WO2022127170A1 - Large-caliber flexible optical metasurface structure and processing method therefor - Google Patents

Large-caliber flexible optical metasurface structure and processing method therefor Download PDF

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WO2022127170A1
WO2022127170A1 PCT/CN2021/113819 CN2021113819W WO2022127170A1 WO 2022127170 A1 WO2022127170 A1 WO 2022127170A1 CN 2021113819 W CN2021113819 W CN 2021113819W WO 2022127170 A1 WO2022127170 A1 WO 2022127170A1
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flexible optical
processing
optical metasurface
metasurface structure
diameter
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PCT/CN2021/113819
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French (fr)
Chinese (zh)
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罗先刚
蒲明博
高平
李雄
马晓亮
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中国科学院光电技术研究所
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2059—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam
    • G03F7/2063—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a scanning corpuscular radiation beam, e.g. an electron beam for the production of exposure masks or reticles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams

Definitions

  • the present disclosure belongs to the technical field of processing of metasurface devices, and in particular relates to a large-diameter flexible optical metasurface structure and a processing method thereof.
  • Optical metasurfaces are artificial two-dimensional structures composed of micro-nano units with dimensions ranging from tens to hundreds of nanometers.
  • typical photolithography processes can rapidly replicate mask patterns, but cannot provide sufficient pattern resolution due to the diffraction limit.
  • Electron beam lithography (EBL) and focused ion beam (FIB) milling are less efficient in fabrication.
  • nanoimprinting improves the fabrication efficiency of metasurfaces, while the resolution has no physical limit.
  • hot embossing is widely used, but it puts forward higher requirements for the low thermal expansion coefficient and pressure shrinkage coefficient of the material.
  • high pressure and heating temperature are required, which is likely to cause damage to the pattern structure of the template and adhesive layer.
  • Ultraviolet nanoimprint technology solves the problems existing in hot embossing, but the bubbles in the ultraviolet curing adhesive are difficult to discharge, which will cause defects in the micro-nano structure.
  • the roll-to-roll nanoimprinting proposed by UV imprinting technology high-throughput fabrication of micro-nanostructures is realized.
  • the roll-to-roll imprint template is bent and fixed on the roller, so the positional accuracy of the nanostructures on the template will be reduced, which will affect the optical properties of the imprinted optical metasurface.
  • the stencil pattern can be copied to the embossing rubber through the embossing method, and the graphic structure of the embossing rubber generally does not directly have functions. It is necessary to transfer the embossing rubber pattern to other functional materials, which will increase the process steps. and difficulty.
  • the main difficulty of the existing metasurface preparation technology is how to reduce the complexity of the process and improve the device preparation efficiency and the micro-nano structure pattern quality under the premise of meeting its performance requirements.
  • the present disclosure provides a large-diameter flexible optical metasurface structure and a processing method thereof.
  • a method for processing a large-diameter flexible optical metasurface structure comprising:
  • the flexible substrate After curing and forming, the flexible substrate is separated from the template to obtain a large-diameter flexible optical metasurface structure.
  • the high refractive index nanoparticles comprise at least one of titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, ceria and silicon.
  • the diameter of the high refractive index nanoparticles is no greater than 50 nm.
  • the material of the flexible substrate comprises an optically clear polymer or metallic glass.
  • the thickness of the flexible substrate is not greater than 500 ⁇ m.
  • the ultraviolet light is a surface light source or a line light source.
  • a large-aperture flexible optical metasurface structure is provided, and the large-aperture flexible optical metasurface structure is prepared by using the above-mentioned processing method for a large-aperture flexible optical metasurface structure.
  • the large-aperture flexible optical metasurface structure can be directly used as an optical device.
  • a method for processing a large-diameter flexible optical metasurface structure is provided, and the steps of the method are as follows:
  • Step (1) coating photoresist on the base template
  • Step (2) exposing through a photolithography system, and then developing
  • Step (3) the graphics are transferred to the base material, and used as a template
  • Step (4) by being mixed with the UV-curable glue of high refractive index nanoparticle coating on template and covering a layer of flexible substrate, adopting roller shaft while applying mechanical pressure while utilizing the mode of UV lamp exposure to cure UV-curing glue;
  • step (5) the flexible substrate and the template are separated to prepare a large-diameter flexible optical metasurface structure.
  • the photoresist in the step (1) is electron beam photoresist and ultraviolet photoresist.
  • the lithography system in the step (2) is an electron beam lithography system, an ultraviolet super-resolution lithography system and an ultraviolet super-resolution direct writing system.
  • the pattern transfer in the step (3) is stripping, metal-assisted chemical etching, gas-assisted ion beam etching and high-density plasma etching.
  • the high-refractive-index nanoparticles are titanium oxide, zirconia, zirconium oxide, zinc oxide, cerium oxide, and silicon, and the diameter of the high-refractive-index nanoparticles is less than or equal to 50 nm.
  • the flexible base material is optically transparent polymer and metallic glass, and the thickness of the flexible base is ⁇ 500 ⁇ m; the ultraviolet light source is a surface light source and a line light source.
  • a template is formed by etching an optical metasurface pattern on a substrate, and the template is placed flat on the bottom, and a roller is used to apply pressure on the flexible substrate and the intermediate UV-curable glue covered on it, while performing Ultraviolet light curing improves the positional accuracy and pattern size accuracy of the micro-nano unit pattern structure in a simple and efficient way.
  • the present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the dependence on the high depth of the original pattern of the template, and reduces the processing difficulty and flexibility of the template
  • the possibility of pattern damage when the metasurface is demolded overcomes the defect of low optical properties of the obtained metasurface due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method.
  • the present disclosure adopts ultraviolet light irradiation to cure the ultraviolet curing glue filled with the micro-nano structure to realize the preparation of the optical metasurface.
  • the preparation cycle is short and the efficiency is high, and the prepared large-diameter flexible optical metasurface structure can be directly used as an optical device. use.
  • FIG. 1 shows a flowchart of a method for processing a large-diameter flexible optical metasurface structure according to an embodiment of the present disclosure
  • Figure 2-1 is a schematic diagram of spin-coating photoresist on a substrate
  • Figure 2-3 is a schematic diagram of the metasurface structure transferred to the template by etching
  • Figure 2-4 is a schematic diagram of applying UV-curable glue to a template and covering a layer of flexible substrate
  • Figure 2-5 is a schematic diagram of the process of UV curing while flattening the UV curing glue with a roller;
  • Figure 2-6 is a schematic structural diagram after UV curing is completed
  • 2-7 are schematic diagrams of the process of separating the flexible substrate from the template
  • the present disclosure provides a processing method of a large-aperture flexible optical metasurface structure and a large-aperture flexible optical metasurface structure, in order to at least partially solve the above technical problems.
  • FIG. 1 schematically shows a flow chart of a method for processing a large-diameter flexible optical metasurface structure according to an embodiment of the present disclosure.
  • the method for processing a large-diameter flexible optical metasurface structure includes steps S110 to S130.
  • Step S110 etching the preset pattern on the substrate to form a template.
  • the so-called preset pattern here refers to the metasurface pattern structure to be etched, that is, the metasurface pattern structure to be prepared. According to actual needs, metasurface patterns of different sizes can be selected as preset patterns, and then the preset patterns can be transferred to the substrate by etching to form a template.
  • an existing etching method can be used, such as ion beam etching, inductively coupled plasma etching, reactive ion etching, etc.
  • an appropriate etching method and etching equipment can be selected according to actual needs, which is not limited here.
  • step S120 the UV-curable adhesive mixed with the high-refractive-index nanoparticles is coated on the template and covered with a flexible substrate, and the UV-curable adhesive is subjected to UV light curing while applying pressure.
  • High refractive index nanoparticles include, but are not limited to, titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, cerium oxide, silicon.
  • the high-refractive-index nanoparticles may adopt any one of the above-described materials, or any combination of any of them, which is not limited herein.
  • the diameter of the high-refractive-index nanoparticles is not greater than 50 nm.
  • the mass ratio refers to the percentage of the mass of the high-refractive-index nanoparticles to the total mass of the high-refractive-index nanoparticles mixed with the UV-curable glue
  • the high-refractive-index nanoparticles are mixed with the UV-curable adhesive, for example, 1% to 20% or even higher proportions of the high-refractive-index nanoparticles are mixed with the UV-curable adhesive.
  • the present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the processing difficulty of the original pattern depth of the template and the pattern damage during demolding, and overcomes the traditional method Due to the low refractive index of the UV-curable adhesive, the optical properties of the processed metasurface are low.
  • the material of the flexible substrate includes, but is not limited to, optically transparent polymer or metallic glass, for example, the optically transparent polymer can be polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), etc.
  • the optically transparent polymer can be polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), etc.
  • a flexible substrate is used to apply pressure to the UV-curable adhesive, and then UV-curing is performed, and finally a metasurface is formed. Therefore, the thickness of the flexible substrate has a certain influence on the quality of the metasurface.
  • the thickness of the flexible substrate can be designed not to be greater than 500 ⁇ m, which can not only ensure a good curing effect of the UV-curable adhesive, but also ensure the accuracy of the metasurface.
  • the ultraviolet light source for ultraviolet curing may be selected, for example, as a surface light source or a line light source.
  • Step S130 after curing and forming, the flexible substrate is separated from the template to obtain a large-diameter flexible optical metasurface structure.
  • the optical metasurface pattern is etched on the substrate to form a template, and the template is placed on the bottom, and the flexible substrate and the middle UV curing glue covered on the template are pressed by a roller, and the UV curing is carried out at the same time.
  • the machining accuracy of large-diameter flexible optical metasurface structures is improved in a simple and efficient manner.
  • the present disclosure mixes high-refractive-index nanoparticles with UV-curable glue, which increases the equivalent refractive index of the metasurface structure and reduces the dependence on the high depth of the original pattern of the template, thereby reducing the difficulty of template processing and the flexibility of metastructures.
  • the possibility of pattern damage when the surface is demolded overcomes the defect that the optical properties of the obtained metasurface are low due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method.
  • the large-diameter flexible optical metasurface structure prepared by the processing method in the embodiment of the present disclosure can directly form an optical device without the need for a subsequent etching and transfer process.
  • the present disclosure further provides a large-aperture flexible optical metasurface structure, and the large-aperture flexible optical metasurface structure adopts the above-mentioned large-aperture flexible optical metasurface structure
  • the surface structure is prepared by the processing method, and the large-diameter flexible optical metasurface structure can be directly used as an optical device.
  • the large-diameter flexible optical metasurface structure in the embodiment of the present disclosure includes high-refractive-index nanoparticles, and based on the high-refractive-index nanoparticles, the equivalent refractive index of the metasurface structure is increased, and the high depth of the original pattern of the template is reduced. Therefore, the difficulty of template processing and the possibility of pattern damage when the flexible metasurface is demolded are reduced, which overcomes the traditional method due to the low refractive index of the UV-curable glue and the limited processing means, the obtained metasurface has Defects with low optical performance.
  • a method for processing a large-diameter flexible optical metasurface structure is provided.
  • the steps of this method are as follows:
  • Step (1) coating photoresist on the base template.
  • the photoresist can be, for example, electron beam photoresist and ultraviolet photoresist.
  • other types of photoresist can be selected according to the actual situation, which is not limited here.
  • step (2) exposure is performed through a photolithography system, and then developed.
  • a suitable lithography system can be selected according to the lithography method, for example, an electron beam lithography system, an ultraviolet super-resolution lithography system or an ultraviolet super-resolution direct writing system can be selected, etc., which are not limited herein.
  • step (3) the graphic is transferred to the base material and used as a template.
  • the transfer of the metasurface pattern to the base material can be carried out by means of stripping, metal-assisted chemical etching, gas-assisted ion beam etching, or high-density plasma etching, which is not limited herein.
  • Step (4) by coating the UV-curable adhesive mixed with high-refractive-index nanoparticles on the template and covering it with a layer of flexible substrate, and curing the UV-curable adhesive by exposing the UV-curable adhesive with a roller while applying mechanical pressure.
  • High refractive index nanoparticles include, but are not limited to, titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, cerium oxide, silicon. Wherein, the diameter of the high-refractive-index nanoparticles is not greater than 50 nm.
  • the mass ratio refers to the percentage of the mass of the high-refractive-index nanoparticles to the total mass of the high-refractive-index nanoparticles mixed with the UV-curable glue
  • the high-refractive-index nanoparticles are mixed with the UV-curable glue, eg, 1% or 20% of the high-refractive-index nanoparticles are mixed with the UV-curable glue.
  • the present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the processing difficulty of the original pattern depth of the template and the pattern damage during demolding, and overcomes the traditional method Due to the low refractive index of the UV-curable adhesive, the optical properties of the processed metasurface are low.
  • step (5) after curing and forming, the flexible substrate is separated from the template to prepare a large-diameter flexible optical metasurface structure.
  • the present disclosure realizes the preparation of a 200mm aperture flexible optical metasurface structure.
  • Electron beam lithography system is used to expose the large-area metasurface pattern structure.
  • the pattern diameter is 180mm
  • the pattern period is 420nm
  • the pattern line width is 130nm.
  • development is performed.
  • the photoresist pattern after development is shown in Figure 2-2. shown.
  • the developed pattern is transferred to the silicon substrate 7 by the reactive ion etching equipment to obtain the imprint master (ie the template 6, see Fig. 2-3), the etching power is 50W, and the etching chamber pressure is 0.5Pa , SF6 flow 25SCCM, CHF3 flow 5SCCM, etching depth 150nm.
  • the present disclosure is used to realize the fabrication of 8-inch aperture flexible optical metasurface structures.
  • a chromium layer (not shown in the figure) with a thickness of 40 nm was plated on a silicon substrate 7 with a diameter of 8 inches by a magnetron sputtering device, the power was 400 W, and the cavity pressure was 1 mTorr.
  • a layer of electron beam photoresist 5 with a thickness of 80 nm is spin-coated on a silicon substrate 7 with a diameter of 8 inches coated with a chromium layer with a thickness of 40 nm.
  • Electron beam lithography system is used to expose the large-area metasurface pattern structure.
  • the pattern diameter is 180mm
  • the pattern period is 450nm
  • the unit pattern width is 100nm
  • the length is 330nm.
  • development is performed.
  • the photoresist pattern after development is referenced shown in Figure 2-2.
  • the pattern is transferred to the silicon substrate 7 by reactive ion etching equipment to obtain an imprinted master plate, the etching power is 100W, the etching chamber pressure is 0.5Pa, the flow rate of SF6 is 25SCCM, the flow rate of CHF3 is 5SCCM, and the etching depth is 720nm.
  • the chromium layer on the surface is removed by wet etching with a chromium removing solution to obtain an imprint master (namely, the template 6, as shown in Fig. 2-3).
  • the UV-curable glue 2 mixed with 20% mass ratio of titanium dioxide nanoparticles 3 is coated on the imprint master (ie, the template 6), and polyethylene terephthalate ( PET) flexible substrate 1 (thickness 100 ⁇ m) is covered on its surface, and the UV curing glue 2 is flattened by the pressing roller 4, and the UV light 8 is irradiated and cured to complete the imprinting and curing of the entire diameter, and after demolding, the required
  • the large-aperture flexible optical metasurface structure 9 (see Figure 2-4 to Figure 2-8 for the above process).
  • the power of ultraviolet light is 184W
  • the moving speed of the roller is 3.4mm/s
  • the pressing pressure of the roller is 0.2MPa.
  • the present disclosure provides a large-diameter flexible optical metasurface structure and a processing method thereof.
  • the optical metasurface pattern is etched on the substrate to form a template, and the template is placed on the bottom, and the flexible substrate and the middle UV curing glue covered on the template are pressed by a roller, and the UV curing is carried out at the same time. , thereby improving the processing accuracy of the large-aperture flexible optical metasurface structure in a simple and efficient manner, and the prepared large-aperture flexible optical metasurface structure can be directly used as an optical device.
  • the present disclosure mixes high-refractive-index nanoparticles with UV-curable glue, which increases the equivalent refractive index of the metasurface structure and reduces the dependence on the high depth of the original pattern of the template, thereby reducing the difficulty of template processing and the flexibility of metastructures.
  • the possibility of pattern damage when the surface is demolded overcomes the defect that the optical properties of the obtained metasurface are low due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method.

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Abstract

A large-caliber flexible optical metasurface structure (9) and a processing method therefor. The processing method comprises: (S110) etching a preset pattern onto a substrate (7) to form a die plate (6); (S120) coating an ultraviolet curing adhesive (2) mixed with high refractive index nanoparticles (3) on the die plate (6), covering a flexible substrate (1), and performing ultraviolet light (8) curing while applying pressure to the ultraviolet curing adhesive (2); and (S130) after curing and molding, separating the flexible substrate (1) from the die plate (6) to obtain a large-caliber flexible optical metasurface structure (9). This simple and efficient method implements the preparation of a high-precision large-caliber flexible optical metasurface structure (9), and is applicable to the field of processing of large-area flexible metasurface surface devices.

Description

大口径柔性光学超构表面结构及其加工方法Large aperture flexible optical metasurface structure and its processing method 技术领域technical field
本公开属于超构表面器件的加工技术领域，具体涉及一种大口径柔性光学超构表面结构及其加工方法。The present disclosure belongs to the technical field of processing of metasurface devices, and in particular relates to a large-diameter flexible optical metasurface structure and a processing method thereof.
本公开要求于2020年12月18日在中国申请的申请号为202011507346.2的发明专利申请的优先权，并在此援引其内容。The present disclosure claims the priority of the invention patent application with application number 202011507346.2 filed in China on December 18, 2020, and the content of which is incorporated herein by reference.
背景技术Background technique
光学超构表面是由具有几十到百纳米尺寸的微纳单元构成的人工二维结构。常用的制备超表面的方法中，典型光刻工艺虽然可以快速复制掩模图案，但由于衍射极限，不能提供足够的图形分辨率。电子束光刻(EBL)和聚焦离子束(FIB)铣削虽然具有高分辨率，但制备效率较低。Optical metasurfaces are artificial two-dimensional structures composed of micro-nano units with dimensions ranging from tens to hundreds of nanometers. Among the commonly used methods for fabricating metasurfaces, typical photolithography processes can rapidly replicate mask patterns, but cannot provide sufficient pattern resolution due to the diffraction limit. Electron beam lithography (EBL) and focused ion beam (FIB) milling, despite their high resolution, are less efficient in fabrication.
纳米压印与上述方法相比，提高了超表面的制备效率，同时分辨率没有物理极限。其中，热压印应用较为广泛，但对材料的低热膨胀系数和压力收缩系数提出了较高要求，压印过程中需要较高的压力和加热温度，容易造成模板、胶层图形结构的损坏。紫外纳米压印技术解决了热压印中存在的问题，但紫外固化胶中的气泡难以排出，会对微纳结构造成缺陷。根据紫外压印技术提出的卷对卷纳米压印，实现了微纳结构高通量制备。但卷对卷的压印模板是弯曲固定在辊轴上，这样模板上纳米结构的位置精度将降低，影响压印得到的光学超构表面的光学性能。另一方面，通过压印方法只能将模板图形复制到压印胶上，而压印胶的图形结构一般不直接具备功能，需要将此压印胶图形转移到其他功能材料，会增加工艺步骤和难度。Compared with the above methods, nanoimprinting improves the fabrication efficiency of metasurfaces, while the resolution has no physical limit. Among them, hot embossing is widely used, but it puts forward higher requirements for the low thermal expansion coefficient and pressure shrinkage coefficient of the material. During the embossing process, high pressure and heating temperature are required, which is likely to cause damage to the pattern structure of the template and adhesive layer. Ultraviolet nanoimprint technology solves the problems existing in hot embossing, but the bubbles in the ultraviolet curing adhesive are difficult to discharge, which will cause defects in the micro-nano structure. According to the roll-to-roll nanoimprinting proposed by UV imprinting technology, high-throughput fabrication of micro-nanostructures is realized. However, the roll-to-roll imprint template is bent and fixed on the roller, so the positional accuracy of the nanostructures on the template will be reduced, which will affect the optical properties of the imprinted optical metasurface. On the other hand, only the stencil pattern can be copied to the embossing rubber through the embossing method, and the graphic structure of the embossing rubber generally does not directly have functions. It is necessary to transfer the embossing rubber pattern to other functional materials, which will increase the process steps. and difficulty.
综上来看，现有的超表面制备技术的主要难点在于，如何在满足其性能需求的前提下，降低工艺复杂程度，提高器件制备效率和微纳结构图形质量。To sum up, the main difficulty of the existing metasurface preparation technology is how to reduce the complexity of the process and improve the device preparation efficiency and the micro-nano structure pattern quality under the premise of meeting its performance requirements.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本公开提供了一种大口径柔性光学超构表面结构及其加工方法。In view of this, the present disclosure provides a large-diameter flexible optical metasurface structure and a processing method thereof.
根据本公开的一个方面，提供了一种大口径柔性光学超构表面结构的加工方法，包括：According to one aspect of the present disclosure, a method for processing a large-diameter flexible optical metasurface structure is provided, comprising:
将预设图形刻蚀到基底上，以形成模板；etching a preset pattern onto a substrate to form a template;
将混合有高折射率纳米颗粒的紫外固化胶涂覆在模板上，并覆盖一柔性基底，对紫外固化胶边施加压力，边进行紫外光固化；Coating the UV-curable adhesive mixed with high-refractive-index nanoparticles on the template, and covering a flexible substrate, applying pressure to the UV-curable adhesive while performing UV-curing;
固化成型后，将柔性基底与模板分离，以获取大口径柔性光学超构表面结构。After curing and forming, the flexible substrate is separated from the template to obtain a large-diameter flexible optical metasurface structure.
优选地，高折射率纳米颗粒包括氧化钛、氧化铪、氧化锆、氧化锌、氧化铈和硅中的至少一种。Preferably, the high refractive index nanoparticles comprise at least one of titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, ceria and silicon.
优选地，高折射率纳米颗粒的直径不大于50nm。Preferably, the diameter of the high refractive index nanoparticles is no greater than 50 nm.
优选地，柔性基底的材料包括光学透明的聚合物或金属玻璃。Preferably, the material of the flexible substrate comprises an optically clear polymer or metallic glass.
优选地，柔性基底的厚度不大于500μm。Preferably, the thickness of the flexible substrate is not greater than 500 μm.
优选地，紫外光为面光源或线光源。Preferably, the ultraviolet light is a surface light source or a line light source.
根据本公开的另一方面，提供了一种大口径柔性光学超构表面结构，该大口径柔性光学超构表面结构采用如上所述的大口径柔性光学超构表面结构的加工方法制备得到，所述大口径柔性光学超构表面结构能够直接作为光学器件使用。According to another aspect of the present disclosure, a large-aperture flexible optical metasurface structure is provided, and the large-aperture flexible optical metasurface structure is prepared by using the above-mentioned processing method for a large-aperture flexible optical metasurface structure. The large-aperture flexible optical metasurface structure can be directly used as an optical device.
根据本公开的另一方面，提供了一种大口径柔性光学超构表面结构的加工方法，该方法的步骤如下：According to another aspect of the present disclosure, a method for processing a large-diameter flexible optical metasurface structure is provided, and the steps of the method are as follows:
步骤(1)、在基底模板上涂覆光刻胶；Step (1), coating photoresist on the base template;
步骤(2)、通过光刻***进行曝光，然后显影；Step (2), exposing through a photolithography system, and then developing;
步骤(3)、将图形转移至基底材料上，并作为模板；Step (3), the graphics are transferred to the base material, and used as a template;
步骤(4)、通过把混合有高折射率纳米颗粒的紫外固化胶涂覆在模板上并覆盖一层柔性基底，采用辊轴一边施加机械压力一边利用紫外灯 曝光的方式固化紫外固化胶；Step (4), by being mixed with the UV-curable glue of high refractive index nanoparticle coating on template and covering a layer of flexible substrate, adopting roller shaft while applying mechanical pressure while utilizing the mode of UV lamp exposure to cure UV-curing glue;
步骤(5)、然后将柔性基底与模板分离，即可制备出大口径柔性光学超构表面结构。In step (5), the flexible substrate and the template are separated to prepare a large-diameter flexible optical metasurface structure.
进一步地，所述步骤(1)中的光刻胶为电子束光刻胶和紫外光刻胶。Further, the photoresist in the step (1) is electron beam photoresist and ultraviolet photoresist.
进一步地，所述步骤(2)中光刻***为电子束光刻***、紫外超分辨光刻***和紫外超分辨直写***。Further, the lithography system in the step (2) is an electron beam lithography system, an ultraviolet super-resolution lithography system and an ultraviolet super-resolution direct writing system.
进一步地，所述步骤(3)中的图形转移为溶脱剥离、金属辅助化学腐蚀、气体辅助离子束刻蚀和高密度等离子体刻蚀。Further, the pattern transfer in the step (3) is stripping, metal-assisted chemical etching, gas-assisted ion beam etching and high-density plasma etching.
进一步地，所述步骤(4)中高折射率纳米颗粒为氧化钛、氧化哈、氧化锆、氧化锌、氧化铈、硅，高折射率纳米颗粒的直径≤50nm。Further, in the step (4), the high-refractive-index nanoparticles are titanium oxide, zirconia, zirconium oxide, zinc oxide, cerium oxide, and silicon, and the diameter of the high-refractive-index nanoparticles is less than or equal to 50 nm.
进一步地，所述步骤(5)中柔性基底材料为光学透明聚合物和金属玻璃，柔性基底厚度≤500μm；所述紫外光源为面光源和线光源。Further, in the step (5), the flexible base material is optically transparent polymer and metallic glass, and the thickness of the flexible base is ≤500 μm; the ultraviolet light source is a surface light source and a line light source.
与传统的超表面制备方法相比，本公开中的技术方案具有如下优势：Compared with the traditional metasurface preparation method, the technical solution in the present disclosure has the following advantages:
(1)本公开通过将光学超构表面图形刻蚀到基底上以形成模板，并将模板平置于底部，采用辊轴对其上覆盖的柔性基底和中间紫外固化胶边施加压力，边进行紫外光固化，以简单、高效的方式提高了微纳单元图形结构的位置精度和图形尺寸精度。(1) In the present disclosure, a template is formed by etching an optical metasurface pattern on a substrate, and the template is placed flat on the bottom, and a roller is used to apply pressure on the flexible substrate and the intermediate UV-curable glue covered on it, while performing Ultraviolet light curing improves the positional accuracy and pattern size accuracy of the micro-nano unit pattern structure in a simple and efficient way.
(2)本公开通过将高折射率纳米颗粒与紫外固化胶混合，提高了超构表面结构的等效折射率，降低了对模板原始图形高深度的依赖性，从而降低了模板加工难度以及柔性超构表面脱模时存在的图形损伤的可能性，克服了传统方法中由于紫外固化胶折射率低，加工工艺手段有限，得到的超构表面的光学性能偏低的缺陷。(2) The present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the dependence on the high depth of the original pattern of the template, and reduces the processing difficulty and flexibility of the template The possibility of pattern damage when the metasurface is demolded overcomes the defect of low optical properties of the obtained metasurface due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method.
(3)本公开采用紫外光照射固化填充微纳结构的紫外固化胶实现光学超构表面的制备，制备周期短、效率高，而且所制备的大口径柔性光学超构表面结构能够直接作为光学器件使用。(3) The present disclosure adopts ultraviolet light irradiation to cure the ultraviolet curing glue filled with the micro-nano structure to realize the preparation of the optical metasurface. The preparation cycle is short and the efficiency is high, and the prepared large-diameter flexible optical metasurface structure can be directly used as an optical device. use.
附图说明Description of drawings
附图用于更好地理解本方案，不构成对本公开的限定。其中：The accompanying drawings are used for better understanding of the present solution, and do not constitute a limitation to the present disclosure. in:
图1示出了根据本公开实施例的大口径柔性光学超构表面结构的加工方法的流程图；1 shows a flowchart of a method for processing a large-diameter flexible optical metasurface structure according to an embodiment of the present disclosure;
图2-1是基底上旋涂光刻胶的示意图；Figure 2-1 is a schematic diagram of spin-coating photoresist on a substrate;
图2-2是显影后的光刻胶图形的示意图；2-2 is a schematic diagram of the photoresist pattern after development;
图2-3是通过刻蚀传递到模板上的超表面结构示意图；Figure 2-3 is a schematic diagram of the metasurface structure transferred to the template by etching;
图2-4是涂覆紫外固化胶到模板上并覆盖一层柔性基底的示意图；Figure 2-4 is a schematic diagram of applying UV-curable glue to a template and covering a layer of flexible substrate;
图2-5是边采用辊轴压平紫外固化胶边进行紫外光固化的过程示意图；Figure 2-5 is a schematic diagram of the process of UV curing while flattening the UV curing glue with a roller;
图2-6是紫外光固化完成后的结构示意图；Figure 2-6 is a schematic structural diagram after UV curing is completed;
图2-7是将柔性基底与模板分离的过程示意图；2-7 are schematic diagrams of the process of separating the flexible substrate from the template;
图2-8是制备完成的大口径柔性光学超构表面结构的示意图；2-8 are schematic diagrams of the prepared large-aperture flexible optical metasurface structure;
图中：1、柔性基底；2、紫外固化胶；3、高折射率纳米颗粒；4、压紧辊轴；5、光刻胶；6、模板；7、基底；8、紫外光；9、大口径柔性光学超构表面结构。In the figure: 1. Flexible substrate; 2. UV-curable adhesive; 3. Nanoparticles with high refractive index; 4. Press roller; 5. Photoresist; 6. Template; 7. Substrate; 8. Ultraviolet light; 9. Large-aperture flexible optical metasurface structures.
具体实施方式Detailed ways
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本公开作进一步的详细说明。In order to make the objectives, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure will be further described in detail below with reference to the specific embodiments and the accompanying drawings.
需要说明的是，在附图或说明书描述中，相似或相同的部分都使用相同的图号。附图中未绘示或描述的实现方式，为所属技术领域中普通技术人员所知的形式。另外，虽然本文可提供包含特定值的参数的示范，但应了解，参数无需确切等于相应的值，而是可在可接受的误差容限或设计约束内近似于相应的值。此外，以下实施例中提到的方向用语，例如“上”、“下”、“前”、“后”、“左”、“右”等，仅是参考附图的方向。因此，使用的方向用语是用来说明并非用来限制本公开。It should be noted that, in the drawings or descriptions in the specification, the same drawing numbers are used for similar or identical parts. Implementations not shown or described in the drawings are forms known to those of ordinary skill in the art. Additionally, although examples of parameters including specific values may be provided herein, it should be understood that the parameters need not be exactly equal to the corresponding values, but may be approximated within acceptable error tolerances or design constraints. In addition, the directional terms mentioned in the following embodiments, such as "up", "down", "front", "rear", "left", "right", etc., only refer to the directions of the drawings. Accordingly, the directional terms used are illustrative and not limiting of the present disclosure.
正如背景技术所介绍的，现有的超构表面制备方法难以兼顾加工效 率以及超构表面的加工精度(即所制备微纳结构的图形质量)。鉴于此，本公开提供了一种大口径柔性光学超构表面结构的加工方法以及大口径柔性光学超构表面结构，以期至少部分解决上述技术问题。As described in the background art, it is difficult for the existing metasurface preparation methods to take into account both the processing efficiency and the processing accuracy of the metasurface (that is, the pattern quality of the prepared micro-nano structures). In view of this, the present disclosure provides a processing method of a large-aperture flexible optical metasurface structure and a large-aperture flexible optical metasurface structure, in order to at least partially solve the above technical problems.
图1示意性示出了本公开实施例的一种大口径柔性光学超构表面结构的加工方法的流程图。FIG. 1 schematically shows a flow chart of a method for processing a large-diameter flexible optical metasurface structure according to an embodiment of the present disclosure.
如图1所示，大口径柔性光学超构表面结构的加工方法，包括步骤S110～S130。As shown in FIG. 1 , the method for processing a large-diameter flexible optical metasurface structure includes steps S110 to S130.
步骤S110，将预设图形刻蚀到基底上，以形成模板。Step S110, etching the preset pattern on the substrate to form a template.
这里所谓的预设图形是指待刻蚀的超构表面图形结构，也即待制备的超构表面图形结构。根据实际需要，可以选择不同尺寸的超构表面图形作为预设图形，然后可以通过刻蚀的方式将预设图形转移到基底上，以形成模板。The so-called preset pattern here refers to the metasurface pattern structure to be etched, that is, the metasurface pattern structure to be prepared. According to actual needs, metasurface patterns of different sizes can be selected as preset patterns, and then the preset patterns can be transferred to the substrate by etching to form a template.
在本公开实施例中，将预设图形通过刻蚀的方式转移到基底上，可以采用现有的刻蚀方法，例如，离子束刻蚀、电感耦合等离子体刻蚀、反应离子刻蚀等等，可以根据实际需要选择合适的刻蚀方式及刻蚀设备，在此不做限定。In the embodiment of the present disclosure, to transfer the preset pattern to the substrate by etching, an existing etching method can be used, such as ion beam etching, inductively coupled plasma etching, reactive ion etching, etc. , an appropriate etching method and etching equipment can be selected according to actual needs, which is not limited here.
步骤S120，将混合有高折射率纳米颗粒的紫外固化胶涂覆在模板上，并覆盖一柔性基底，对紫外固化胶边施加压力，边进行紫外光固化。In step S120, the UV-curable adhesive mixed with the high-refractive-index nanoparticles is coated on the template and covered with a flexible substrate, and the UV-curable adhesive is subjected to UV light curing while applying pressure.
高折射率纳米颗粒包括但不限于氧化钛、氧化铪、氧化锆、氧化锌、氧化铈、硅。在本公开实施例中，高折射率纳米颗粒可以采用以上所描述的材料中的任意一种，或者其中任意多种的组合，在此不做限定。其中，高折射率纳米颗粒的直径不大于50nm。High refractive index nanoparticles include, but are not limited to, titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, cerium oxide, silicon. In the embodiments of the present disclosure, the high-refractive-index nanoparticles may adopt any one of the above-described materials, or any combination of any of them, which is not limited herein. Wherein, the diameter of the high-refractive-index nanoparticles is not greater than 50 nm.
在本公开实施例中，可以根据实际需要，将一定质量占比(该质量占比是指高折射率纳米颗粒的质量占高折射率纳米颗粒与紫外固化胶混合后的总质量的百分比)的高折射率纳米颗粒与紫外固化胶混合，例如将1％～20％甚至更高比例的高折射率纳米颗粒与紫外固化胶混合。本公开通过将高折射率纳米颗粒与紫外固化胶混合，提高了超构表面结构的等效折射率，降低了对模板原始图形深度的加工难度以及脱模时存在的图形损伤，克服了传统方法中由于紫外固化胶折射率低，加工得到的 超构表面的光学性能偏低的缺陷。In the embodiment of the present disclosure, according to actual needs, a certain mass ratio (the mass ratio refers to the percentage of the mass of the high-refractive-index nanoparticles to the total mass of the high-refractive-index nanoparticles mixed with the UV-curable glue) The high-refractive-index nanoparticles are mixed with the UV-curable adhesive, for example, 1% to 20% or even higher proportions of the high-refractive-index nanoparticles are mixed with the UV-curable adhesive. The present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the processing difficulty of the original pattern depth of the template and the pattern damage during demolding, and overcomes the traditional method Due to the low refractive index of the UV-curable adhesive, the optical properties of the processed metasurface are low.
在一些实施例中，柔性基底的材料包括但不限于光学透明的聚合物或金属玻璃，例如光学透明的聚合物可采用聚对苯二甲酸乙二醇酯(PET)、聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)等。In some embodiments, the material of the flexible substrate includes, but is not limited to, optically transparent polymer or metallic glass, for example, the optically transparent polymer can be polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), etc.
在本公开实施例中，通过柔性基底向紫外固化胶边施加压力，边进行紫外光固化，最终形成超构表面。因此，柔性基底的厚度对于超构表面的质量具有一定的影响。在本实施例中，可以设计柔性基底的厚度不大于500μm，这样既可以保证紫外固化胶具有较好的固化效果，也可以保证超构表面的精度。In the embodiment of the present disclosure, a flexible substrate is used to apply pressure to the UV-curable adhesive, and then UV-curing is performed, and finally a metasurface is formed. Therefore, the thickness of the flexible substrate has a certain influence on the quality of the metasurface. In this embodiment, the thickness of the flexible substrate can be designed not to be greater than 500 μm, which can not only ensure a good curing effect of the UV-curable adhesive, but also ensure the accuracy of the metasurface.
在本公开实施例中，进行紫外光固化的紫外光源例如可以选择为面光源或线光源。In the embodiment of the present disclosure, the ultraviolet light source for ultraviolet curing may be selected, for example, as a surface light source or a line light source.
需要说明的是，上述对于超构表面制备过程中的参数和方法等的举例，仅是为了便于本领域技术人员理解本公开的方案，并非用以限定本公开的保护范围。It should be noted that the above examples of parameters and methods in the preparation process of the metasurface are only for the convenience of those skilled in the art to understand the solution of the present disclosure, and are not intended to limit the protection scope of the present disclosure.
步骤S130，固化成型后，将柔性基底与模板分离，以获取大口径柔性光学超构表面结构。Step S130, after curing and forming, the flexible substrate is separated from the template to obtain a large-diameter flexible optical metasurface structure.
本公开通过将光学超构表面图形刻蚀到基底上以形成模板，并将模板平置于底部，采用辊轴对其上覆盖的柔性基底和中间紫外固化胶边施加压力，边进行紫外光固化，以简单、高效的方式提高了大口径柔性光学超构表面结构的加工精度。另外，本公开将高折射率纳米颗粒与紫外固化胶混合，提高了超构表面结构的等效折射率，降低了对模板原始图形高深度的依赖性，从而降低了模板加工难度以及柔性超构表面脱模时存在的图形损伤的可能性，克服了传统方法中由于紫外固化胶折射率低，加工工艺手段有限，得到的超构表面的光学性能偏低的缺陷。此外，采用本公开实施例中的加工方法所制备的大口径柔性光学超构表面结构，可以直接形成光学器件，而不需要后续的刻蚀传递制程。In the present disclosure, the optical metasurface pattern is etched on the substrate to form a template, and the template is placed on the bottom, and the flexible substrate and the middle UV curing glue covered on the template are pressed by a roller, and the UV curing is carried out at the same time. , the machining accuracy of large-diameter flexible optical metasurface structures is improved in a simple and efficient manner. In addition, the present disclosure mixes high-refractive-index nanoparticles with UV-curable glue, which increases the equivalent refractive index of the metasurface structure and reduces the dependence on the high depth of the original pattern of the template, thereby reducing the difficulty of template processing and the flexibility of metastructures. The possibility of pattern damage when the surface is demolded overcomes the defect that the optical properties of the obtained metasurface are low due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method. In addition, the large-diameter flexible optical metasurface structure prepared by the processing method in the embodiment of the present disclosure can directly form an optical device without the need for a subsequent etching and transfer process.
基于上述大口径柔性光学超构表面结构的加工方法，本公开还提供了一种大口径柔性光学超构表面结构，该大口径柔性光学超构表面结构采用如上所述的大口径柔性光学超构表面结构的加工方法制备得到，该 大口径柔性光学超构表面结构能够直接作为光学器件使用。Based on the above-mentioned processing method of the large-aperture flexible optical metasurface structure, the present disclosure further provides a large-aperture flexible optical metasurface structure, and the large-aperture flexible optical metasurface structure adopts the above-mentioned large-aperture flexible optical metasurface structure The surface structure is prepared by the processing method, and the large-diameter flexible optical metasurface structure can be directly used as an optical device.
本公开实施例中的大口径柔性光学超构表面结构包含有高折射率纳米颗粒，基于该高折射率纳米颗粒，提高了超构表面结构的等效折射率，降低了对模板原始图形高深度的依赖性，从而降低了模板加工难度以及柔性超构表面脱模时存在的图形损伤的可能性，克服了传统方法中由于紫外固化胶折射率低，加工工艺手段有限，得到的超构表面的光学性能偏低的缺陷。The large-diameter flexible optical metasurface structure in the embodiment of the present disclosure includes high-refractive-index nanoparticles, and based on the high-refractive-index nanoparticles, the equivalent refractive index of the metasurface structure is increased, and the high depth of the original pattern of the template is reduced. Therefore, the difficulty of template processing and the possibility of pattern damage when the flexible metasurface is demolded are reduced, which overcomes the traditional method due to the low refractive index of the UV-curable glue and the limited processing means, the obtained metasurface has Defects with low optical performance.
本公开的另一方面，提供了一种大口径柔性光学超构表面结构的加工方法。该方法的步骤如下：In another aspect of the present disclosure, a method for processing a large-diameter flexible optical metasurface structure is provided. The steps of this method are as follows:
步骤(1)、在基底模板上涂覆光刻胶。Step (1), coating photoresist on the base template.
其中，光刻胶例如可以采用电子束光刻胶和紫外光刻胶，在其他实施例中，可以根据实际选择其他类型的光刻胶，在此不做限定。Among them, the photoresist can be, for example, electron beam photoresist and ultraviolet photoresist. In other embodiments, other types of photoresist can be selected according to the actual situation, which is not limited here.
步骤(2)、通过光刻***进行曝光，然后显影。In step (2), exposure is performed through a photolithography system, and then developed.
在本公开实施例中，可以根据光刻方式选择合适的光刻***，例如可以选择电子束光刻***、紫外超分辨光刻***或紫外超分辨直写***，等等，在此不作限定。In the embodiments of the present disclosure, a suitable lithography system can be selected according to the lithography method, for example, an electron beam lithography system, an ultraviolet super-resolution lithography system or an ultraviolet super-resolution direct writing system can be selected, etc., which are not limited herein.
步骤(3)、将图形转移至基底材料上，并作为模板。In step (3), the graphic is transferred to the base material and used as a template.
其中，将超构表面图形转移至基底材料上可以采用溶脱剥离、金属辅助化学腐蚀、气体辅助离子束刻蚀或高密度等离子体刻蚀等方式，在此不做限定。The transfer of the metasurface pattern to the base material can be carried out by means of stripping, metal-assisted chemical etching, gas-assisted ion beam etching, or high-density plasma etching, which is not limited herein.
步骤(4)、通过把混合有高折射率纳米颗粒的紫外固化胶涂覆在模板上并覆盖一层柔性基底，采用辊轴一边施加机械压力一边利用紫外灯曝光的方式固化紫外固化胶。Step (4), by coating the UV-curable adhesive mixed with high-refractive-index nanoparticles on the template and covering it with a layer of flexible substrate, and curing the UV-curable adhesive by exposing the UV-curable adhesive with a roller while applying mechanical pressure.
高折射率纳米颗粒包括但不限于氧化钛、氧化铪、氧化锆、氧化锌、氧化铈、硅。其中，高折射率纳米颗粒的直径不大于50nm。High refractive index nanoparticles include, but are not limited to, titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, cerium oxide, silicon. Wherein, the diameter of the high-refractive-index nanoparticles is not greater than 50 nm.
在本公开实施例中，可以根据实际需要，将一定质量占比(该质量占比是指高折射率纳米颗粒的质量占高折射率纳米颗粒与紫外固化胶混合后的总质量的百分比)的高折射率纳米颗粒与紫外固化胶混合，例如将1％或20％的高折射率纳米颗粒与紫外固化胶混合。In the embodiment of the present disclosure, according to actual needs, a certain mass ratio (the mass ratio refers to the percentage of the mass of the high-refractive-index nanoparticles to the total mass of the high-refractive-index nanoparticles mixed with the UV-curable glue) The high-refractive-index nanoparticles are mixed with the UV-curable glue, eg, 1% or 20% of the high-refractive-index nanoparticles are mixed with the UV-curable glue.
本公开通过将高折射率纳米颗粒与紫外固化胶混合，提高了超构表面结构的等效折射率，降低了对模板原始图形深度的加工难度以及脱模时存在的图形损伤，克服了传统方法中由于紫外固化胶折射率低，加工得到的超构表面的光学性能偏低的缺陷。The present disclosure improves the equivalent refractive index of the metasurface structure by mixing the high-refractive-index nanoparticles with the UV-curable glue, reduces the processing difficulty of the original pattern depth of the template and the pattern damage during demolding, and overcomes the traditional method Due to the low refractive index of the UV-curable adhesive, the optical properties of the processed metasurface are low.
步骤(5)、固化成型后，将柔性基底与模板分离，即可制备出大口径柔性光学超构表面结构。In step (5), after curing and forming, the flexible substrate is separated from the template to prepare a large-diameter flexible optical metasurface structure.
下面将结合实施例1、实施例2以及图2-1至图2-8对本公开实施例的大口径柔性光学超构表面结构的加工方法进行详细介绍。The processing method of the large-aperture flexible optical metasurface structure according to the embodiment of the present disclosure will be described in detail below with reference to Embodiment 1, Embodiment 2 and FIGS. 2-1 to 2-8 .
实施例1：Example 1:
利用本公开实现200mm口径柔性光学超构表面结构制备。The present disclosure realizes the preparation of a 200mm aperture flexible optical metasurface structure.
(1)在直径200mm的硅基底7上旋涂一层200nm厚度的电子束光刻胶5(该过程参见图2-1所示)。(1) Spin-coat a layer of electron beam photoresist 5 with a thickness of 200 nm on a silicon substrate 7 with a diameter of 200 mm (see FIG. 2-1 for this process).
(2)采用电子束光刻***曝光大面积超构表面图形结构，图形口径为180mm，图形周期420nm，图形线宽130nm，曝光完成后进行显影，显影后的光刻胶图形见图2-2所示。(2) Electron beam lithography system is used to expose the large-area metasurface pattern structure. The pattern diameter is 180mm, the pattern period is 420nm, and the pattern line width is 130nm. After exposure, development is performed. The photoresist pattern after development is shown in Figure 2-2. shown.
(3)通过反应离子刻蚀设备将显影后的图形转移至硅基底7，获得压印母板(即模板6，参见图2-3所示)，刻蚀功率50W，刻蚀腔压0.5Pa，SF6流量25SCCM，CHF3流量5SCCM，刻蚀深度150nm。(3) The developed pattern is transferred to the silicon substrate 7 by the reactive ion etching equipment to obtain the imprint master (ie the template 6, see Fig. 2-3), the etching power is 50W, and the etching chamber pressure is 0.5Pa , SF6 flow 25SCCM, CHF3 flow 5SCCM, etching depth 150nm.
(4)将混合有1％质量比二氧化钛纳米颗粒3(粒径21nm)的紫外固化胶2涂敷在压印母板(即模板6)上，并将聚对苯二甲酸乙二醇酯(PET)柔性基底1(厚度100μm)覆盖在其表面，通过压紧辊轴4一边压平紫外固化胶2，紫外光8一边照射固化，完成整个口径的压印和固化，并脱模后得到需要的大口径柔性光学超构表面结构9(上述过程参见图2-4至图2-8所示)。其中，紫外光功率124W，辊轴移动速度3.4mm/s，辊轴下压压力0.2MPa。(4) Coat the UV-curable glue 2 mixed with 1% mass ratio of titanium dioxide nanoparticles 3 (particle size: 21 nm) on the imprint master (ie template 6), and apply polyethylene terephthalate ( PET) flexible substrate 1 (thickness 100μm) is covered on its surface, and the UV curing glue 2 is flattened by the pressing roller 4, and the UV light 8 is irradiated and cured to complete the imprinting and curing of the entire diameter, and after demolding, the required The large-aperture flexible optical metasurface structure 9 (see Figure 2-4 to Figure 2-8 for the above process). Among them, the power of ultraviolet light is 124W, the moving speed of the roller is 3.4mm/s, and the pressing pressure of the roller is 0.2MPa.
实施例2：Example 2:
利用本公开实现8英寸口径柔性光学超构表面结构制备。The present disclosure is used to realize the fabrication of 8-inch aperture flexible optical metasurface structures.
(1)通过磁控溅射设备在直径8英寸的硅基底7上镀一层40nm厚度的铬层(图中未示出)，功率400W，腔压1mTorr。(1) A chromium layer (not shown in the figure) with a thickness of 40 nm was plated on a silicon substrate 7 with a diameter of 8 inches by a magnetron sputtering device, the power was 400 W, and the cavity pressure was 1 mTorr.
(2)在镀有40nm厚度铬层的直径8英寸的硅基底7上旋涂一层80nm厚度的电子束光刻胶5。(2) A layer of electron beam photoresist 5 with a thickness of 80 nm is spin-coated on a silicon substrate 7 with a diameter of 8 inches coated with a chromium layer with a thickness of 40 nm.
(3)采用电子束光刻***进行曝光大面积超构表面图形结构，图形口径为180mm，图形周期450nm，单元图形宽100nm，长330nm，曝光完成后进行显影，显影后的光刻胶图形参考图2-2所示。(3) Electron beam lithography system is used to expose the large-area metasurface pattern structure. The pattern diameter is 180mm, the pattern period is 450nm, the unit pattern width is 100nm, and the length is 330nm. After exposure, development is performed. The photoresist pattern after development is referenced shown in Figure 2-2.
(4)通过离子束刻蚀设备去除暴露出来的铬层，束流150mA，倾斜角度10度。(4) Remove the exposed chromium layer by ion beam etching equipment, the beam current is 150mA, and the inclination angle is 10 degrees.
(5)通过反应离子刻蚀设备去除残余电子束光刻胶，刻蚀功率5W，刻蚀腔压1Pa，O 2流量10SCCM，刻蚀时间5min； (5) remove residual electron beam photoresist by reactive ion etching equipment, etching power 5W, etching chamber pressure 1Pa, O flow 10SCCM , etching time 5min;
(6)通过反应离子刻蚀设备将图形转移至硅基底7，获得压印母板，刻蚀功率100W，刻蚀腔压0.5Pa，SF6流量25SCCM，CHF3流量5SCCM，刻蚀深度720nm。(6) The pattern is transferred to the silicon substrate 7 by reactive ion etching equipment to obtain an imprinted master plate, the etching power is 100W, the etching chamber pressure is 0.5Pa, the flow rate of SF6 is 25SCCM, the flow rate of CHF3 is 5SCCM, and the etching depth is 720nm.
(7)通过去铬液湿法腐蚀去除表面铬层，获得压印母板(即模板6，参见图2-3所示)。(7) The chromium layer on the surface is removed by wet etching with a chromium removing solution to obtain an imprint master (namely, the template 6, as shown in Fig. 2-3).
(8)将混合有20％质量比二氧化钛纳米颗粒3(粒径21nm)的紫外固化胶2涂敷在压印母板(即模板6)上，并将聚对苯二甲酸乙二醇酯(PET)柔性基底1(厚度100μm)覆盖在其表面，通过压紧辊轴4一边压平紫外固化胶2，紫外光8一边照射固化，完成整个口径的压印和固化，并脱模后得到需要的大口径柔性光学超构表面结构9(上述过程参见图2-4至图2-8所示)。其中，紫外光功率184W，辊轴移动速度3.4mm/s，辊轴下压压力0.2MPa。(8) The UV-curable glue 2 mixed with 20% mass ratio of titanium dioxide nanoparticles 3 (particle size: 21 nm) is coated on the imprint master (ie, the template 6), and polyethylene terephthalate ( PET) flexible substrate 1 (thickness 100μm) is covered on its surface, and the UV curing glue 2 is flattened by the pressing roller 4, and the UV light 8 is irradiated and cured to complete the imprinting and curing of the entire diameter, and after demolding, the required The large-aperture flexible optical metasurface structure 9 (see Figure 2-4 to Figure 2-8 for the above process). Among them, the power of ultraviolet light is 184W, the moving speed of the roller is 3.4mm/s, and the pressing pressure of the roller is 0.2MPa.
综上所述，本公开提供了一种大口径柔性光学超构表面结构及其加工方法。本公开通过将光学超构表面图形刻蚀到基底上以形成模板，并将模板平置于底部，采用辊轴对其上覆盖的柔性基底和中间紫外固化胶边施加压力，边进行紫外光固化，从而以简单、高效的方式提高了大口径柔性光学超构表面结构的加工精度，而且所制备的大口径柔性光学超构表面结构能够直接作为光学器件使用。另外，本公开将高折射率纳米颗粒与紫外固化胶混合，提高了超构表面结构的等效折射率，降低了对模板原始图形高深度的依赖性，从而降低了模板加工难度以及柔性超构 表面脱模时存在的图形损伤的可能性，克服了传统方法中由于紫外固化胶折射率低，加工工艺手段有限，得到的超构表面的光学性能偏低的缺陷。In conclusion, the present disclosure provides a large-diameter flexible optical metasurface structure and a processing method thereof. In the present disclosure, the optical metasurface pattern is etched on the substrate to form a template, and the template is placed on the bottom, and the flexible substrate and the middle UV curing glue covered on the template are pressed by a roller, and the UV curing is carried out at the same time. , thereby improving the processing accuracy of the large-aperture flexible optical metasurface structure in a simple and efficient manner, and the prepared large-aperture flexible optical metasurface structure can be directly used as an optical device. In addition, the present disclosure mixes high-refractive-index nanoparticles with UV-curable glue, which increases the equivalent refractive index of the metasurface structure and reduces the dependence on the high depth of the original pattern of the template, thereby reducing the difficulty of template processing and the flexibility of metastructures. The possibility of pattern damage when the surface is demolded overcomes the defect that the optical properties of the obtained metasurface are low due to the low refractive index of the UV-curable adhesive and the limited processing means in the traditional method.
以上对本公开的实施例进行了描述。但是，这些实施例仅仅是为了说明的目的，而并非为了限制本公开的范围。尽管在以上分别描述了各实施例，但是这并不意味着各个实施例中的措施不能有利地结合使用。本公开的范围由所附权利要求及其等同物限定。不脱离本公开的范围，本领域技术人员可以做出多种替代和修改，这些替代和修改都应落在本公开的范围之内。Embodiments of the present disclosure have been described above. However, these examples are for illustrative purposes only, and are not intended to limit the scope of the present disclosure. Although the various embodiments are described above separately, this does not mean that the measures in the various embodiments cannot be used in combination to advantage. The scope of the present disclosure is defined by the appended claims and their equivalents. Without departing from the scope of the present disclosure, those skilled in the art can make various substitutions and modifications, and these substitutions and modifications should all fall within the scope of the present disclosure.

Claims (13)

  1. 一种大口径柔性光学超构表面结构的加工方法，其特征在于，包括：A method for processing a large-diameter flexible optical metasurface structure, characterized by comprising:
    将预设图形刻蚀到基底上，以形成模板；etching a preset pattern onto a substrate to form a template;
    将混合有高折射率纳米颗粒的紫外固化胶涂覆在所述模板上，并覆盖一柔性基底，对所述紫外固化胶边施加压力，边进行紫外光固化；Coating the UV-curable glue mixed with high-refractive-index nanoparticles on the template, covering a flexible substrate, and applying pressure to the UV-curable glue while performing UV-curing;
    固化成型后，将所述柔性基底与所述模板分离，以获取所述大口径柔性光学超构表面结构。After curing and forming, the flexible substrate is separated from the template to obtain the large-diameter flexible optical metasurface structure.
  2. 根据权利要求1所述的大口径柔性光学超构表面结构的加工方法，其特征在于，所述高折射率纳米颗粒包括氧化钛、氧化铪、氧化锆、氧化锌、氧化铈和硅中的至少一种。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the high-refractive-index nanoparticles comprise at least one of titanium oxide, hafnium oxide, zirconium oxide, zinc oxide, cerium oxide and silicon A sort of.
  3. 根据权利要求1或2所述的大口径柔性光学超构表面结构的加工方法，其特征在于，所述高折射率纳米颗粒的直径不大于50nm。The method for processing a large-diameter flexible optical metasurface structure according to claim 1 or 2, wherein the diameter of the high-refractive-index nanoparticles is not greater than 50 nm.
  4. 根据权利要求1所述的大口径柔性光学超构表面结构的加工方法，其特征在于，所述柔性基底的材料包括光学透明的聚合物或金属玻璃。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the material of the flexible substrate comprises optically transparent polymer or metallic glass.
  5. 根据权利要求1所述的大口径柔性光学超构表面结构的加工方法，其特征在于，所述柔性基底的厚度不大于500μm。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the thickness of the flexible substrate is not greater than 500 μm.
  6. 根据权利要求1所述的大口径柔性光学超构表面结构的加工方法，其特征在于，所述紫外光为面光源或线光源。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the ultraviolet light is a surface light source or a line light source.
  7. 一种大口径柔性光学超构表面结构，其特征在于，采用如权利要求1至6中任一项所述的大口径柔性光学超构表面结构的加工方法制备得到，所述大口径柔性光学超构表面结构能够直接作为光学器件使用。A large-aperture flexible optical metasurface structure, characterized in that, the large-aperture flexible optical metasurface structure is prepared by using the processing method for a large-aperture flexible optical metasurface structure according to any one of claims 1 to 6, and the large-aperture flexible optical metasurface structure is obtained. The structured surface structure can be used directly as an optical device.
  8. 一种大口径柔性光学超构表面结构的加工方法，其特征在于，该方法的步骤如下：A method for processing a large-diameter flexible optical metasurface structure, characterized in that the steps of the method are as follows:
    步骤(1)、在基底模板上涂覆光刻胶；Step (1), coating photoresist on the base template;
    步骤(2)、通过光刻***进行曝光，然后显影；Step (2), exposing through a photolithography system, and then developing;
    步骤(3)、将图形转移至基底材料上，并作为模板；Step (3), the graphics are transferred to the base material, and used as a template;
    步骤(4)、通过把混合有高折射率纳米颗粒的紫外固化胶涂覆在模 板上并覆盖一层柔性基底，采用辊轴一边施加机械压力一边利用紫外灯曝光的方式固化紫外固化胶；Step (4), by being mixed with the UV-curable glue of high refractive index nanoparticles and coating on the template and covering one deck of flexible substrates, adopting the roller shaft while applying mechanical pressure while utilizing the mode of UV lamp exposure to cure the UV-curable glue;
    步骤(5)、然后将柔性基底与模板分离，即可制备出大口径柔性光学超构表面结构。In step (5), the flexible substrate and the template are separated to prepare a large-diameter flexible optical metasurface structure.
  9. 根据权利要求1所述的一种大口径柔性光学超构表面结构的加工方法，其特征在于，所述步骤(1)中的光刻胶为电子束光刻胶和紫外光刻胶。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the photoresist in the step (1) is electron beam photoresist and ultraviolet photoresist.
  10. 根据权利要求1所述的一种大口径柔性光学超构表面结构的加工方法，其特征在于，所述步骤(2)中光刻***为电子束光刻***、紫外超分辨光刻***和紫外超分辨直写***。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the lithography system in the step (2) is an electron beam lithography system, an ultraviolet super-resolution lithography system, and an ultraviolet super-resolution lithography system. Super-resolution direct writing system.
  11. 根据权利要求1所述的一种大口径柔性光学超构表面结构的加工方法，其特征在于，所述步骤(3)中的图形转移为溶脱剥离、金属辅助化学腐蚀、气体辅助离子束刻蚀和高密度等离子体刻蚀。The method for processing a large-diameter flexible optical metasurface structure according to claim 1, wherein the pattern transfer in the step (3) is stripping, metal-assisted chemical corrosion, and gas-assisted ion beam etching. and high-density plasma etching.
  12. 根据权利要求1所述的一种大口径柔性光学超构表面器件的加工方法，其特征在于，所述步骤(4)中高折射率纳米颗粒为氧化钛、氧化哈、氧化锆、氧化锌、氧化铈、硅，高折射率纳米颗粒的直径≤50nm。The method for processing a large-diameter flexible optical metasurface device according to claim 1, wherein the high-refractive-index nanoparticles in the step (4) are titanium oxide, titanium oxide, zirconium oxide, zinc oxide, oxide Cerium, silicon, high refractive index nanoparticles with diameter ≤50nm.
  13. 根据权利要求1所述的一种大口径柔性光学超构表面器件的加工方法，其特征在于，所述步骤(4)中柔性基底材料为光学透明聚合物和金属玻璃，柔性基底厚度≤500μm；所述紫外光源为面光源和线光源。The method for processing a large-diameter flexible optical metasurface device according to claim 1, wherein in the step (4), the flexible base material is optically transparent polymer and metallic glass, and the thickness of the flexible base is ≤500 μm; The ultraviolet light sources are surface light sources and line light sources.
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