方法领域method field
本发明属于材料科学技术领域，具体涉及一种具有宽频带、全方位减反射性质的多孔半球形阵列膜及其制备方法。The invention belongs to the technical field of material science, and specifically relates to a porous hemispherical array film with broadband and omnidirectional anti-reflection properties and a preparation method thereof.
背景方法background method
在基底上的减反射膜层吸引了人们众多的注意力，因为它在照相机镜头[1]、太阳能电池[2]、LEDs[3]、光检测器[4]、光传感和图像[5,6]等应用中发挥了巨大的作用。大量的硅[7]、金属氧化物[8]、聚合物[9]和碳[10]等材料制备的微纳锥和柱结构具有很好的减反射性能。最近，人们发现金属纳微结构与入射光相互作用产生的表面等离子体共振[11]具有很好的减反射性质，称之为等离子减反射。随后，一些新型的等离子体减反射膜层被制备出来并且对其宽频带、全方位减反射性能进行了研究[12]。Anti-reflection coatings on substrates have attracted much attention because of their applications in camera lenses[1] , solar cells[2] , LEDs[3] , photodetectors[4] , light sensing and imaging[5 ],6] and other applications have played a huge role. The micro-nano-cone and pillar structures prepared by a large number of materials such as silicon[7] , metal oxide[8] , polymer[9] and carbon[10] have good anti-reflection properties. Recently, it was found that the surface plasmon resonance generated by the interaction between metal nanostructures and incident light[11] has good anti-reflection properties, which is called plasmon anti-reflection. Subsequently, some new plasma anti-reflection coatings were prepared and their broadband and omni-directional anti-reflection properties were studied[12] .
但是对这种等离子体减反射膜层在弯曲表面上的制备还没有实现。为满足更多的潜在的应用，还需要对等离子体减反射性质有更深层次的理解和进一步的探索。其中一个特别的挑战就是在弯曲表面上制备宽频带、全方位等离子体减反射膜层。这种等离子体膜可以在光电器件和显示器件中发挥特殊的作用。But the preparation of this plasma anti-reflection coating layer on the curved surface has not been realized yet. In order to meet more potential applications, a deeper understanding and further exploration of the anti-reflective properties of plasmons are needed. One particular challenge is the fabrication of broadband, omnidirectional plasmonic antireflection coatings on curved surfaces. This plasmonic film can play a special role in optoelectronic devices and display devices.
发明内容Contents of the invention
本发明的目的是提供一种具有宽频带、全方位减反射性质的多孔半球形阵列膜及其制备方法。The object of the present invention is to provide a porous hemispherical array film with broadband and omnidirectional anti-reflection properties and a preparation method thereof.
本发明利用掩模刻蚀方法、物理气相沉积方法、胶体自组装方法等，整个过程操作简便，过程低耗清洁，可控性高。通过控制刻蚀的时间和条件，可以制备不同孔径大小和深度的多孔半球形阵列，从而实现其减反射性质。The invention utilizes a mask etching method, a physical vapor deposition method, a colloid self-assembly method, etc., and the whole process is easy to operate, low in consumption and clean, and highly controllable. By controlling the etching time and conditions, porous hemispherical arrays with different pore sizes and depths can be prepared to achieve its anti-reflection properties.
本发明以实现多孔半球形阵列膜为例，实现具有宽频带、全方位减反射性质的多孔半球形阵列膜的制备，具体步骤如下：The present invention takes the realization of a porous hemispherical array membrane as an example to realize the preparation of a porous hemispherical array membrane with broadband and omnidirectional anti-reflection properties. The specific steps are as follows:
1)取亲水处理过的基底(平整基底：玻璃、石英片、硅片；弯曲基底：聚二甲基硅氧烷(PDMS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)等)，以1000～3000rpm的转速将10～100mg/mL的聚苯乙烯(PS)的甲苯溶液旋涂到该基底上，然后将该基底放在室温环境中自然干燥，从而在基底上得到厚度为200～2000nm的聚苯乙烯/甲苯薄膜；1) Take a hydrophilic treated substrate (flat substrate: glass, quartz wafer, silicon wafer; curved substrate: polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polypropylene (PP) etc.), spin-coat a toluene solution of 10-100 mg/mL polystyrene (PS) onto the substrate at a speed of 1000-3000 rpm, and then place the substrate at room temperature to dry naturally, so that the A polystyrene/toluene film with a thickness of 200-2000nm was obtained;
2)在1～5mL、浓度为1～20wt％、直径为0.2～0.8μm的聚苯乙烯微球的去离子水分散液中加入1～3mL的去离子水，在9000～14000rpm转速下离心3～5分钟，在离心后得到的固态物中再加入1～3mL去离子水并再次进行离心，重复加入去离子水和离心过程4～7次；在最后离心得到的固态物中加入1～5mL体积比为1：1的乙醇和去离子水的混合液，在9000～14000rpm转速下离心5～10分钟，重复加入乙醇和去离子水混合液和离心过程4～20次，在最后离心得到的固态物中再加入1～5mL体积比为1：1的乙醇和去离子水的混合液，从而得到疏水聚苯乙烯微球的乙醇和去离子水分散液；用一次性注射器吸取0.1～0.5mL疏水聚苯乙烯微球的乙醇和去离子水分散液，滴加到盛有去离子水的容器中，疏水聚苯乙烯微球在空气-去离子水的气液界面排列为单层，再加入50～200μL、浓度为1～10wt％的十二烷基磺酸钠表面活性剂使疏水聚苯乙烯微球彼此紧密排列，用亲水处理过的基底(平整基底：玻璃、石英片、硅片；弯曲基底：聚二甲基硅氧烷(PDMS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)等)将单层紧密排列的疏水聚苯乙烯微球托起，放在倾斜面上自然干燥，从而在基底上得到二维有序的直径为0.2～0.8μm单层紧密排列的疏水聚苯乙烯微球阵列；2) Add 1 to 3 mL of deionized water to 1 to 5 mL of deionized water dispersion of polystyrene microspheres with a concentration of 1 to 20 wt % and a diameter of 0.2 to 0.8 μm, and centrifuge at 9000 to 14000 rpm for 3 ~5 minutes, add 1~3mL deionized water to the solid obtained after centrifugation and centrifuge again, repeat the process of adding deionized water and centrifuging 4~7 times; add 1~5mL to the solid obtained by final centrifugation The mixture of ethanol and deionized water with a volume ratio of 1:1 is centrifuged at 9000-14000rpm for 5-10 minutes, and the mixture of ethanol and deionized water and centrifugation are repeated for 4-20 times, and finally obtained by centrifugation Add 1-5mL of a mixture of ethanol and deionized water with a volume ratio of 1:1 to the solid to obtain a dispersion of hydrophobic polystyrene microspheres in ethanol and deionized water; use a disposable syringe to draw 0.1-0.5mL The ethanol and deionized water dispersion of hydrophobic polystyrene microspheres is added dropwise to a container filled with deionized water. The hydrophobic polystyrene microspheres are arranged in a single layer at the air-deionized water gas-liquid interface, and then added 50～200μL, the concentration is 1～10wt% sodium dodecylsulfonate surfactant makes hydrophobic polystyrene microspheres closely arrange each other, with the substrate (flat substrate: glass, quartz wafer, silicon wafer) that has been treated with hydrophilic ; Curved substrate: polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polypropylene (PP), etc.) hold up a single layer of closely arranged hydrophobic polystyrene microspheres, Put it on an inclined surface to dry naturally, so as to obtain a two-dimensional ordered array of hydrophobic polystyrene microspheres with a diameter of 0.2-0.8 μm and a single layer closely arranged on the substrate;
在1～5mL、浓度为1～20wt％、直径为2～5μm的聚苯乙烯微球的去离子水分散液中加入1～3mL的去离子水，在4000～8800rpm转速下离心3～5分钟，在离心后得到的固态物中再加入1～3mL去离子水并再次进行离心，重复加入去离子水和离心过程4～7次；在最后离心得到的固态物中加入1～5mL体积比为1：1的乙醇和去离子水的混合液，在4000～8800rpm转速下离心5～10分钟，重复加入乙醇和去离子水混合液和离心过程4～20次，在最后离心得到的固态物中再加入1～5mL体积比为1：1的乙醇和去离子水的混合液，从而得到疏水聚苯乙烯微球的乙醇和去离子水分散液；用一次性注射器吸取0.1～0.5mL疏水聚苯乙烯微球的乙醇和去离子水分散液，滴加到盛有去离子水的容器中，疏水聚苯乙烯微球在空气-去离子水的气液界面排列为单层，再加入50～200μL、浓度为1～10wt％的十二烷基磺酸钠表面活性剂使疏水聚苯乙烯微球彼此紧密排列，用步骤1)制备的聚苯乙烯/甲苯薄膜基底将单层紧密排列的疏水聚苯乙烯微球托起，放在倾斜面上自然干燥，从而在基底上得到二维有序的直径为2～5μm单层紧密排列的疏水聚苯乙烯微球阵列；Add 1 to 3 mL of deionized water to 1 to 5 mL of deionized water dispersion of polystyrene microspheres with a concentration of 1 to 20 wt % and a diameter of 2 to 5 μm, and centrifuge at 4000 to 8800 rpm for 3 to 5 minutes , add 1 to 3 mL of deionized water to the solid obtained after centrifugation and centrifuge again, repeat the process of adding deionized water and centrifuging for 4 to 7 times; 1:1 mixture of ethanol and deionized water, centrifuge at 4000-8800rpm for 5-10 minutes, repeat the process of adding ethanol and deionized water mixture and centrifuging for 4-20 times, in the final centrifuged solid Then add 1-5mL of ethanol and deionized water mixture with a volume ratio of 1:1 to obtain the ethanol and deionized water dispersion of hydrophobic polystyrene microspheres; use a disposable syringe to draw 0.1-0.5mL of hydrophobic polystyrene Add the ethanol and deionized water dispersion of ethylene microspheres dropwise into a container filled with deionized water. The hydrophobic polystyrene microspheres are arranged in a single layer at the gas-liquid interface of air-deionized water, and then add 50-200μL 1. The sodium dodecylsulfonate surfactant with a concentration of 1 to 10 wt% makes the hydrophobic polystyrene microspheres closely arranged with each other, and the hydrophobic polystyrene microspheres arranged in a single layer are closely arranged with the polystyrene/toluene film substrate prepared in step 1). Styrene microspheres are held up and placed on an inclined surface to dry naturally, so as to obtain a two-dimensional orderly array of hydrophobic polystyrene microspheres with a diameter of 2-5 μm and a single layer closely arranged on the substrate;
3)将步骤2)制得的二维有序的直径为0.2～0.8μm单层紧密排列的疏水聚苯乙烯微球阵列基底置于反应性等离子体刻蚀机中，在刻蚀气压为5～10mTorr、刻蚀温度为10～20℃、氧气流速为10～50sccm、刻蚀功率为30～100W的条件下，刻蚀100～300秒；在这个过程中，聚苯乙烯微球被刻蚀逐渐变小；然后将刻蚀过的样品放置在真空蒸发镀膜设备的样品台上，样品法线与沉积方向的夹角(即入射角)为0～50°，在5×10-4～1×10-3Pa的真空度下热蒸发沉积金属金，沉积速度为沉积金膜的厚度为50～100nm；将热蒸发沉积完金膜的基底放入甲苯中超声3～10min，超声功率为40～100W，除去聚苯乙烯微球得到周期为0.2～0.8μm、孔径为100～200nm的金纳米孔膜阵列基底；3) Place the two-dimensional ordered hydrophobic polystyrene microsphere array substrate with a diameter of 0.2-0.8 μm in a single layer closely arranged in a reactive plasma etching machine, and the etching pressure is 5 ～10mTorr, etching temperature 10～20℃, oxygen flow rate 10～50sccm, etching power 30～100W, etch for 100～300 seconds; during this process, polystyrene microspheres are etched gradually become smaller; then place the etched sample on the sample stage of the vacuum evaporation coating equipment, the angle between the sample normal and the deposition direction (that is, the angle of incidence) is 0-50°, at 5×10-4 ～1 Thermal evaporation deposition of metallic gold under a vacuum degree of ×10-3 Pa, the deposition rate is The thickness of the deposited gold film is 50-100nm; put the substrate on which the thermally evaporated gold film has been deposited into toluene for 3-10 minutes, and the ultrasonic power is 40-100W, and remove the polystyrene microspheres to obtain a period of 0.2-0.8μm 100-200nm gold nanoporous membrane array substrate;
4)将步骤2)制得的二维有序的直径为2～5μm单层紧密排列的疏水聚苯乙烯微球阵列基底置于80～110℃烘箱中0.1～1小时，然后取出待用；4) Place the two-dimensional ordered hydrophobic polystyrene microsphere array substrate with a diameter of 2-5 μm in a single layer closely arranged in step 2) in an oven at 80-110° C. for 0.1-1 hour, and then take it out for use;
5)将步骤3)制得的金纳米孔膜阵列基底倾斜后慢慢地浸入到用水稀释了10～20倍的氢氟酸的水溶液中(氢氟酸为商业化分析纯产品，质量分数为40％)，使金纳米孔膜阵列脱离基底而悬浮在水/空气界面；然后用步骤4)得到的基底轻轻捞起悬浮的金纳米孔膜阵列，在室温环境中自然风干；5) Slowly immerse the base of the gold nanoporous membrane array prepared in step 3) into an aqueous solution of hydrofluoric acid diluted 10 to 20 times with water (hydrofluoric acid is a commercial analytically pure product with a mass fraction of 40%), the gold nanoporous membrane array is separated from the substrate and suspended on the water/air interface; then gently scoop up the suspended gold nanoporous membrane array with the substrate obtained in step 4), and air-dry naturally at room temperature;
6)将步骤5)制得的基底置于反应性等离子体刻蚀机中，在刻蚀气压为5～10mTorr、刻蚀温度为10～20℃、氧气流速为10～50sccm、刻蚀功率为30～100W的条件下，刻蚀100～300秒；在这个过程中，以金纳米孔膜阵列为掩膜，将下面的直径为2～5μm单层紧密排列的疏水聚苯乙烯微球阵列刻蚀成多孔形貌，再用金刻蚀剂除去金纳米孔膜阵列；然后将刻蚀过的样品放置在真空蒸发镀膜设备的样品台上，样品法线与沉积方向的夹角(即入射角)为0～50°，在5×10-4～1×10-3Pa的真空度下热蒸发沉积金属银，沉积速度为沉积银膜的厚度为50～100nm，得到本发明所述的一种具有宽频带、全方位减反射性质的多孔半球形阵列膜；6) Place the substrate prepared in step 5) in a reactive plasma etching machine, under an etching pressure of 5-10 mTorr, an etching temperature of 10-20° C., an oxygen flow rate of 10-50 sccm, and an etching power of Under the condition of 30-100W, etch for 100-300 seconds; in this process, use the gold nanoporous membrane array as a mask, and engrave the hydrophobic polystyrene microsphere array with a diameter of 2-5 μm in a single layer closely arranged below. etched into a porous morphology, and then remove the gold nanoporous membrane array with a gold etchant; then place the etched sample on the sample stage of the vacuum evaporation coating equipment, and the angle between the sample normal and the deposition direction (ie, the incident angle ) is 0～50°, thermal evaporation deposits metal silver under vacuum degree of 5×10-4 ～1×10-3 Pa, and the deposition rate is The thickness of the deposited silver film is 50-100nm, and a porous hemispherical array film with broadband and omni-directional anti-reflection properties according to the present invention is obtained;
另取步骤4得到的样品放置在真空蒸发镀膜设备的样品台上，样品法线与沉积方向的夹角(即入射角)为0～50°，在5×10-4～1×10-3Pa的真空度下进行热蒸发沉积金属银，沉积速度为沉积厚度为50～100nm，得到半球壳阵列膜，作为参比样品；In addition, take the sample obtained in step 4 and place it on the sample stage of the vacuum evaporation coating equipment. The angle between the normal line of the sample and the deposition direction (that is, the angle of incidence) is 0 to 50°, and it is between 5×10-4 and 1×10-3 Under the vacuum degree of Pa, metal silver is deposited by thermal evaporation, and the deposition rate is The deposition thickness is 50-100nm to obtain a hemispherical shell array film as a reference sample;
将步骤6)制备的样品放置在光纤光谱仪的样品台上，测试其反射性质；改变入射光的方向，测试不同方向入射光的反射性质。Place the sample prepared in step 6) on the sample stage of the fiber optic spectrometer to test its reflective properties; change the direction of the incident light to test the reflective properties of the incident light in different directions.
将步骤6)制备的样品放置在与屏幕垂直，水平距离屏幕10～30cm的位置。然后用一束波长为635nm的激光照射，证明其在实际应用中的减反射性质。Place the sample prepared in step 6) vertically to the screen and 10-30 cm horizontally away from the screen. It was then irradiated with a laser beam with a wavelength of 635nm to demonstrate its anti-reflection properties for practical applications.
步骤1)所述的平整基底为玻璃片、石英片、硅片；弯曲基底为聚二甲基硅氧烷(PDMS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)等。基底的亲水处理是将基底放入质量分数98％的浓硫酸和质量分数30％的过氧化氢的混合溶液中水浴加热至70～90℃，保持3～8小时，然后用去离子水反复洗涤，氮气吹干；浓硫酸溶液和过氧化氢溶液的体积比为7：3。The flat substrate described in step 1) is a glass sheet, a quartz sheet, a silicon sheet; the curved substrate is polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polypropylene (PP) Wait. The hydrophilic treatment of the substrate is to put the substrate into a mixed solution of concentrated sulfuric acid with a mass fraction of 98% and hydrogen peroxide with a mass fraction of 30% and heat it in a water bath to 70-90°C, keep it for 3-8 hours, and then use deionized water repeatedly Wash and dry with nitrogen; the volume ratio of concentrated sulfuric acid solution and hydrogen peroxide solution is 7:3.
本发明各个步骤操作简单，可控性强，在制备的多孔半球形阵列上有多孔层次结构，使样品表面随着入射光角度增加反射率减小，从而在弯曲的半球形表面上得到宽频带、全方位减反射等离子体薄膜。制备得到的层次等离子体结构，可以应用到光电器件、显示器件等实际应用中。Each step of the present invention is easy to operate and has strong controllability. There is a porous hierarchical structure on the prepared porous hemispherical array, so that the reflectance of the sample surface decreases with the increase of the incident light angle, thereby obtaining a broadband on the curved hemispherical surface. , All-round anti-reflection plasma film. The prepared hierarchical plasma structure can be applied to practical applications such as optoelectronic devices and display devices.
附图说明Description of drawings
图1为制备多孔半球形阵列的流程图；图中标示了各种利用的材料和主要操作步骤；其中，基底1、聚苯乙烯/甲苯薄膜2、330nm聚苯乙烯微球3、3μm聚苯乙烯微球4、金纳米孔膜5、多孔半球形阵列6、银膜7；Figure 1 is a flow chart for the preparation of porous hemispherical arrays; the various materials used and the main operating steps are marked in the figure; among them, substrate 1, polystyrene/toluene film 2, 330nm polystyrene microspheres 3, 3 μm polystyrene Ethylene microspheres 4, gold nanoporous membranes 5, porous hemispherical arrays 6, silver membranes 7;
图2为多孔半球形阵列扫描电子显微镜(SEM)照片(A顶视图、B侧视图和45°倾斜图(图B中的插图)、C(A局部放大1倍图，标尺为1μm))；D多孔半球形结构单元的结构参数示意(聚苯乙烯微球4、银膜7，D代表多孔半球形阵列膜的周期(即大球尺寸2～5μm)、P代表金纳米孔膜掩板的周期(即小球尺寸0.2～0.8nm)、H代表刻蚀孔的深度(100～200nm)、d代表多空半球形阵列膜的孔直径(100～200nm))；Figure 2 is a scanning electron microscope (SEM) photo of a porous hemispherical array (A top view, B side view and 45° tilted view (inset in Figure B), C (A local magnified 1 times, the scale bar is 1 μm)); D shows the structural parameters of the porous hemispherical structural unit (polystyrene microsphere 4, silver film 7, D represents the period of the porous hemispherical array film (that is, the size of the large ball is 2 ~ 5 μm), P represents the gold nanoporous film mask Period (that is, the size of the ball is 0.2-0.8nm), H represents the depth of the etched hole (100-200nm), d represents the hole diameter of the porous hemispherical array membrane (100-200nm));
图3用光纤光谱仪测得的光谱图。(A黑线表示半球壳阵列膜的反射光谱，红线代表多孔半球形阵列膜的反射光谱，说明多孔半球形阵列膜的减反性能在波长范围为400～1000nm之间的宽频带都很好、B不同角度的入射光时，多孔半球形阵列膜的反射光谱，说明多孔半球形阵列膜具有全方位的减反性能)；Figure 3 is the spectrogram measured with a fiber optic spectrometer. (A black line represents the reflectance spectrum of the hemispherical shell array film, and the red line represents the reflectance spectrum of the porous hemispherical array film, indicating that the antireflection performance of the porous hemispherical array film is all very good in the broadband between 400～1000nm in the wavelength range, During the incident light of B different angles, the reflection spectrum of the porous hemispherical array film shows that the porous hemispherical array film has a full range of anti-reflection properties);
图4为多孔半球形阵列膜的减反射性质示例图，对应是实施例11。(A激光(波长为635nm)照射到常规银镜上，可以看到屏幕(屏幕与银镜的位置关系为垂直，水平距离10～30cm)上反射光斑很强、B激光照射到半球壳阵列膜上可以看到屏幕上反射光斑很弱，说明多孔半球形阵列膜的减反性能、C激光一半照射在银镜上，另一半照射在多孔半球形阵列膜上，可以看到照射银镜部分的屏幕上反射光斑很强，而照射多孔半球形阵列膜部分的屏幕上反射光斑几乎看不到，通过对比说明多孔半球形阵列膜的减反性能、D激光完全照射在多孔半球形阵列膜上，可以看到屏幕上反射光斑几乎看不到，说明多孔半球形阵列膜的减反性能非常好)。FIG. 4 is an illustration of the anti-reflection property of the porous hemispherical array film, corresponding to Example 11. FIG. (A laser (wavelength: 635nm) is irradiated on the conventional silver mirror, and the reflection spot on the screen (the positional relationship between the screen and the silver mirror is vertical, and the horizontal distance is 10-30cm) can be seen, and B laser is irradiated on the hemispherical shell array film It can be seen that the reflection spot on the screen is very weak, indicating the anti-reflection performance of the porous hemispherical array film. Half of the C laser is irradiated on the silver mirror, and the other half is irradiated on the porous hemispherical array film. It can be seen that the silver mirror is irradiated. The reflection spot on the screen is very strong, but the reflection spot on the screen that irradiates the porous hemispherical array film is almost invisible. The anti-reflection performance of the porous hemispherical array film is illustrated by comparison. The D laser is completely irradiated on the porous hemispherical array film. It can be seen that the reflected light spots on the screen are almost invisible, indicating that the anti-reflection performance of the porous hemispherical array film is very good).
具体实施方式detailed description
实施例1：亲水玻璃片的制备Embodiment 1: the preparation of hydrophilic glass sheet
所用玻璃片用玻璃刀裁至2.5cm长，3.5cm宽大小，放入浓硫酸(质量分数98％)与过氧化氢(质量分数30％)的混合溶液(体积比为7：3)中水浴加热至80℃，保持5小时，即得到亲水玻璃片；将混合溶液倒入废液瓶中，得到的玻璃片用去离子水反复洗涤4次，并用氮气吹干。The glass sheet used was cut to 2.5cm long and 3.5cm wide with a glass knife, and placed in a mixed solution (volume ratio of 7:3) of concentrated sulfuric acid (98% by mass fraction) and hydrogen peroxide (30% by mass fraction) in a water bath Heat to 80°C and keep for 5 hours to obtain hydrophilic glass flakes; pour the mixed solution into a waste liquid bottle, wash the obtained glass flakes with deionized water four times, and dry them with nitrogen.
实施例2：聚苯乙烯PS/甲苯薄膜的制备Embodiment 2: the preparation of polystyrene PS/toluene film
将聚苯乙烯微球溶于甲苯中，配制成浓度为10mg/mL的溶液。利用台式匀胶机以3000rpm的转速旋涂30秒，旋涂到亲水玻璃片上，然后将其放置在室温环境中自然风干，得到200nm厚的聚苯乙烯PS/甲苯薄膜。Dissolve polystyrene microspheres in toluene to prepare a solution with a concentration of 10 mg/mL. Spin-coat at a speed of 3000rpm for 30 seconds with a desktop glue homogenizer, spin-coat onto a hydrophilic glass sheet, and then place it at room temperature to air-dry naturally to obtain a 200nm thick polystyrene PS/toluene film.
实施例3：疏水聚苯乙烯微球的制备Embodiment 3: Preparation of hydrophobic polystyrene microspheres
在常温下，在1mL、5wt％、直径为330nm的聚苯乙烯微球水分散液中加入3mL去离子水，用14000rpm转速离心5分钟，吸取上层清液，在遗留下的固态物中再加入3mL去离子水并再次进行离心，此后重复此过程7次。在最后一次吸取上层清液之后，在固态物中加入1mL的乙醇和1mL去离子水的混合液，用14000rpm转速离心5分钟，吸取上层清液，然后在遗留的固态物中再加入相同的乙醇和去离子水的混合液并用相同的方法离心，此后重复此离心过程16次，在最后一次吸取上层清液后，在固态物中最后加入1mL乙醇和1mL去离子水，得到疏水的10wt％的直径为330nm聚苯乙烯微球的乙醇和去离子水的分散液；At room temperature, add 3 mL of deionized water to 1 mL of 5 wt % polystyrene microsphere dispersion with a diameter of 330 nm, centrifuge at 14,000 rpm for 5 minutes, absorb the supernatant, and add 3 mL of deionized water and centrifuged again, after which the process was repeated 7 times. After absorbing the supernatant for the last time, add a mixture of 1 mL of ethanol and 1 mL of deionized water to the solid, centrifuge at 14,000 rpm for 5 minutes, absorb the supernatant, and then add the same ethanol to the remaining solid The mixed solution with deionized water was centrifuged in the same way, and then this centrifugation process was repeated 16 times. After the supernatant was drawn for the last time, 1 mL of ethanol and 1 mL of deionized water were finally added to the solid to obtain a hydrophobic 10 wt % Ethanol and deionized water dispersion of polystyrene microspheres with a diameter of 330nm;
在常温下，在1mL、5wt％、直径为3μm的聚苯乙烯微球水分散液中加入3mL去离子水，分别用8000rpm转速离心5分钟，吸取上层清液，在遗留下的固态物中再加入3mL去离子水并再次进行离心，此后重复此过程7次。在最后一次吸取上层清液之后，在固态物中加入1mL的乙醇和1mL去离子水，用8000rpm转速离心5分钟，吸取上层清液，然后在遗留的固态物中再加入相同的乙醇和去离子水的混合液并用相同的方法离心，此后重复此离心过程16次，在最后一次吸取上层清液后，在固态物中最后加入1mL乙醇和1mL去离子水，得到疏水的10wt％的直径为3μm聚苯乙烯微球乙醇和去离子水的分散液。At room temperature, add 3mL deionized water to 1mL, 5wt%, polystyrene microsphere dispersion with a diameter of 3μm, centrifuge at 8000rpm for 5 minutes, absorb the supernatant, and redistribute it in the remaining solid matter. 3 mL of deionized water was added and centrifuged again, after which the process was repeated 7 times. After absorbing the supernatant for the last time, add 1 mL of ethanol and 1 mL of deionized water to the solid matter, centrifuge at 8000 rpm for 5 minutes, absorb the supernatant, and then add the same ethanol and deionized water to the remaining solid matter The water mixture was centrifuged in the same way, and the centrifugation process was repeated 16 times thereafter. After the last suction of the supernatant, 1 mL of ethanol and 1 mL of deionized water were finally added to the solid to obtain a hydrophobic 10 wt% with a diameter of 3 μm. Dispersion of polystyrene microspheres in ethanol and deionized water.
实施例4：六方紧密堆积的单层聚苯乙烯胶体晶体的制备Example 4: Preparation of hexagonal close-packed monolayer polystyrene colloidal crystals
用一次性注射器吸取0.2mL实施例3制备的直径为330nm的疏水聚苯乙烯微球的乙醇水分散液，缓慢滴到培养皿的空气-去离子水的界面上，静置片刻，沿着培养皿一侧加入50μL浓度为10wt％的十二烷基硫酸钠的水溶液，聚苯乙烯微球会随之形成六方紧密堆积的单层。以亲水玻璃片为基底，伸入到水面以下，从紧密的单层聚苯乙烯微球下方缓慢向上提起，置于斜面自然干燥，从而在玻璃基底上得到直径为330nm单层紧密堆积的聚苯乙烯胶体晶体；Use a disposable syringe to draw 0.2mL of the ethanol water dispersion of hydrophobic polystyrene microspheres with a diameter of 330nm prepared in Example 3, slowly drop it onto the air-deionized water interface of the culture dish, let it stand for a while, along the culture Add 50 μL of 10 wt% sodium lauryl sulfate aqueous solution to one side of the dish, and the polystyrene microspheres will form a hexagonal close-packed monolayer. With the hydrophilic glass sheet as the base, it extends below the water surface, slowly lifts up from the bottom of the compact single-layer polystyrene microspheres, and puts it on an inclined plane to dry naturally, so that a single-layer tightly packed polystyrene microsphere with a diameter of 330nm is obtained on the glass substrate. Styrene colloidal crystals;
用一次性注射器吸取0.2mL实施例3制备的直径为3μm的疏水聚苯乙烯微球的乙醇水分散液，缓慢滴到培养皿的空气-去离子水的界面上，静置片刻，沿着培养皿一侧加入50μL浓度为10wt％的十二烷基硫酸钠的水溶液，聚苯乙烯微球会随之形成六方紧密堆积的单层。以实施例2制备的旋涂有PS/甲苯的玻璃片为基底，伸入到水面以下，从紧密的单层聚苯乙烯微球下方缓慢向上提起，置于斜面自然干燥，从而在PS/甲苯玻璃基底上得到3μm单层紧密堆积的聚苯乙烯胶体晶体。Use a disposable syringe to draw 0.2 mL of the ethanol water dispersion of hydrophobic polystyrene microspheres with a diameter of 3 μm prepared in Example 3, slowly drop it onto the air-deionized water interface of the petri dish, let it stand for a while, Add 50 μL of 10 wt% sodium lauryl sulfate aqueous solution to one side of the dish, and the polystyrene microspheres will form a hexagonal close-packed monolayer. Spin-coated with PS/toluene prepared in Example 2 as the substrate, extend below the water surface, slowly lift up from the bottom of the tight monolayer polystyrene microspheres, and place it on an inclined plane to dry naturally, so that the PS/toluene A 3 μm monolayer closely packed polystyrene colloidal crystals were obtained on the glass substrate.
实施例5：金纳米孔膜阵列的制备Embodiment 5: the preparation of gold nanoporous membrane array
将上述制得的直径为330nm的二维有序单层聚苯乙烯微球阵列的玻璃基底置于反应性等离子体刻蚀机中，在刻蚀气压为10mTorr，刻蚀温度为20℃，氧气流速为50sccm，刻蚀功率为100W的条件下，刻蚀180秒；在这个过程中，微球被刻蚀逐渐变小；然后将刻蚀过的样品放置在真空蒸发镀膜设备的样品台上，样品法线与沉积方向的夹角(即入射角)为0°，在5×10-4Pa的真空度下进行热蒸发沉积金属金，沉积速度为沉积厚度为100nm；将蒸镀完的基底放入甲苯中超声3min，功率为40w，除去微球得到周期为330nm，孔径为200nm的金纳米孔膜阵列基底；The glass substrate of the two-dimensional ordered single-layer polystyrene microsphere array with a diameter of 330 nm prepared above was placed in a reactive plasma etching machine, the etching pressure was 10 mTorr, the etching temperature was 20 ° C, and oxygen The flow rate is 50sccm, and the etching power is 100W, etch for 180 seconds; during this process, the microspheres are etched and gradually become smaller; then the etched sample is placed on the sample stage of the vacuum evaporation coating equipment, The angle between the normal line of the sample and the deposition direction (i.e., the incident angle) is 0°, and the thermal evaporation deposition of metal gold is carried out under a vacuum degree of 5×10-4 Pa, and the deposition rate is The deposition thickness is 100nm; the evaporated substrate is placed in toluene and ultrasonicated for 3min with a power of 40w, and the microspheres are removed to obtain a gold nanoporous film array substrate with a period of 330nm and a pore diameter of 200nm;
实施例6：增加胶体晶体与基底的粘附性的方法Embodiment 6: the method that increases the adhesion of colloidal crystal and substrate
将实施例4制得的直径为3μm的二维有序单层聚苯乙烯微球阵列的PS/甲苯玻璃基底置于110℃烘箱中20min，然后取出待用；The PS/toluene glass substrate of the two-dimensional ordered single-layer polystyrene microsphere array with a diameter of 3 μm obtained in Example 4 was placed in an oven at 110° C. for 20 minutes, and then taken out for use;
实施例7：金纳米孔膜的转移Example 7: Transfer of gold nanoporous membranes
将实施例5制得的金纳米孔膜阵列基底倾斜慢慢地浸入到用水稀释了10倍的氢氟酸水溶液(稀释前溶液的质量分数40％)中10s，使金纳米孔膜阵列脱离基底而悬浮在水/空气界面。用实施例6得到的基底轻轻捞起悬浮的金纳米孔膜阵列，在室温环境中自然风干。The gold nanoporous membrane array substrate that embodiment 5 is made tilts and slowly immerses in the hydrofluoric acid aqueous solution (40% of the mass fraction of the solution before dilution) that has been diluted 10 times with water for 10s, and the gold nanopore membrane array is detached from the substrate while suspended at the water/air interface. Using the substrate obtained in Example 6, gently scoop up the suspended gold nanoporous membrane array, and let it dry naturally at room temperature.
实施例8：多孔半球形阵列的制备Example 8: Preparation of Porous Hemispherical Arrays
将实施例7制备的样品置于反应性等离子体刻蚀机中，在刻蚀气压为10mTorr，刻蚀温度为20℃，氧气流速为50sccm，刻蚀功率为100W的条件下，刻蚀240秒；在这个过程中，金纳米孔膜阵列作为掩膜，刻蚀下面的3μm微球为多孔形貌，用金刻蚀剂除去金纳米孔膜阵列，得到多孔半球形阵列(多孔半球形阵列结构单元的结构参数为(如图2D)：D代表多孔半球形阵列膜的周期(即大球尺寸3μm)、P代表金纳米孔膜掩板的周期(即小球尺寸330nm)、H代表刻蚀孔的深度(150nm)、d代表多空半球形阵列膜的孔直径(200nm))。The sample prepared in Example 7 was placed in a reactive plasma etching machine, and etched for 240 seconds under the conditions that the etching pressure was 10mTorr, the etching temperature was 20°C, the oxygen flow rate was 50 sccm, and the etching power was 100W. ; In this process, the gold nanoporous membrane array is used as a mask, and the 3 μm microspheres below are etched to be porous, and the gold nanoporous membrane array is removed with a gold etchant to obtain a porous hemispherical array (porous hemispherical array structure The structural parameters of the unit are (as shown in Figure 2D): D represents the period of the porous hemispherical array membrane (that is, the size of the large ball is 3 μm), P represents the period of the gold nanoporous membrane mask (that is, the size of the small ball is 330 nm), and H represents the etching The depth of the hole (150nm), d represents the hole diameter (200nm) of the porous hemispherical array membrane).
实施例9：金属银的蒸镀方法Embodiment 9: the vapor deposition method of metallic silver
将实施例8的样品放置在真空蒸发镀膜设备的样品台上，样品法线与沉积方向的夹角(即入射角)为0°，在5×10-4的真空度下进行热蒸发沉积金属银，沉积速度为沉积厚度为50nm，得到多孔半球形阵列膜。The sample of Example 8 was placed on the sample stage of the vacuum evaporation coating equipment, the angle between the normal line of the sample and the deposition direction (that is, the angle of incidence) was 0°, and the metal was deposited by thermal evaporation at a vacuum degree of 5×10-4 Silver, deposited at a rate of The deposition thickness is 50 nm, and a porous hemispherical array film is obtained.
实施例10：检测多孔半球形阵列膜宽频带、全方位减发射性质的方法Example 10: Method for detecting broadband and omni-directional emission reduction properties of porous hemispherical array membrane
将实施例9的样品放置在光纤光谱仪的样品台上，测试其反射性质；在波长为400～1000nm范围，当入射角为0°时，多孔半球形阵列膜的反射率在0.5％左右，证明了其宽频带减反射性质，对应图3A。改变入射光的方向(入射角分别为0°、15°、25°、35°、45°)，测试不同入射光方向时的反射性质。发现随着入射光角度增加，多孔半球形阵列膜的反射率也减小，而且最小值达到0.05％。证明了其全方位减反射性质，对应图3B。The sample of Example 9 is placed on the sample stage of a fiber optic spectrometer to test its reflection properties; in the wavelength range of 400 to 1000 nm, when the angle of incidence is 0°, the reflectivity of the porous hemispherical array film is about 0.5%, proving that Its broadband anti-reflection properties, corresponding to Figure 3A. Change the direction of incident light (incident angles are 0°, 15°, 25°, 35°, 45° respectively), and test the reflection properties in different incident light directions. It is found that as the incident light angle increases, the reflectance of the porous hemispherical array film also decreases, and the minimum value reaches 0.05%. Its omni-directional anti-reflection properties are demonstrated, corresponding to Fig. 3B.
实施例11：证明多孔半球形阵列膜减反射性质在实际生活中应用的方法Example 11: A method for proving the application of the anti-reflection properties of the porous hemispherical array film in real life
制备的样品放置在与屏幕垂直，水平距离屏幕20cm的位置。然后用一束波长为635nm的激光照射样品，证明其在实际应用中的减反射性质，对应图4。The prepared sample is placed at a position vertical to the screen and 20 cm away from the screen horizontally. The sample is then irradiated with a laser beam with a wavelength of 635nm to demonstrate its anti-reflection properties in practical applications, corresponding to Figure 4.
以上所述，仅是本发明的较佳实施例而已，并非对本发明的方法方案作任何形式上的限制。凡是依据本发明的方法实质对以上实施例所作的任何简单修改、等同改变与修饰，均落入本发明的保护范围内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the method scheme of the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the essence of the method of the present invention fall within the protection scope of the present invention.
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| CN201610547064.2ACN106199775B (en) | 2016-07-13 | 2016-07-13 | It is a kind of that there are broadband, porous hemispherical array films of comprehensive its antireflective properties and preparation method thereof |
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| CN201610547064.2ACN106199775B (en) | 2016-07-13 | 2016-07-13 | It is a kind of that there are broadband, porous hemispherical array films of comprehensive its antireflective properties and preparation method thereof |
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