and low haze properties of glass antireflective structures simultaneously.
Disclosure of Invention
The invention provides the anti-reflection film with the ceramic hole array structure, which has high transmittance and low haze under the light irradiation of wide spectrum and large angle, and the preparation method is simple and efficient.
A ceramic hole array structure antireflection film comprises a substrate and an antireflection film;
the substrate is a transparent substrate, and one or more layers of antireflection films are formed from the substrate to the outside in a one-way or two-way mode; the anti-reflection film structure is a ceramic hole array structure;
the thickness of the ceramic pore array structure is 50-300nm, and the ceramic pore array structure comprises a ceramic matrix phase and a vertically arranged air pore array;
the diameter of the holes of the air hole array is not less than 2nm, the average distance of the holes is 1.5-30nm, and the filling rate of the hole array is not less than 6%.
The size of the pore diameter and the average spacing of the pores can reduce the scattering of light and reduce the haze at the nanometer scale. The designed porous ceramic structure antireflection layer realizes graded transition of refractive index from air to the surface of the ceramic substrate, and ensures the large-angle and wide-spectrum permeability of the structure. And the refractive index of the antireflection layer can be conveniently regulated and controlled by changing the filling rate of the holes, so that the transmittance is regulated and controlled. The position of an interference peak can be designed by regulating the thickness of the antireflection layer and the numerical value of the refractive index of the antireflection layer, and the shape of a transmittance curve and the position of a transmission peak are changed.
The ceramic mother phase is Al2O3Or SiO2。
The refractive index of the antireflection film is 1.2-1.4.
Furthermore, the thickness of the ceramic hole array structure is 70-180 nm.
Furthermore, in the air hole array layer, the diameter of the holes is 2-12nm, the average distance of the holes is 2.5-15nm, and the filling rate of the hole array is 6% -60%.
The invention also provides a preparation method of the anti-reflection film with the ceramic hole array structure, which comprises the following steps:
(1) carrying out ultrasonic cleaning on the substrate, and then bombarding and activating the surface of the substrate by using heating or plasma;
(2) selecting metal and ceramic as co-sputtering target materials respectively, and performing multi-target magnetron co-sputtering on the substrate to obtain a metal nanowire array-ceramic composite layer;
(3) and placing the transparent substrate deposited with the metal nanowire array-ceramic composite layer in chemical etching liquid to prepare the anti-reflection film with the ceramic hole array structure.
The preparation method provided by the invention comprises the steps of using metal and ceramic as targets, co-sputtering the targets into a transparent substrate to form a metal nanowire array-ceramic composite layer, and then carrying out chemical reaction on the metal in the metal nanowire array-ceramic composite layer through chemical etching liquid to obtain the porous ceramic antireflection layer structure.
After the substrate is pretreated, the surface cleanliness of the substrate and the film-substrate binding force can be improved, and the high-quality growth of a magnetron sputtering film on the substrate is facilitated.
Under the synergistic action of co-sputtering and chemical etching, the porous ceramic antireflection film with proper pore diameter and pore distance is prepared, and the sizes of the prepared pores are in the nanometer level and are uniform, so that the antireflection film has high stability. By regulating and controlling the deposition parameters of magnetron sputtering, the hole filling rate in the antireflection layer can be changed, the refractive index of the antireflection film can be regulated and controlled, the size and the position of a transmission peak can be regulated and controlled by combining the thickness of the antireflection layer, and an antireflection structure with corresponding performance can be obtained.
And (2) in the step (1), sequentially using acetone, ethanol and deionized water to carry out ultrasonic cleaning on the substrate.
In the step (2), the metal is one of Mo, Au, Ag, Cu and Al.
In the step (2), the substrate is subjected to multi-target magnetron co-sputtering, and simultaneously, ion bombardment assistance is applied to the substrate, the co-sputtering is carried out in an argon atmosphere, and a metal target is driven by a pulse, radio frequency or direct current power supply; the ceramic target is driven by a radio frequency power supply; the ion bombardment assistance is argon particle bombardment.
Further, the power density used for sputtering the metal target is in the range of 0.2 to 4W/cm2(ii) a The power density range for sputtering the ceramic target is 2-20W/cm2The sputtering pressure range is 0.1-1Pa, and the target base distance is higher than 50 mm.
Further preferably, the power density for sputtering the metal target is in the range of 0.5 to 3.5W/cm2(ii) a The power density range of the sputtering ceramic target is 5-15W/cm2The sputtering air pressure range is 0.15-0.6Pa, and the target base distance is higher than 100 mm; the bombardment power density range of the argon particles is 1-2.5W/cm2And the bombardment energy of the argon particles is not less than-40 eV.
By regulating and controlling the sputtering power of the metal target and the ceramic target and controlling the deposition time, and applying proper ion bombardment assistance to the substrate while co-sputtering, the metal nanowire array-ceramic composite layer with proper metal nanowire filling rate and proper thickness can be obtained.
In the step (3), the chemical etching liquid comprises HNO3、H2SO4、HCl、H2O2、NH3·H2And one or more of O.
In the step (3), the chemical etching conditions are as follows: the temperature is 20-60 ℃ and the time is 0.3-3 h. Under the condition of the same concentration of the etching solution, the over-high etching temperature can cause the over-high etching speed and damage the microscopic hole structure; too short etching time can result in incomplete etching of the metal in the structure, and the antireflection effect is affected.
And (3) carrying out post-treatment on the etched nanowire antireflection structure to optimize the antireflection effect of the antireflection film. The post-treatment comprises vacuum annealing treatment, plasma treatment or cleaning by cleaning solution.
The cleaning solution comprises one or more of deionized water, ethanol, acetone, nitric acid and sulfuric acid, and the cleaning time is 5-20 min.
Compared with the prior art, the invention has the following advantages:
(1) the anti-reflection film system designed by the invention has a simple structure, can realize an effective anti-reflection effect in a wide spectrum (380-1700nm) range by utilizing a refractive index matching condition, and can realize low haze of 0.05% in a visible light range.
(2) In the anti-reflection film with the ceramic hole array structure, the sizes of the holes are in the nanometer level, and the holes are uniform in size and are uniformly distributed.
(3) The invention adopts the magnetron sputtering method to prepare the metal nanowire array-ceramic composite film layer, can flexibly regulate and control the filling rate of metal in the composite film layer, has simple process and low cost, and is easy for large-scale integrated preparation.
(4) The invention combines the magnetron sputtering method and the chemical etching method, can conveniently prepare ceramic hole array structures with different hole filling coefficients on the transparent substrate, and realizes the refractive index regulation of the antireflection film layer.
Drawings
FIG. 1 is a graph showing transmittance at an incident angle of 0 ℃ of the antireflection film of example 1;
FIG. 2 is a graph of haze test results for the antireflective film of example 1;
FIG. 3 is an SEM photograph of the surface of the anti-reflection film of example 1;
FIG. 4 is a graph showing transmittance at an incident angle of 0 ° for the antireflection film of example 2;
FIG. 5 is a graph of haze test results for the antireflective film of example 2;
FIG. 6 is an SEM photograph of the surface of an antireflection film of example 2;
FIG. 7 is a graph showing transmittance at incident angles of 0 ° and 45 °, respectively, of the antireflection film of example 3;
FIG. 8 is a graph of haze test results for the antireflective film of example 3;
FIG. 9 is an SEM photograph of the surface of an antireflection film of example 3;
FIG. 10 is a graph showing transmittance at an incident angle of 0 ℃ for the antireflection film of example 4;
FIG. 11 is a graph of haze test results for the antireflective film of example 4;
fig. 12 is an SEM picture of the surface of the antireflection film of example 4.
Detailed Description
The present invention is described in detail below with reference to examples, and it should be understood that the embodiments described herein are only for illustrating the present invention and do not limit the scope of the present invention.
Example 1
In this embodiment, a transparent substrateIs SiO2The glass and the antireflection film are a single-layer ceramic hole array structure layer, the film thickness is 140nm, and the filling rate of nano holes is 30%.
In this embodiment, the single-layer anti-reflection film with the ceramic hole array structure is prepared by depositing a metal nanowire array-ceramic composite film on quartz glass by magnetron co-sputtering, wherein the metal is Ag and the ceramic phase is SiO2Finally, the metal in the composite layer is etched by a chemical etching method to obtain porous SiO2The ceramic layer is prepared by the following specific preparation method:
(1) ultrasonically cleaning the substrate for 15min by sequentially using acetone, ethanol and deionized water, removing pollutants on the surface of the substrate, drying and then fixing the substrate on a substrate tray;
(2) loading the tray into a deposition chamber of a magnetron sputtering device, bombarding the surface of the substrate by using plasma for 8min, and activating the substrate;
(3) adopts magnetron co-sputtering of Ag and SiO2The metal target is driven by a direct current power supply, and the sputtering power density is 2W/cm2The ceramic target is driven by a radio frequency power supply, and the sputtering power density is 9W/cm2Simultaneously, a substrate argon ion bombardment is carried out, and the power density is 1W/cm2After 0.7h of deposition, closing a metal target, a ceramic target and a driving power supply for argon ion bombardment to obtain a metal nanowire array-ceramic composite layer with the metal filling rate of 30%;
(4) placing the quartz glass prepared with the metal nanowire array-ceramic composite layer in etching liquid for etching, wherein the etching liquid is 1mol/L nitric acid, and the etching time is 1 h;
(5) placing the etched quartz glass in alkaline solution, and performing alkaline washing at room temperature for 5min, wherein the alkaline solution is ammonia water solution with the concentration of 0.5 mol/L;
(6) and ultrasonically cleaning the quartz glass subjected to alkali cleaning for 5min by using deionized water, and drying by blowing to obtain the quartz plate plated with the single-layer antireflection layer.
As shown in fig. 1, the average transmission of visible region-near infrared (380nm to 1700nm) is 95.2% at an incident angle of 0 °, and the transmittance of the prepared antireflection film fluctuates little over the whole test spectral range. As shown in fig. 2, the haze value of the antireflective structure was about 0.20%. As shown in fig. 3, the porous ceramic structure in a columnar shape stands upright on the surface of the substrate.
Example 2
The main difference between the antireflection film with a ceramic pore array structure prepared in this embodiment and embodiment 1 is that the film thickness and the porosity are different, and the antireflection film in this embodiment is a double-layer porous SiO film2A ceramic layer. Wherein SiO is directly deposited in the bottom anti-reflection layer of the substrate surface2The porosity is low, the thickness of the film layer is 106nm, and the top layer is made of porous SiO2The ceramic layer has a porosity greater than that of the bottom layer and a thickness of 120 nm.
The specific preparation method of this example is as follows:
(1) ultrasonically cleaning the substrate for 15min by sequentially using acetone, ethanol and deionized water, removing pollutants on the surface of the substrate, drying and then fixing the substrate on a substrate tray;
(2) loading the tray into a deposition chamber of a magnetron sputtering device, bombarding the substrate for 8min by using plasma, and activating the surface of the substrate;
(3) the magnetron co-sputtering of Cu and SiO metals is adopted2The metal target is driven by a direct current power supply, and the sputtering power density is 2W/cm2The ceramic target is driven by a radio frequency power supply, and the sputtering power density is 9.5W/cm2Simultaneously, a substrate argon ion bombardment is carried out, and the power density is 2W/cm2After 0.6h of deposition, closing a metal target, a ceramic target and a driving power supply for argon ion bombardment, obtaining a metal nanowire array-ceramic composite layer with the metal filling rate of about 15% on the surface of the quartz substrate, and taking out the substrate;
(4) placing the quartz glass prepared with the metal nanowire array-ceramic composite layer in etching liquid for etching, wherein the etching liquid is 1mol/L nitric acid, and the etching time is 1 h;
(5) placing the etched quartz glass into a pickling solution, pickling for 5min at room temperature, wherein the pickling solution is HNO with the concentration of 0.5mol/L3A solution;
(6) ultrasonically cleaning the quartz glass subjected to acid cleaning with acetone, ethanol and deionized water for 5min, and drying for later use;
(7) fixing the etched substrate on a magnetron sputtering tray again, and continuously depositing a metal nanowire array-ceramic composite structure layer with a higher metal filling coefficient on the etched surface, wherein the metal filling rate is about 35 percent, and the sputtering power density of a metal target is 3.5W/cm2The sputtering power density of the ceramic target is 9.5W/cm2The argon ion bombardment power density of the substrate is 2W/cm2After 0.7h of deposition, closing the metal target, the ceramic target and a driving power supply for argon ion bombardment, and taking out the quartz plate;
(8) putting the quartz wafer into a vacuum annealing furnace for annealing treatment, wherein the annealing temperature is 300 ℃, and the heat preservation time is 1 h;
(9) the annealed quartz glass is etched in etching liquid again, wherein the etching liquid is 1mol/L nitric acid, and the etching time is 1.5 h;
(10) placing the etched quartz glass into a pickling solution, pickling for 5min at room temperature, wherein the pickling solution is HNO with the concentration of 0.5mol/L3A solution;
(11) and ultrasonically cleaning the quartz glass subjected to acid cleaning by using deionized water for 5min, and drying by blowing to obtain the quartz glass with the gradient ceramic hole array structure antireflection film.
As shown in fig. 4, the average transmittance in the visible-near infrared range (380nm to 1700nm) was 96.3% at an incident angle of 0 °. As shown in fig. 5, the haze value was about 0.13%. As shown in fig. 6, the two-layered columnar ceramic void structure stands on the surface of the ceramic substrate.
Example 3
The antireflection film prepared in this example is different from example 1 mainly in that the antireflection film is prepared on both sides of the transparent substrate. Porous SiO with two-side antireflection film structure being single-layer2The porosity and thickness of the film were the same and were all 100 nm.
The specific preparation method of this example is as follows:
(1) ultrasonically cleaning the substrate for 15min by sequentially using acetone, ethanol and deionized water, removing pollutants on the surface of the substrate, drying and then fixing the substrate on a substrate tray;
(2) loading the tray into a deposition chamber of a magnetron sputtering device, bombarding the substrate for 8min by using plasma, and activating the surface of the substrate;
(3) adopts magnetron co-sputtering of Ag and SiO2The metal target is driven by a direct current power supply, and the sputtering power density is 2W/cm2The ceramic target is driven by a radio frequency power supply, and the sputtering power density is 9W/cm2Simultaneously, a substrate argon ion bombardment is carried out, and the power density is 1W/cm2After 0.5h of deposition, closing a metal target, a ceramic target and a driving power supply for argon ion bombardment to obtain a metal nanowire array-ceramic composite layer with a specific metal filling rate, and taking out the substrate;
(4) turning over the quartz glass with the prepared metal nanowire array-ceramic composite layer, fixing the quartz glass on the tray again, and bombarding the surface of the substrate by using plasma for 8 min. A metal nanowire array-ceramic composite layer is also deposited on the back surface of the quartz glass, and the deposition parameters of the composite layer on the back surface are consistent with those of the front surface;
(5) placing the quartz glass prepared with the metal nanowire array-ceramic composite layer into etching liquid for etching, wherein the etching liquid is a mixed liquid of hydrogen peroxide and ammonia water, and the volume ratio of the hydrogen peroxide to the ammonia water is 1: 1, etching for 1.5 h;
(6) placing the etched quartz glass into a pickling solution, pickling for 5min at room temperature, wherein the pickling solution is HNO with the concentration of 0.5mol/L3A solution;
(7) and ultrasonically cleaning the quartz glass subjected to acid cleaning by using deionized water for 5min, and drying the quartz glass by blowing to obtain the quartz plate with two surfaces both plated with the single-layer ceramic hole array structure antireflection film.
Fig. 7 shows the transmittance of the antireflection structure prepared in this example at incident angles of 0 ° and 45 °, respectively, and it can be seen from the graph that the average transmittance in the visible light range is 98.19% and the average transmittance in the visible-near infrared range (380nm to 1700nm) exceeds 95% at an incident angle of 0 °. When the incident angle is changed from 0 degrees to 45 degrees, the antireflection effect of the prepared antireflection film is reduced, but the transmittance is kept high in the whole tested spectral range. As shown in fig. 8, the haze value was about 0.05%. As shown in FIG. 9, nano-scale (diameter of 3-10nm) holes are uniformly distributed on the surface of the anti-reflection film.
Example 4
The antireflection film prepared in this example is mainly different from example 2 in that the same two-layer gradient antireflection film is prepared on both sides of the transparent substrate, and the side close to the transparent substrate is porous SiO with low porosity2The film has a porosity of 20% and a thickness of 80 nm. Far from the substrate is porous SiO with high porosity2The film has porosity of 40% and thickness of 100 nm.
The specific preparation method of this example is as follows:
(1) ultrasonic cleaning the transparent substrate by sequentially using acetone, ethanol and deionized water for 15min, and fixing the transparent substrate on a substrate tray after blow-drying;
(2) loading the tray into a deposition chamber of a magnetron sputtering device, bombarding the substrate for 8min by using plasma, and activating the surface of the substrate;
(3) adopts magnetron co-sputtering of Ag and SiO2The metal target is driven by a direct current power supply, and the sputtering power density is 1.5W/cm2The ceramic target is driven by a radio frequency power supply, and the sputtering power density is 9W/cm2Simultaneously, a substrate argon ion bombardment is carried out, and the power density is 1W/cm2After 0.4h of deposition, closing a metal target, a ceramic target and a driving power supply for argon ion bombardment to obtain a metal nanowire array-ceramic composite layer with a specific metal filling rate, and taking out the substrate;
(4) and turning over the quartz glass prepared with the metal nanowire array-ceramic composite layer, fixing the quartz glass on the tray again, and cleaning the surface for 8min by utilizing the substrate bias. A metal nanowire array-ceramic composite layer is also deposited on the back surface of the quartz glass, and the deposition parameters of the composite layer on the back surface are consistent with those of the front surface;
(5) placing the quartz glass prepared with the metal nanowire array-ceramic composite layer in etching liquid for etching, wherein the etching liquid is 1mol/L nitric acid, and the etching time is 1 h;
(6) placing the etched quartz glass into a pickling solution, pickling for 5min at room temperature, wherein the pickling solution is HNO with the concentration of 0.5mol/L3Solutions of；
(7) Ultrasonically cleaning the quartz glass subjected to acid cleaning by using acetone, ethanol and deionized water for 5min, and drying for later use;
(8) fixing the cleaned substrate with the film coated with porous layers on the substrate tray, and continuously coating the metal nanowire array-ceramic composite layer on the surface of the film, wherein the sputtering power density of the metal is 3W/cm2The ceramic target is driven by a radio frequency power supply, and the sputtering power density is 8W/cm2Simultaneously, a substrate argon ion bombardment is carried out, and the power density is 1W/cm2After depositing for 0.5h, closing the metal target, the ceramic target and a driving power supply for argon ion bombardment to obtain a metal nanowire array-ceramic composite layer with high metal filling rate;
(9) after the quartz glass is turned over, plating a metal nanowire array-ceramic composite layer on the back of the quartz glass again, wherein the sputtering parameters of the quartz glass are consistent with those of the front of the quartz glass;
(10) putting the quartz glass prepared with the nanowire film into an annealing furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing heat preservation time is 1 h;
(11) placing the annealed quartz glass in an etching solution for etching, wherein the etching solution is 1mol/L nitric acid, and the etching time is 1.5 h;
(12) placing the etched quartz glass into a pickling solution, pickling for 5min at room temperature, wherein the pickling solution is HNO with the concentration of 0.5mol/L3A solution;
(13) ultrasonically cleaning the quartz glass after acid cleaning by deionized water for 5min and drying to obtain porous SiO with double-layer gradient on both sides2The anti-reflection film with the ceramic hole array structure is a film.
As shown in fig. 10, when the incident angle is 0 °, the transmittance of the prepared anti-reflection film in the range of 380nm to 1700nm is higher than 96%, and high absorption in a wide spectrum range is realized. As shown in fig. 11, the haze value was about 0.22%. As shown in FIG. 12, nano-scale (diameter of 4-12nm) holes are uniformly distributed on the surface of the anti-reflection film.
While the foregoing detailed description has described the technical solutions and advantages of the present invention in detail, it should be understood that the above is only the most preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The anti-reflection film with the ceramic hole array structure is characterized by comprising a substrate and an anti-reflection film;
the substrate is a transparent substrate, and one or more layers of antireflection films are formed from the substrate to the outside in a one-way or two-way mode; the anti-reflection film structure is a ceramic hole array structure;
the thickness of the ceramic hole array structure is 50-300nm, and the ceramic hole array structure comprises a ceramic mother phase and a columnar air hole array which is erected on a transparent substrate;
the diameter of the holes of the air hole array layer is not less than 2nm, and the average distance between the holes is 1.5-30 nm.
2. The antireflection film with a ceramic hole array structure as claimed in claim 1, wherein the ceramic matrix phase is Al2O3Or SiO2。
3. The reflection reducing film with a ceramic pore array structure as claimed in claim 1, wherein the diameter of the pores in the air pore array layer is 2-12nm, the average distance of the pores is 2.5-15nm, and the filling rate of the pore array is 6% -60%.
4. The method for preparing the anti-reflection film with the ceramic hole array structure according to any one of claims 1 to 3, comprising:
(1) carrying out ultrasonic cleaning on the substrate, and then bombarding and activating the surface of the substrate by using heating or plasma;
(2) selecting metal and ceramic as co-sputtering target materials respectively, and performing multi-target magnetron co-sputtering on the substrate to obtain a metal nanowire array-ceramic composite layer;
(3) and placing the transparent substrate deposited with the metal nanowire array-ceramic composite layer in chemical etching liquid to prepare the porous ceramic antireflection film layer.
5. The method for preparing the anti-reflection film with the ceramic hole array structure according to claim 4, wherein in the step (1), the substrate is sequentially subjected to ultrasonic cleaning by using acetone, ethanol and deionized water.
6. The method for preparing the anti-reflection film with the ceramic hole array structure according to claim 4, wherein in the step (2), the substrate is subjected to multi-target magnetron co-sputtering while ion bombardment assistance is applied to the substrate, the co-sputtering is performed in an argon atmosphere, and the metal target is driven by a pulse, radio frequency or direct current power supply; the ceramic target is driven by a radio frequency power supply; the ion bombardment assistance is argon particle bombardment.
7. The method as claimed in claim 6, wherein the sputtering power density of the metal target is in the range of 0.2-4W/cm2(ii) a The power density range of the sputtering ceramic target is 2-20W/cm2The sputtering pressure range is 0.1-1Pa, and the target base distance is higher than 50 mm.
8. The method according to claim 7, wherein the sputtering power density of the metal target is in the range of 0.5-3.5W/cm2(ii) a The power density range of the sputtering ceramic target is 5-15W/cm2The sputtering air pressure range is 0.15-0.6Pa, and the target base distance is higher than 100 mm; the bombardment power density range of the argon particles is 1-2.5W/cm2And the bombardment energy of the argon particles is not less than-40 eV.
9. The method for preparing a reflection reducing film with a ceramic hole array structure according to claim 4, wherein in the step (3), the chemical etching solution comprises HNO3、H2SO4、HCl、H2O2、NH3〃H2And one or more of O.
10. The method for preparing the antireflection film with the ceramic hole array structure according to claim 4, wherein in the step (3), the chemical etching conditions are as follows: the temperature is 20-60 ℃ and the time is 0.3-3 h.
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Publication number Priority date Publication date Assignee Title
CN103762248A (en) * 2014-01-23 2014-04-30 中国科学院半导体研究所 Solar cell component with anti-reflective coating and preparation method thereof
CN105242334A (en) * 2015-10-27 2016-01-13 中国科学院宁波材料技术与工程研究所 Multilayer metal ceramic thin film having wide-spectrum ultrafast nonlinear optical response performance and preparation method thereof
CN107393977A (en) * 2017-08-09 2017-11-24 西安交通大学 A kind of ultra wide band antireflective film and preparation method thereof
CN110183113A (en) * 2019-05-22 2019-08-30 湖南天羿领航科技有限公司 The preparation method of glare proof glass
US20200333593A1 (en) * 2017-10-10 2020-10-22 Central Glass Co., Ltd. Head-up display with improved anti-reflection functional coating on windshield

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103762248A (en) * 2014-01-23 2014-04-30 中国科学院半导体研究所 Solar cell component with anti-reflective coating and preparation method thereof
CN105242334A (en) * 2015-10-27 2016-01-13 中国科学院宁波材料技术与工程研究所 Multilayer metal ceramic thin film having wide-spectrum ultrafast nonlinear optical response performance and preparation method thereof
CN107393977A (en) * 2017-08-09 2017-11-24 西安交通大学 A kind of ultra wide band antireflective film and preparation method thereof
US20200333593A1 (en) * 2017-10-10 2020-10-22 Central Glass Co., Ltd. Head-up display with improved anti-reflection functional coating on windshield
CN110183113A (en) * 2019-05-22 2019-08-30 湖南天羿领航科技有限公司 The preparation method of glare proof glass

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