CN111175857A - Method for improving infrared band transmittance by processing micro-nano structure on chalcogenide glass surface - Google Patents
Method for improving infrared band transmittance by processing micro-nano structure on chalcogenide glass surface Download PDFInfo
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- CN111175857A CN111175857A CN201811331178.9A CN201811331178A CN111175857A CN 111175857 A CN111175857 A CN 111175857A CN 201811331178 A CN201811331178 A CN 201811331178A CN 111175857 A CN111175857 A CN 111175857A
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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Abstract
The invention relates to a method for improving the transmittance of an infrared band by processing a micro-nano structure on the surface of chalcogenide glass, belonging to the technical field of infrared optical glass processing and application. The method directly prepares the micro-nano structure with proper refractive index on the chalcogenide glass surface, avoids introducing new film materials, and solves the problems of the limitation of multilayer film materials and the quality of film layers in the traditional infrared antireflection film plating process; the reactive ion etching adopted in the method is mainly based on the chemical reaction of gas and chalcogenide glass, does not generate any effect on the part covered by the polymer coating, avoids the generation of stress, and is carried out at normal temperature and in a vacuum state, so that the gasification and leakage of toxic components are avoided; the method can also realize the micro-nano structure pattern imprinting of the non-planar surface, expand the range of optical elements for large-area micro-nano processing, and realize the high-efficiency anti-reflection of chalcogenide glass in each infrared wave band by changing the target graphic structure and the process parameters.
Description
Technical Field
The invention particularly relates to a method for processing a three-dimensional regularly arranged micro-nano structure on the surface of chalcogenide glass to improve the transmittance of an infrared band, belonging to the technical field of infrared optical glass processing and application.
Background
The chalcogenide glass is binary or ternary compound glass formed by combining three elements of sulfur, selenium and tellurium and other glass networks (such as arsenic, antimony, germanium and the like). In the fifth and sixty years of the 20 th century, arsenic sulfide glass is produced in large quantities by several companies in multiple countries such as the United states, the United kingdom and the Europe and is used for 3-5 mu m intermediate infrared window materials. At the same time, the concept and technology of infrared thermal imaging gradually appeared, so people mainly turn to the research of chalcogenide glass transmitting longer wave bands. Then selenide and telluride chalcogenide glasses which can well transmit in 8-14 mu m wave band and wider wave band are developed successively. The refractive index of chalcogenide glass is lower than that of Ge and Si which are commonly used infrared materials at present, the transmittance of infrared materials in medium wave and long wave is higher, the dispersion characteristic is good, and the temperature coefficient of the refractive index of chalcogenide glass material is lower by one order of magnitude compared with that of Ge, so that the chalcogenide glass material is an excellent athermalized and achromatic infrared optical lens material.
Although the refractive index of chalcogenide glass materials is lower than that of common germanium and silicon, the reflection loss is still large, the transmittance of a bare substrate in medium-wavelength and long-wavelength infrared bands is still only about 65%, and surface anti-reflection is the first technology of lenses and windows. The existing method for solving the problem of chalcogenide glass is to plate an infrared antireflection film, and due to the fact that the thermal expansion mismatch between a film material and a substrate exists, the stress is extremely high, the film layer firmness is poor, and the application range of an infrared chalcogenide glass optical element is greatly limited. It has been reported that a sharp mold is used to mechanically stamp non-toxic chalcogenide glass at a certain temperature and pressure to obtain a micron-sized linear grating microstructure for realizing polarized light phase retardation. Although the microstructure processing method can realize the microstructure processing of the surface of the chalcogenide glass, the method also has the following defects: mechanical stamping is adopted, the hardness of the template is higher than that of chalcogenide glass, and the whole processing surface generates deformation and stress; heating the chalcogenide glass to a temperature higher than the glass transition temperature of the chalcogenide glass during mould pressing, and carrying out the mould pressing process at a high temperature; the ingredients of the chalcogenide glass must be low or non-toxic to prevent volatilization of toxic ingredients at high temperatures; the processing mode is only suitable for chalcogenide glass flat sheets; because the one-time stamping is successful, the parameters of the microstructure are fixed, and the shape of the microstructure cannot be controlled by changing parameters such as etching time and the like etching; the method is suitable for simple linear structures and is not suitable for three-dimensional structures with smaller and more complex dimensions.
Disclosure of Invention
Aiming at the problem that the linear microstructure obtained by adopting a plating infrared anti-reflection film method or a die pressing process is used for improving the infrared band transmittance of the surface of chalcogenide glass, the invention provides a method for improving the infrared band transmittance by processing a micro-nano structure on the surface of colored glaze glass.
The purpose of the invention is realized by the following technical scheme.
A method for improving infrared band transmittance by processing a micro-nano structure on the surface of chalcogenide glass comprises the following steps:
(1) coating a polymer coating on the surface of chalcogenide glass;
wherein the polymer coating is made of PMMA (polymethyl methacrylate), PS (polystyrene) or ultraviolet light cured polymer; the thickness of the polymer coating is preferably 100nm to 300 nm;
(2) imprinting a transfer printing template by using a template with a target pattern, preserving heat for 80-120 s at 135-160 ℃, then cooling to 100-130 ℃, preserving heat for 80-120 s, continuously cooling to 80-100 ℃, completing imprinting, and transferring the target pattern to the transfer printing template;
further, the temperature difference of two adjacent cooling processes is not less than 10 ℃, and the template with the target pattern is made of SiC and Si3N4Or SiO2The material of the transfer template is thermoplastic plastics; wherein the target pattern is consistent with the shape of a micro-nano structure etched on chalcogenide glass;
(3) imprinting a polymer coating on the surface of chalcogenide glass by using a transfer printing template with a target pattern, keeping the temperature and the pressure for 60-120 s at 50-100 ℃ and 500-5000 KPa, and transferring the target pattern to the polymer coating;
when the polymer coating is made of ultraviolet curing polymer, the transfer can be assisted by ultraviolet irradiation curing in the process of heat preservation and pressure maintaining; or, the curing and transferring are directly carried out under the irradiation of ultraviolet light, and heating and pressurization are not needed;
(4) removing the polymer coating outside the target pattern area on the chalcogenide glass by adopting reactive ion etching to expose the surface of the chalcogenide glass;
further, the etching parameters are: etching gas O2The flow is 50sccm, the etching power is 100W, the bias power is 50W, and the etching time is changed along with the type and the thickness of the polymer coating until the chalcogenide glass surface is exposed; the etching time is about 20 s-60 s relative to the polymer coating with the thickness of 100 nm-300 nm;
(5) performing reactive ion etching on the residual polymer coating according to the target pattern structure, wherein the etching process parameters are different according to different chalcogenide glass components and micro-nano structure parameters, and transferring the target pattern imprinted on the polymer coating to the surface of chalcogenide glass through etching;
(6) and removing the residual polymer coating to obtain the chalcogenide glass with the micro-nano structure and the anti-reflection function on the surface.
Further, soaking the deeply etched chalcogenide glass by using an acetone or sulfuric acid aqueous solution to remove the residual polymer coating.
The micro-nano structure is formed by repeatedly arranging three-dimensional structure units with rectangular, circular, triangular, hexagonal or parabolic cross sections, the arrangement period is 0.6-4 mu m, the etching depth is 0.9-3.6 mu m, and the infrared anti-reflection effect on a wave band of 2.5-15 mu m can be realized.
Has the advantages that:
(1) according to the invention, the micro-nano structure with a proper refractive index is directly prepared on the surface of chalcogenide glass, and is recessed into the chalcogenide glass, so that the micro-nano structure is regular and ordered, has an obvious anti-reflection effect and good anti-reflection micro-nano structure stability, avoids introducing a new film material, and solves the problems of limitation of a multilayer film material and film quality existing in the traditional infrared anti-reflection film plating process;
(2) in the method, the reactive ion etching adopted for the chalcogenide glass is mainly based on the chemical reaction of gas and the chalcogenide glass, does not generate any effect on the part covered by the polymer coating, and avoids the generation of stress; the etching process does not need heating and is carried out under a certain vacuum degree state, and the gasification and leakage of toxic components are avoided; in addition, due to the adoption of the transfer printing template, the method can process a complex three-dimensional micro-nano structure on the chalcogenide glass of a plane or a curved surface, and avoids the contact damage of the template and a hard substrate;
(3) the method can flexibly adjust each process parameter in the processing process, and can realize the adjustability of the peak value of the chalcogenide glass in each infrared wave band and the infrared anti-reflection of a wide wave band by combining the change of the target graph structure.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the chalcogenide glass surface having a micro-nano structure on the surface prepared in example 1.
Fig. 2 is a graph comparing transmittance of chalcogenide glass having a micro-nano structure on the surface prepared in example 1 with untreated bare chalcogenide glass.
Detailed Description
The invention is further illustrated by the following figures and detailed description, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public disclosure without further specification.
Example 1
Aiming at chalcogenide glass As40Se60(As40Se60, Chengdu information engineering university & Chengdu blue tenon photoelectric technology limited company combined research center), a regularly arranged three-dimensional bowl-shaped micro-nano structure is designed, aiming at realizing the anti-reflection of a wide wave band of 3-12 mu m, and the specific processing process is As follows:
(1) coating an ultraviolet imprint glue (code 04n, Obducat micro-nano imprint corporation) coating with the thickness of 100nm on the surface of chalcogenide glass As40Se60 in a spin coating manner;
(2) impressing a Polyethylene (PE) transfer printing template by using a SiC printing plate engraved with a target pattern (formed by arranging three-dimensional bowl-shaped structure units and consistent with a micro-nano structure etched on the surface of chalcogenide glass As40Se 60), preserving heat at 155 ℃ for 100s, then cooling to 100 ℃ and preserving heat for 90s, then cooling to 90 ℃, and transferring the target pattern to the PE transfer printing template;
(3) imprinting an ultraviolet imprinting adhesive coating on the surface of chalcogenide glass As40Se60 by using a PE (polyethylene) transfer printing template with a target pattern, keeping the temperature and the pressure for 100s at 75 ℃ and 4000KPa, transferring the target pattern to the ultraviolet imprinting adhesive coating, and pulling out the PE transfer printing template;
(4) removing the ultraviolet imprinting glue coating outside the target pattern on the chalcogenide glass As40Se60 by adopting reactive ion etching to expose the surface of the chalcogenide glass As40Se 60; wherein, the etching parameters are as follows: etching gas O2The flow is 50sccm, the ICP power is 100W, the bias power is 50W, and the etching time is 45 s;
(5) coating with residual polymerPerforming reactive ion deep etching by taking the layer As a mask, and transferring a target pattern imprinted on the ultraviolet imprinting glue coating to the surface of chalcogenide glass As40Se60 through etching; wherein, the etching parameters are as follows: etching gas Cl2Flow rate of 30sccm, etching gas BCl3Flow rate of 30sccm, inert gas Ar2The flow is 30sccm, the ICP power is 100W, the bias power is 30W, the pressure is 3Pa, and the etching time is 120 s;
(6) and soaking the deeply etched chalcogenide glass As40Se60 in acetone for 2h, and removing the residual ultraviolet imprint glue coating to obtain the chalcogenide glass As40Se60 with the anti-reflection surface and the micro-nano structure.
The prepared chalcogenide glass As40Se60 with the surface having the micro-nano structure is subjected to topography characterization by a scanning electron microscope, and the result is shown in figure 1. As can be seen from the SEM photograph in FIG. 1, a bowl-shaped micro-nano structure array with regular arrangement is obtained on the surface of chalcogenide glass As40Se60, the arrangement period of three-dimensional bowl-shaped structure units of the micro-nano structure is 1.2 μm, the radius of a bowl opening is 550nm, and the depth of the bowl is 3 μm.
Transmittance characterization is respectively carried out on untreated bare chalcogenide glass As40Se60 and treated chalcogenide glass As40Se60 with a micro-nano structure on the surface by using a WGH-30/6 type double-beam infrared spectrophotometer, and the results are shown in figure 2. According to the test result, after the micro-nano structure is processed on the surface of the chalcogenide glass As40Se60, the transmittance of the chalcogenide glass in a wave band of 3-12 microns is improved by about 7% on average, and the anti-reflection effect is obvious.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for improving the transmittance of an infrared band by processing a micro-nano structure on the surface of chalcogenide glass is characterized by comprising the following steps: the method comprises the following steps of,
(1) coating a polymer coating on the surface of chalcogenide glass;
(2) imprinting a transfer printing template by using a template with a target pattern, preserving heat for 80-120 s at 135-160 ℃, then cooling to 100-130 ℃, preserving heat for 80-120 s, continuously cooling to 80-100 ℃, completing imprinting, and transferring the target pattern to the transfer printing template;
(3) imprinting a polymer coating on the surface of chalcogenide glass by using a transfer printing template with a target pattern, keeping the temperature and the pressure for 60-120 s at 50-100 ℃ and 500-5000 KPa, and transferring the target pattern to the polymer coating;
(4) removing the polymer coating outside the target pattern area on the chalcogenide glass by adopting reactive ion etching to expose the surface of the chalcogenide glass;
(5) performing reactive ion etching on the residual polymer coating according to the target pattern structure, and etching the target pattern imprinted on the polymer coating on the surface of chalcogenide glass;
(6) removing the residual polymer coating to obtain chalcogenide glass with a micro-nano structure and an anti-reflection function on the surface;
wherein the polymer coating is made of polymethyl methacrylate, polystyrene or ultraviolet light cured polymer; the target graph is consistent with the shape of the micro-nano structure, the micro-nano structure is formed by repeatedly arranging three-dimensional structure units with micro-nano sizes, the arrangement period of the three-dimensional structure units is 0.6-4 mu m, and the depth of the three-dimensional structure units etched on chalcogenide glass is 0.9-3.6 mu m.
2. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: the thickness of the polymer coating in the step (1) is 100 nm-300 nm.
3. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: in the step (2), the temperature difference of the temperature reduction is not less than 10 ℃ in two temperature reduction processes of reducing the temperature from 135 ℃ to 160 ℃ to 100 ℃ to 130 ℃ and reducing the temperature from 100 ℃ to 130 ℃ to 80 ℃ to 100 ℃.
4. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: the template with the target pattern is made of SiC and Si3N4Or SiO2。
5. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: the material of the transfer template is thermoplastic plastics.
6. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: when the material of the polymer coating is an ultraviolet curing polymer, the step (3) can further perform the following operations: and (3) imprinting the polymer coating on the surface of the chalcogenide glass by using a transfer printing template with a target pattern, curing and transferring under the irradiation of ultraviolet light, and transferring the target pattern onto the polymer coating.
7. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: in step (4), with O2For etching gases at O2And performing reactive ion etching under the flow rate of 50sccm, the etching power of 100W and the bias power of 50W until the chalcogenide glass surface is exposed.
8. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: the cross section of the three-dimensional structure unit is rectangular, circular, triangular, hexagonal or parabolic.
9. The method for improving the transmittance of the infrared band by processing the micro-nano structure on the surface of the chalcogenide glass according to claim 1, which is characterized in that: and soaking the deeply etched chalcogenide glass in acetone or sulfuric acid water solution to remove the residual polymer coating.
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Cited By (3)
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| CN112859209A (en) * | 2021-02-05 | 2021-05-28 | 业成科技（成都）有限公司 | Cover plate structure and manufacturing method thereof |
| CN113754313A (en) * | 2021-09-27 | 2021-12-07 | 中国建筑材料科学研究总院有限公司 | Chalcogenide glass infrared electromagnetic shielding window and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020240546A1 (en) * | 2019-05-29 | 2020-12-03 | B.G. Negev Technologies & Applications Ltd., At Ben-Gurion University | A method for imprinting micropatterns on a substrate of a chalcogenide glass |
| CN112859209A (en) * | 2021-02-05 | 2021-05-28 | 业成科技（成都）有限公司 | Cover plate structure and manufacturing method thereof |
| CN113754313A (en) * | 2021-09-27 | 2021-12-07 | 中国建筑材料科学研究总院有限公司 | Chalcogenide glass infrared electromagnetic shielding window and preparation method thereof |
| CN113754313B (en) * | 2021-09-27 | 2023-06-30 | 中国建筑材料科学研究总院有限公司 | Chalcogenide glass infrared electromagnetic shielding window and preparation method thereof |
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