WO2019200861A1 - Plasmon composite anti-reflection film enhanced solar cell and preparation method therefor - Google Patents

Plasmon composite anti-reflection film enhanced solar cell and preparation method therefor Download PDF

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WO2019200861A1
WO2019200861A1 PCT/CN2018/110980 CN2018110980W WO2019200861A1 WO 2019200861 A1 WO2019200861 A1 WO 2019200861A1 CN 2018110980 W CN2018110980 W CN 2018110980W WO 2019200861 A1 WO2019200861 A1 WO 2019200861A1
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solar cell
reflection film
plasmon
composite anti
sol
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French (fr)
Chinese (zh)
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李国强
张曙光
温雷
徐珍珠
黎翊君
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华南理工大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/07—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the Schottky type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of solar cells, and particularly relates to a plasmon-activated composite anti-reflection film reinforced solar cell and a preparation method thereof.
  • solar cells are the way we mainly use solar energy. How to further improve the photoelectric conversion efficiency is the focus of attention. Most solar cells have a high reflectivity on the surface and a weak ability to capture and absorb light, which causes the solar cell's energy source to be greatly dissipated.
  • anti-reflection coatings as optical gain structures to enhance the absorption of light by solar cells.
  • a single-layer anti-reflection film can only have the greatest anti-reflection effect for a single wavelength of light, and has no maximum anti-reflection effect for other wavelengths of light.
  • the multilayer anti-reflection film can have an anti-reflection effect on light of a plurality of wavelengths, the solar spectrum is continuous, and the multilayer anti-reflection film itself has problems such as interface loss between the film and the film. Therefore, it is necessary to study how to obtain better anti-reflection effect on sunlight in a wider solar spectrum.
  • Another object of the present invention is to provide a method for producing the above plasmonic composite antireflection film.
  • a plasmon-activated composite anti-reflection film reinforced solar cell comprises, in order from bottom to top, a solar cell, a metal nanoparticle layer and an anti-reflection film layer.
  • the metal nanoparticles in the metal nanoparticle layer are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles, preferably silver nanoparticles;
  • the anti-reflection film layer is preferably titanium dioxide.
  • the anti-reflection film layer completely covers the metal nanoparticle layer.
  • the solar cell is a Schottky junction solar cell, preferably a graphene Schottky junction solar cell, and the Schottky junction solar cell includes a bottom electrode, a GaAs substrate, a graphene layer and a top from bottom to top. electrode.
  • the metal nanoparticle layer is disposed on the surface of the solar cell, particularly the electrode and the graphene layer not covered by the electrode.
  • the antireflection film has a thickness of 30 to 300 nm.
  • the thickness of the anti-reflection film layer is preferably larger than the thickness of the metal nanoparticle layer.
  • the preparation method of the plasmon composite anti-reflection film solar cell comprises the following steps:
  • the sol solution of the metal nanoparticles is preferably a nanosilver sol, and the nanosilver sol is prepared by a conventional method.
  • the specific preparation method of the nano silver sol is: using water as a solvent, sodium citrate as a buffering agent, reducing the silver nitrate with a reducing agent to obtain a sol stock solution; centrifuging the sol stock solution, removing the supernatant liquid, dispersing the lower layer with water, and centrifuging again. Dispersion, repeating this, after the last centrifugation, the nanosilver is mixed with an organic solvent to obtain a nanosilver sol solution.
  • the reducing agent is ascorbic acid; the reducing agent is added in the form of a drop, and the pH of the solution is 6 when the reduction is carried out.
  • the sol solution of the anti-reflection film layer material is preferably a titania sol; the titania sol is obtained by a conventional preparation method.
  • the rotational speed of the spin coating is 2500-4500 r/min, and the spin coating time is 20-100 seconds; the sol solution of the anti-reflective coating material is spin-coated during spin coating.
  • the rotation speed is 2500 to 4500 r/min, and the spin coating time is 50 to 100 seconds.
  • the present invention has the following advantages and benefits:
  • the present invention enhances the scattering effect on sunlight by using a scattering cross section of the alloy particles by spin-coating metal nanoparticles (such as Ag nanoparticles) on the surface of the solar cell, while enhancing the solar cell by using a strong local field around the nanoparticles. Light absorption, ultimately achieving high photoelectric conversion efficiency of the battery;
  • the invention effectively reduces the reflection of light by spin-coating the titanium dioxide anti-reflection film, enhances the absorption of light by the solar cell, increases the photocurrent of the solar cell, and finally improves the photoelectric conversion efficiency of the solar cell;
  • FIG. 1 is a schematic structural view of a plasmon-activated composite anti-reflection film reinforced solar cell according to an embodiment of the present invention
  • FIG. 2 is a scanning electron micrograph of a nano-silver particle in a plasmon-activated composite anti-reflection film reinforced solar cell according to Embodiment 1 of the present invention
  • FIG. 3 is an optical microscopic view of a plasmon-activated composite anti-reflection film reinforced solar cell according to Embodiment 1 of the present invention.
  • Embodiment 4 is a solar cell (without anti-reflection film layer and metal nanoparticle layer) (ie, an intrinsic cell) and a plasmon-activated composite anti-reflection film-enhanced solar cell (ie, a composite anti-reflection film cell) according to Embodiment 1 of the present invention; Current-voltage relationship graph.
  • FIG. 1 A schematic diagram of the structure of the plasmon-activated composite anti-reflection film-enhancing solar cell of the present invention is shown in FIG. 1.
  • the solar cell, the metal nano-particle layer 5 and the anti-reflection film layer 6 are sequentially arranged from bottom to top.
  • the metal nanoparticles in the metal nanoparticle layer are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles, preferably silver nanoparticles;
  • the anti-reflection film layer is preferably titanium dioxide.
  • the anti-reflection film layer completely covers the metal nanoparticle layer.
  • the solar cell is a Schottky junction solar cell, preferably a graphene Schottky junction solar cell, and the Schottky junction solar cell includes a bottom electrode 1, a GaAs substrate 2, and a graphene layer in order from bottom to top. 3 and top electrode 4.
  • the metal nanoparticle layer is disposed on the surface of the solar cell, particularly the electrode and the graphene layer not covered by the electrode.
  • the plasmon composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode 1 (Au), a GaAs substrate 2, a graphene film 3, a top electrode 4, and metal nanoparticles from bottom to top. Layer 5, titanium dioxide anti-reflection film 6.
  • the bottom electrode 1 (Au), the GaAs substrate 2, the graphene film 3, and the top electrode 4 constitute a graphene Schottky junction solar cell.
  • a graphene Schottky junction solar cell is obtained by a conventional method.
  • titanium dioxide sol 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
  • the thickness of the titanium dioxide antireflection layer was 120 nm.
  • FIG. 2 is a scanning electron micrograph of the silver nanoparticles in the plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment. It can be seen from the figure that the distribution of the silver nanoparticles is relatively small, and the particle diameter is about 80 nm.
  • 3 is an optical micrograph of a plasmon-activated composite anti-reflection film reinforced solar cell of Example 1;
  • FIG. 4 is a solar cell of Example 1 (without anti-reflection film layer and metal nano-particle layer) and plasmon composite anti-reflection A graph of the current-voltage relationship of a membrane-enhanced solar cell.
  • the surface morphology of the nano-silver particle composite titanium dioxide anti-reflection film can be seen from FIG.
  • Figure 4 is a solar cell current-voltage curve, from which it can be seen that the solar cell's photocurrent has increased by about 27.33%.
  • the invention introduces silver nano particles and titanium dioxide anti-reflection film in the solar cell. Due to the local surface plasmon effect of the nanoparticles, the scattering effect on the incident sunlight can be enhanced on the one hand, and the propagation distance of the sunlight inside the active region is enhanced. Thereby increasing light absorption. At the same time, after the local surface plasmon of the silver nanoparticles is excited, a strong local electric field is formed around the particles. According to the Fermi gold rule, this strong local electric field can increase the absorption rate of the incident photons of the battery. At the same time, by introducing an anti-reflection film, the light can be reflected less, which increases the amount of light incident on the solar cell, thereby increasing the spot efficiency of the battery.
  • the plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode (Au), a GaAs substrate, a graphene film, a top electrode, a metal nanoparticle layer, and a titanium dioxide anti-reflection film in this order from bottom to top.
  • a bottom electrode (Au), a GaAs substrate, a graphene film, and a top electrode constitute a graphene Schottky junction solar cell.
  • a graphene Schottky junction solar cell is obtained by a conventional method.
  • titanium dioxide sol 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
  • the thickness of the titanium dioxide antireflection layer was 100 nm.
  • the plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode (Au), a GaAs substrate, a graphene film, a top electrode, a metal nanoparticle layer, and a titanium dioxide anti-reflection film in this order from bottom to top.
  • a bottom electrode (Au), a GaAs substrate, a graphene film, and a top electrode constitute a graphene Schottky junction solar cell.
  • a graphene Schottky junction solar cell is obtained by a conventional method.
  • titanium dioxide sol 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
  • the thickness of the titanium dioxide antireflection layer was 200 nm.
  • the concentration of the sol solution of the metal nanoparticles of the present invention is 0.001 to 10 mol/L, the thickness of the metal nanoparticle layer is 30 to 100 nm, and the particle diameter of the metal nanoparticles is 10 to 80 nm.
  • the metal nanoparticle layer has a thickness of 30 to 100 nm, and the metal nanoparticle has a particle diameter of 10 to 80 nm.

Abstract

Disclosed are a plasmon composite anti-reflection film enhanced solar cell and a preparation method therefor, which belong to the technical field of solar cells. The plasmon composite anti-reflection film enhanced solar cell successively comprises, from bottom to top, a solar cell, a metal nanoparticle layer (5) and an anti-reflection film layer (6), wherein metal nanoparticles in the metal nanoparticle layer (5) are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles; the anti-reflection film layer (6) is made of titanium dioxide; and the solar cell is a Schottky junction solar cell. By spin-coating the surface of the solar cell with the metal nanoparticles, the sunlight scattering effect and the light absorption of the solar cell are enhanced, and the cell achieves a high photoelectric conversion efficiency; and by spin-coating the titanium dioxide anti-reflection film, the reflection of light is effectively reduced, the absorption of light by the solar cell is enhanced, the magnitude of the photocurrent of the solar cell is increased, and the photoelectric conversion efficiency of the solar cell is finally improved.

Description

一种等离子激元复合减反射膜增强太阳电池及其制备方法Plasmon activated composite anti-reflection film reinforced solar cell and preparation method thereof 技术领域Technical field
本发明属于太阳电池领域，特别涉及一种等离子激元复合减反射膜增强太阳电池及其制备方法。The invention belongs to the field of solar cells, and particularly relates to a plasmon-activated composite anti-reflection film reinforced solar cell and a preparation method thereof.
背景技术Background technique
太阳电池作为一种直接利用太阳光进行能量转换的器件，是我们主要利用太阳能的方式。如何对其进一步的提升光电转换效率是人们关注的重点。大部分的太阳电池的表面的反射率较高，对于光的捕获与吸收的能力比较弱，这就使得太阳电池的能量来源被大大的耗散了。传统上我们使用减反射膜作为光学增益结构来增强太阳电池对于光的吸收。然而受限于光学原理，单层减反射膜只能对于单一波长的光有最大的减反射效果，对于其他波长的光则没有最大的减反射效果。虽然多层减反射膜可以对于多个波长的光有增透效果，然而太阳能光谱是连续的，且本身多层减反射膜就存在膜与膜间的界面损耗等问题。因此研究如何在更宽的太阳能光谱上获得更好的对于太阳光的减反射效果是十分必要的。As a device that directly uses sunlight to convert energy, solar cells are the way we mainly use solar energy. How to further improve the photoelectric conversion efficiency is the focus of attention. Most solar cells have a high reflectivity on the surface and a weak ability to capture and absorb light, which causes the solar cell's energy source to be greatly dissipated. Traditionally we have used anti-reflection coatings as optical gain structures to enhance the absorption of light by solar cells. However, limited by the optical principle, a single-layer anti-reflection film can only have the greatest anti-reflection effect for a single wavelength of light, and has no maximum anti-reflection effect for other wavelengths of light. Although the multilayer anti-reflection film can have an anti-reflection effect on light of a plurality of wavelengths, the solar spectrum is continuous, and the multilayer anti-reflection film itself has problems such as interface loss between the film and the film. Therefore, it is necessary to study how to obtain better anti-reflection effect on sunlight in a wider solar spectrum.
发明内容Summary of the invention
为了克服现有技术的上述缺点与不足，本发明的目的在于提供一种等离子激元复合减反射膜，可以提高太阳电池的光电转换效率。In order to overcome the above disadvantages and disadvantages of the prior art, it is an object of the present invention to provide a plasmon composite anti-reflection film which can improve the photoelectric conversion efficiency of a solar cell.
本发明的另一目的在于提供上述等离激元复合减反射膜的制备方法。Another object of the present invention is to provide a method for producing the above plasmonic composite antireflection film.
本发明的目的通过以下技术方案实现：The object of the invention is achieved by the following technical solutions:
一种等离子激元复合减反射膜增强太阳电池，由下至上依次包括太阳电池，金属纳米粒子层以及减反射膜层。A plasmon-activated composite anti-reflection film reinforced solar cell comprises, in order from bottom to top, a solar cell, a metal nanoparticle layer and an anti-reflection film layer.
所述金属纳米粒子层中金属纳米粒子为银纳米粒子、金纳米粒子或铂金属纳米粒子，优选为银纳米粒子；The metal nanoparticles in the metal nanoparticle layer are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles, preferably silver nanoparticles;
所述减反射膜层优选为二氧化钛。The anti-reflection film layer is preferably titanium dioxide.
所述减反射膜层完全覆盖金属纳米粒子层。The anti-reflection film layer completely covers the metal nanoparticle layer.
所述太阳电池为肖特基结太阳电池，优选为石墨烯肖特基结太阳电池，所述肖特基结太阳电池，从下到上依次包括底电极、GaAs衬底、石墨烯层和顶电极。The solar cell is a Schottky junction solar cell, preferably a graphene Schottky junction solar cell, and the Schottky junction solar cell includes a bottom electrode, a GaAs substrate, a graphene layer and a top from bottom to top. electrode.
所述金属纳米粒子层设置在太阳电池的表面，特别是电极以及未被电极覆盖的石墨烯层上。The metal nanoparticle layer is disposed on the surface of the solar cell, particularly the electrode and the graphene layer not covered by the electrode.
所述减反射膜的厚度为30～300nm。减反射膜层的厚度优选大于金属纳米粒子层的厚度。The antireflection film has a thickness of 30 to 300 nm. The thickness of the anti-reflection film layer is preferably larger than the thickness of the metal nanoparticle layer.
所述等离子激元复合减反射膜太阳电池的制备方法，包括以下步骤：The preparation method of the plasmon composite anti-reflection film solar cell comprises the following steps:
(1)配置金属纳米粒子的溶胶溶液；(1) Configuring a sol solution of metal nanoparticles;
(2)配置减反射膜层材料的溶胶溶液；(2) locating the sol solution of the anti-reflection coating material;
(3)将金属纳米粒子的溶胶溶液和减反射膜层材料的溶胶溶液依次旋涂在太阳电池的表面，获得等离子激元复合减反射膜太阳电池。(3) The sol solution of the metal nanoparticles and the sol solution of the anti-reflection film layer material are sequentially spin-coated on the surface of the solar cell to obtain a plasmon-activated composite anti-reflection film solar cell.
金属纳米粒子的溶胶溶液优选为纳米银溶胶，纳米银溶胶采用常规方法制备得到。纳米银溶胶的具体制备方法为：以水为溶剂，柠檬酸钠为缓冲剂，采用还原剂还原硝酸银，获得溶胶原液；将溶胶原液离心，将上层清液去除，下层加水分散，再次离心，分散，如此重复，最后一次离心后，将纳米银与有机溶剂混合，获得纳米银溶胶溶液。所述还原剂为抗坏血酸；所述还原剂采用滴加的形式加入，在进行还原时，溶液的pH为6。The sol solution of the metal nanoparticles is preferably a nanosilver sol, and the nanosilver sol is prepared by a conventional method. The specific preparation method of the nano silver sol is: using water as a solvent, sodium citrate as a buffering agent, reducing the silver nitrate with a reducing agent to obtain a sol stock solution; centrifuging the sol stock solution, removing the supernatant liquid, dispersing the lower layer with water, and centrifuging again. Dispersion, repeating this, after the last centrifugation, the nanosilver is mixed with an organic solvent to obtain a nanosilver sol solution. The reducing agent is ascorbic acid; the reducing agent is added in the form of a drop, and the pH of the solution is 6 when the reduction is carried out.
所述减反射膜层材料的溶胶溶液优选为二氧化钛溶胶；所述二氧化钛溶胶采用常规的制备方法得到。The sol solution of the anti-reflection film layer material is preferably a titania sol; the titania sol is obtained by a conventional preparation method.
金属纳米粒子的溶胶溶液在进行旋涂时，旋涂的转速为2500～4500r/min，旋涂的时间为20～100秒；减反射膜层材料的溶胶溶液在进行旋涂时，旋涂的转速为2500～4500r/min，旋涂的时间为50～100秒。When the sol solution of the metal nanoparticles is spin-coated, the rotational speed of the spin coating is 2500-4500 r/min, and the spin coating time is 20-100 seconds; the sol solution of the anti-reflective coating material is spin-coated during spin coating. The rotation speed is 2500 to 4500 r/min, and the spin coating time is 50 to 100 seconds.
与现有技术相比，本发明具有以下优点和有益效果：Compared with the prior art, the present invention has the following advantages and benefits:
(1)本发明通过在太阳电池表面旋涂金属纳米粒子(如：Ag纳米颗粒)，利用合金颗粒的散射截面增强对太阳光的散射效应，同时利用纳米颗粒周围强的局域场增强太阳电池的光吸收，最终实现电池高的光电转换效率；(1) The present invention enhances the scattering effect on sunlight by using a scattering cross section of the alloy particles by spin-coating metal nanoparticles (such as Ag nanoparticles) on the surface of the solar cell, while enhancing the solar cell by using a strong local field around the nanoparticles. Light absorption, ultimately achieving high photoelectric conversion efficiency of the battery;
(2)本发明通过旋涂二氧化钛减反射膜，有效的减少了光的反射，增强了太阳能电池对于光的吸收，提高了太阳电池光电流的大小，最终提高了太阳电 池的光电转换效率；(2) The invention effectively reduces the reflection of light by spin-coating the titanium dioxide anti-reflection film, enhances the absorption of light by the solar cell, increases the photocurrent of the solar cell, and finally improves the photoelectric conversion efficiency of the solar cell;
(3)本发明的制备方法简单有效，电池光电转换效率增强效果明显。(3) The preparation method of the invention is simple and effective, and the effect of enhancing the photoelectric conversion efficiency of the battery is obvious.
附图说明DRAWINGS
图1为本发明的实施例的等离子激元复合减反射膜增强太阳电池的结构示意图；1 is a schematic structural view of a plasmon-activated composite anti-reflection film reinforced solar cell according to an embodiment of the present invention;
图2为本发明的实施例1的等离子激元复合减反射膜增强太阳电池中纳米银颗粒的扫描电子显微镜图；2 is a scanning electron micrograph of a nano-silver particle in a plasmon-activated composite anti-reflection film reinforced solar cell according to Embodiment 1 of the present invention;
图3为本发明的实施例1的等离子激元复合减反射膜增强太阳电池的光学显微镜图；3 is an optical microscopic view of a plasmon-activated composite anti-reflection film reinforced solar cell according to Embodiment 1 of the present invention;
图4为本发明的实施例1的太阳电池(无减反射膜层和金属纳米粒子层)(即本征电池)以及等离子激元复合减反射膜增强太阳电池(即复合减反射膜电池)的电流-电压关系曲线图。4 is a solar cell (without anti-reflection film layer and metal nanoparticle layer) (ie, an intrinsic cell) and a plasmon-activated composite anti-reflection film-enhanced solar cell (ie, a composite anti-reflection film cell) according to Embodiment 1 of the present invention; Current-voltage relationship graph.
具体实施方式detailed description
下面结合实施例和附图，对本发明作进一步地详细说明，但本发明的实施方式不限于此。The present invention will be further described in detail below with reference to the embodiments and drawings, but the embodiments of the present invention are not limited thereto.
本发明的等离子激元复合减反射膜增强太阳电池的结构示意图如图1所示，由下至上依次包括太阳电池，金属纳米粒子层5以及减反射膜层6。A schematic diagram of the structure of the plasmon-activated composite anti-reflection film-enhancing solar cell of the present invention is shown in FIG. 1. The solar cell, the metal nano-particle layer 5 and the anti-reflection film layer 6 are sequentially arranged from bottom to top.
所述金属纳米粒子层中金属纳米粒子为银纳米粒子、金纳米粒子或铂金属纳米粒子，优选为银纳米粒子；The metal nanoparticles in the metal nanoparticle layer are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles, preferably silver nanoparticles;
所述减反射膜层优选为二氧化钛。The anti-reflection film layer is preferably titanium dioxide.
所述减反射膜层完全覆盖金属纳米粒子层。The anti-reflection film layer completely covers the metal nanoparticle layer.
所述太阳电池为肖特基结太阳电池，优选为石墨烯肖特基结太阳电池，所述肖特基结太阳电池，从下到上依次包括底电极1、GaAs衬底2、石墨烯层3和顶电极4。The solar cell is a Schottky junction solar cell, preferably a graphene Schottky junction solar cell, and the Schottky junction solar cell includes a bottom electrode 1, a GaAs substrate 2, and a graphene layer in order from bottom to top. 3 and top electrode 4.
所述金属纳米粒子层设置在太阳电池的表面，特别是电极以及未被电极覆盖的石墨烯层上。The metal nanoparticle layer is disposed on the surface of the solar cell, particularly the electrode and the graphene layer not covered by the electrode.
实施例1Example 1
如图1所示，本实施例的等离子激元复合减反射膜增强太阳电池，由下至 上依次包括底电极1(Au)，GaAs衬底2，石墨烯薄膜3，顶电极4，金属纳米粒子层5，二氧化钛减反膜6。As shown in FIG. 1, the plasmon composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode 1 (Au), a GaAs substrate 2, a graphene film 3, a top electrode 4, and metal nanoparticles from bottom to top. Layer 5, titanium dioxide anti-reflection film 6.
底电极1(Au)，GaAs衬底2，石墨烯薄膜3以及顶电极4组成石墨烯肖特基结太阳电池。石墨烯肖特基结太阳电池采用常规的方法得到。The bottom electrode 1 (Au), the GaAs substrate 2, the graphene film 3, and the top electrode 4 constitute a graphene Schottky junction solar cell. A graphene Schottky junction solar cell is obtained by a conventional method.
本实施例的等离子激元复合减反射膜的制备方法，包括以下步骤：The preparation method of the plasmon composite anti-reflection film of this embodiment comprises the following steps:
(1)纳米银溶胶的制备：先取100ml的浓度为0.01mol/L的硝酸银溶液，然后加入2ml的1wt％柠檬酸钠溶液作为缓冲剂，在搅拌的条件下(转速为900r/min)，逐滴滴加1ml的浓度为1.4mg/ml的抗坏血酸溶液，并用氢氧化钠溶液调节pH至6，维持搅拌1个小时后，停止搅拌，得到纳米银溶胶原液；取10ml溶胶原液进行离心(转速为7200r/min，离心时间为10分钟)，去除上层清液，留下底部沉淀与浊液(大约为1毫升)后再用去离子水将各个离心管中的液面补充至10毫升，超声分散15分钟，然后离心，分散，如此重复3次后，用8000r/min的转速离心10分钟，去除上层清液后加入丙酮补充液面至5毫升，得到纳米银溶胶；(1) Preparation of nano silver sol: 100 ml of a silver nitrate solution having a concentration of 0.01 mol/L is first taken, and then 2 ml of a 1 wt% sodium citrate solution is added as a buffer under stirring conditions (rotation speed: 900 r/min). 1 ml of a solution of ascorbic acid having a concentration of 1.4 mg/ml was added dropwise, and the pH was adjusted to 6 with a sodium hydroxide solution. After stirring for 1 hour, stirring was stopped to obtain a nanosilver sol stock solution; 10 ml of the sol stock solution was centrifuged (rotation speed) 7200r/min, centrifugation time is 10 minutes), remove the supernatant, leave the bottom sediment and turbid liquid (about 1 ml), then add the liquid level in each centrifuge tube to 10 ml with deionized water, ultrasonic Disperse for 15 minutes, then centrifuge, disperse, and repeat this 3 times, then centrifuge at 8000r/min for 10 minutes, remove the supernatant, and add acetone to add 5 ml to obtain nano-silver sol;
(2)二氧化钛溶胶的制备：将23ml的无水乙醇和0.5ml的乙酸乙酯混合，然后加入10ml的钛酸四丁酯，形成二氧化钛凝胶的前驱体溶液；将12ml的无水乙醇、1.5ml的去离子水和1.5ml的65wt％硝酸溶液混合，得到水解混合溶液；在搅拌的条件下(转速为900r/min)，以每秒1滴到1.5滴的速度逐滴滴加水解混合溶液到处于搅拌状态的前驱体溶液中，将水解混合溶液完全滴入到前驱体溶液中之后，维持搅拌状态2小时，搅拌完成后用铝箔纸覆盖密封烧杯口，并静置在室温下老化24个小时，从而得到二氧化钛溶胶；(2) Preparation of titanium dioxide sol: 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
(3)复合减反射膜的旋涂：设定镀膜机转速为3000r/min，试转5秒，若出现飞片现象则调整太阳电池的位置直至不发生飞片，先令旋涂机在低速状态下工作(2500r/min)，而后用移液枪吸取100μl的纳米银溶胶并往太阳电池上滴一滴，之后进入高速旋涂，转速为3000r/min，时常为60秒，而后再用移液枪吸取100μl的二氧化钛溶胶，先令镀膜机处于低速状态下，而后滴两滴二氧化钛溶胶至太阳电池上，高速旋转一分钟后便可得到纳米银粒子复合二氧化钛减反射膜，即得到等离子激元复合减反射膜增强太阳电池。(3) Spin coating of composite anti-reflection film: set the rotation speed of the coating machine to 3000r/min, test rotation for 5 seconds, if there is a flying film phenomenon, adjust the position of the solar battery until no flying piece occurs, first let the spin coating machine at low speed Working in the state (2500r/min), then pipetting 100μl of nano-silver sol and dropping a drop onto the solar cell, then entering high-speed spin coating at a speed of 3000r/min, often 60 seconds, and then pipetting The gun draws 100μl of titanium dioxide sol, the first coating machine is at a low speed, and then drops two drops of titanium dioxide sol onto the solar cell. After one minute of high-speed rotation, the nano-silver particle composite titanium dioxide anti-reflection film can be obtained, that is, the plasmon compound is obtained. The anti-reflection film enhances the solar cell.
二氧化钛减反射层的厚度为120nm。The thickness of the titanium dioxide antireflection layer was 120 nm.
图2为本实施例的等离子激元复合减反射膜增强太阳电池中银纳米颗粒的扫描电子显微镜照片，从图中可以看出银纳米颗粒的分布比较少，粒径约为80纳米左右。图3为实施例1的等离子激元复合减反射膜增强太阳电池的光学显微镜图；图4为实施例1的太阳电池(无减反射膜层和金属纳米粒子层)以及等离子激元复合减反射膜增强太阳电池的电流-电压关系曲线图。从图3可以看出纳米银粒子复合二氧化钛减反射膜的表面的形貌。图4是太阳电池电流-电压关系曲线，从中可以看出太阳电池的光电流提升了约27.33％2 is a scanning electron micrograph of the silver nanoparticles in the plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment. It can be seen from the figure that the distribution of the silver nanoparticles is relatively small, and the particle diameter is about 80 nm. 3 is an optical micrograph of a plasmon-activated composite anti-reflection film reinforced solar cell of Example 1; FIG. 4 is a solar cell of Example 1 (without anti-reflection film layer and metal nano-particle layer) and plasmon composite anti-reflection A graph of the current-voltage relationship of a membrane-enhanced solar cell. The surface morphology of the nano-silver particle composite titanium dioxide anti-reflection film can be seen from FIG. Figure 4 is a solar cell current-voltage curve, from which it can be seen that the solar cell's photocurrent has increased by about 27.33%.
本发明在太阳电池中引入银纳米颗粒与二氧化钛减反射膜，由于纳米颗粒的局域表面等离子体效应，一方面可以增强对入射太阳光的散射作用，提高太阳光在有源区内部的传播距离从而提高光吸收。同时，银纳米颗粒的局域表面等离激元被激发后，在颗粒周围会形成强的局域电场，根据费米黄金规则，这种强的局域电场可以提高电池入射光子的吸收速率。同时另外通过引入减反射膜，让光的能够更少的被反射掉，增大了入射太阳电池的光的数量，从而增加了电池的光点效率。The invention introduces silver nano particles and titanium dioxide anti-reflection film in the solar cell. Due to the local surface plasmon effect of the nanoparticles, the scattering effect on the incident sunlight can be enhanced on the one hand, and the propagation distance of the sunlight inside the active region is enhanced. Thereby increasing light absorption. At the same time, after the local surface plasmon of the silver nanoparticles is excited, a strong local electric field is formed around the particles. According to the Fermi gold rule, this strong local electric field can increase the absorption rate of the incident photons of the battery. At the same time, by introducing an anti-reflection film, the light can be reflected less, which increases the amount of light incident on the solar cell, thereby increasing the spot efficiency of the battery.
实施例2Example 2
本实施例的等离子激元复合减反射膜增强太阳电池，由下至上依次包括底电极(Au)，GaAs衬底，石墨烯薄膜，顶电极，金属纳米粒子层，二氧化钛减反膜。The plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode (Au), a GaAs substrate, a graphene film, a top electrode, a metal nanoparticle layer, and a titanium dioxide anti-reflection film in this order from bottom to top.
底电极(Au)，GaAs衬底，石墨烯薄膜以及顶电极组成石墨烯肖特基结太阳电池。石墨烯肖特基结太阳电池采用常规的方法得到。A bottom electrode (Au), a GaAs substrate, a graphene film, and a top electrode constitute a graphene Schottky junction solar cell. A graphene Schottky junction solar cell is obtained by a conventional method.
本实施例的等离子激元复合减反射膜的制备方法，包括以下步骤：The preparation method of the plasmon composite anti-reflection film of this embodiment comprises the following steps:
(1)纳米银溶胶的制备：先取100ml的浓度为0.01mol/L的硝酸银溶液，然后加入2ml的1wt％柠檬酸钠溶液作为缓冲剂，在搅拌的条件下(转速为900r/min)，逐滴滴加1ml的浓度为1.4mg/ml的抗坏血酸溶液，并用氢氧化钠溶液调节pH至6，维持搅拌1个小时后，停止搅拌，得到纳米银溶胶原液；取10ml溶胶原液进行离心(转速为7200r/min，离心时间为10分钟)，去除上层清液，留下底部沉淀与浊液(大约为1毫升)后再用去离子水将各个离心管中的液面补充至10毫升，超声分散15分钟，然后离心，分散，如此重复3次后，用8000r/min的转速离心10分钟，去除上层清液后加入丙酮补充液面至5毫升， 得到纳米银溶胶；(1) Preparation of nano silver sol: 100 ml of a silver nitrate solution having a concentration of 0.01 mol/L is first taken, and then 2 ml of a 1 wt% sodium citrate solution is added as a buffer under stirring conditions (rotation speed: 900 r/min). 1 ml of a solution of ascorbic acid having a concentration of 1.4 mg/ml was added dropwise, and the pH was adjusted to 6 with a sodium hydroxide solution. After stirring for 1 hour, stirring was stopped to obtain a nanosilver sol stock solution; 10 ml of the sol stock solution was centrifuged (rotation speed) 7200r/min, centrifugation time is 10 minutes), remove the supernatant, leave the bottom sediment and turbid liquid (about 1 ml), then add the liquid level in each centrifuge tube to 10 ml with deionized water, ultrasonic Disperse for 15 minutes, then centrifuge, disperse, and repeat this 3 times, centrifuge at 8000r/min for 10 minutes, remove the supernatant, and add acetone to add 5 ml to obtain nano-silver sol;
(2)二氧化钛溶胶的制备：将23ml的无水乙醇和0.5ml的乙酸乙酯混合，然后加入10ml的钛酸四丁酯，形成二氧化钛凝胶的前驱体溶液；将12ml的无水乙醇、1.5ml的去离子水和1.5ml的65wt％硝酸溶液混合，得到水解混合溶液；在搅拌的条件下(转速为900r/min)，以每秒1滴到1.5滴的速度逐滴滴加水解混合溶液到处于搅拌状态的前驱体溶液中，将水解混合溶液完全滴入到前驱体溶液中之后，维持搅拌状态2小时，搅拌完成后用铝箔纸覆盖密封烧杯口，并静置在室温下老化24个小时，从而得到二氧化钛溶胶；(2) Preparation of titanium dioxide sol: 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
(3)复合减反射膜的旋涂：设定镀膜机转速为3000r/min，试转5秒，若出现飞片现象则调整太阳电池的位置直至不发生飞片，先令旋涂机在低速状态下工作(2500r/min)，而后用移液枪吸取100μl的纳米银溶胶并往太阳电池上滴一滴，之后进入高速旋涂，转速为3000r/min，时常为60秒，而后再用移液枪吸取100μl的二氧化钛溶胶，先令镀膜机处于低速状态下，而后滴1滴二氧化钛溶胶至太阳电池上，高速旋转一分钟后便可得到纳米银粒子复合二氧化钛减反射膜，即得到等离子激元复合减反射膜增强太阳电池。(3) Spin coating of composite anti-reflection film: set the rotation speed of the coating machine to 3000r/min, test rotation for 5 seconds, if there is a flying film phenomenon, adjust the position of the solar battery until no flying piece occurs, first let the spin coating machine at low speed Working in the state (2500r/min), then pipetting 100μl of nano-silver sol and dropping a drop onto the solar cell, then entering high-speed spin coating at a speed of 3000r/min, often 60 seconds, and then pipetting The gun absorbs 100μl of titanium dioxide sol, the first coating machine is at a low speed, and then drops a drop of titanium dioxide sol onto the solar cell. After high-speed rotation for one minute, the nano-silver particle composite titanium dioxide anti-reflection film can be obtained, that is, the plasmon compound is obtained. The anti-reflection film enhances the solar cell.
二氧化钛减反射层的厚度为100nm。The thickness of the titanium dioxide antireflection layer was 100 nm.
实施例3Example 3
本实施例的等离子激元复合减反射膜增强太阳电池，由下至上依次包括底电极(Au)，GaAs衬底，石墨烯薄膜，顶电极，金属纳米粒子层，二氧化钛减反膜。The plasmon-activated composite anti-reflection film reinforced solar cell of the present embodiment includes a bottom electrode (Au), a GaAs substrate, a graphene film, a top electrode, a metal nanoparticle layer, and a titanium dioxide anti-reflection film in this order from bottom to top.
底电极(Au)，GaAs衬底，石墨烯薄膜以及顶电极组成石墨烯肖特基结太阳电池。石墨烯肖特基结太阳电池采用常规的方法得到。A bottom electrode (Au), a GaAs substrate, a graphene film, and a top electrode constitute a graphene Schottky junction solar cell. A graphene Schottky junction solar cell is obtained by a conventional method.
本实施例的等离子激元复合减反射膜的制备方法，包括以下步骤：The preparation method of the plasmon composite anti-reflection film of this embodiment comprises the following steps:
(1)纳米银溶胶的制备：先取100ml的浓度为0.01mol/L的硝酸银溶液，然后加入2ml的1wt％柠檬酸钠溶液作为缓冲剂，在搅拌的条件下(转速为900r/min)，逐滴滴加1ml的浓度为1.4mg/ml的抗坏血酸溶液，并用氢氧化钠溶液调节pH至6，维持搅拌1个小时后，停止搅拌，得到纳米银溶胶原液；取10ml溶胶原液进行离心(转速为7200r/min，离心时间为10分钟)，去除上层清液，留下底部沉淀与浊液(大约为1毫升)后再用去离子水将各个离心管中 的液面补充至10毫升，超声分散15分钟，然后离心，分散，如此重复3次后，用8000r/min的转速离心10分钟，去除上层清液后加入丙酮补充液面至5毫升，得到纳米银溶胶；(1) Preparation of nano silver sol: 100 ml of a silver nitrate solution having a concentration of 0.01 mol/L is first taken, and then 2 ml of a 1 wt% sodium citrate solution is added as a buffer under stirring conditions (rotation speed: 900 r/min). 1 ml of a solution of ascorbic acid having a concentration of 1.4 mg/ml was added dropwise, and the pH was adjusted to 6 with a sodium hydroxide solution. After stirring for 1 hour, stirring was stopped to obtain a nanosilver sol stock solution; 10 ml of the sol stock solution was centrifuged (rotation speed) 7200r/min, centrifugation time is 10 minutes), remove the supernatant, leave the bottom sediment and turbid liquid (about 1 ml), then add the liquid level in each centrifuge tube to 10 ml with deionized water, ultrasonic Disperse for 15 minutes, then centrifuge, disperse, and repeat this 3 times, then centrifuge at 8000r/min for 10 minutes, remove the supernatant, and add acetone to add 5 ml to obtain nano-silver sol;
(2)二氧化钛溶胶的制备：将23ml的无水乙醇和0.5ml的乙酸乙酯混合，然后加入10ml的钛酸四丁酯，形成二氧化钛凝胶的前驱体溶液；将12ml的无水乙醇、1.5ml的去离子水和1.5ml的65wt％硝酸溶液混合，得到水解混合溶液；在搅拌的条件下(转速为900r/min)，以每秒1滴到1.5滴的速度逐滴滴加水解混合溶液到处于搅拌状态的前驱体溶液中，将水解混合溶液完全滴入到前驱体溶液中之后，维持搅拌状态2小时，搅拌完成后用铝箔纸覆盖密封烧杯口，并静置在室温下老化24个小时，从而得到二氧化钛溶胶；(2) Preparation of titanium dioxide sol: 23 ml of absolute ethanol and 0.5 ml of ethyl acetate were mixed, and then 10 ml of tetrabutyl titanate was added to form a precursor solution of titanium dioxide gel; 12 ml of absolute ethanol, 1.5 Mol of deionized water and 1.5ml of 65wt% nitric acid solution are mixed to obtain a hydrolyzed mixed solution; under stirring conditions (rotation speed of 900r/min), the hydrolyzed mixed solution is added dropwise at a rate of 1 to 1.5 drops per second. After the hydrolyzed mixed solution was completely dropped into the precursor solution in the precursor solution under stirring, the stirring state was maintained for 2 hours. After the stirring was completed, the sealed beaker mouth was covered with aluminum foil paper, and allowed to stand at room temperature for 24 hours. Hours, thereby obtaining a titanium dioxide sol;
(3)复合减反射膜的旋涂：设定镀膜机转速为3000r/min，试转5秒，若出现飞片现象则调整太阳电池的位置直至不发生飞片，先令旋涂机在低速状态下工作(2500r/min)，而后用移液枪吸取100μl的纳米银溶胶并往太阳电池上滴一滴，之后进入高速旋涂，转速为3000r/min，时常为60秒，而后再用移液枪吸取100μl的二氧化钛溶胶，先令镀膜机处于低速状态下，而后滴4滴二氧化钛溶胶至太阳电池上，高速旋转一分钟后便可得到纳米银粒子复合二氧化钛减反射膜，即得到等离子激元复合减反射膜增强太阳电池。(3) Spin coating of composite anti-reflection film: set the rotation speed of the coating machine to 3000r/min, test rotation for 5 seconds, if there is a flying film phenomenon, adjust the position of the solar battery until no flying piece occurs, first let the spin coating machine at low speed Working in the state (2500r/min), then pipetting 100μl of nano-silver sol and dropping a drop onto the solar cell, then entering high-speed spin coating at a speed of 3000r/min, often 60 seconds, and then pipetting The gun sucks 100μl of titanium dioxide sol, the first coating machine is at a low speed, and then drops 4 drops of titanium dioxide sol onto the solar cell. After high-speed rotation for one minute, the nano-silver particle composite titanium dioxide anti-reflection film can be obtained, that is, the plasmon compound is obtained. The anti-reflection film enhances the solar cell.
二氧化钛减反射层的厚度为200nm。The thickness of the titanium dioxide antireflection layer was 200 nm.
本发明的金属纳米粒子的溶胶溶液的浓度为0.001-10mol/L，金属纳米粒子层的厚度为30-100纳米，金属纳米粒子的粒径为10～80nm。The concentration of the sol solution of the metal nanoparticles of the present invention is 0.001 to 10 mol/L, the thickness of the metal nanoparticle layer is 30 to 100 nm, and the particle diameter of the metal nanoparticles is 10 to 80 nm.
所述金属纳米粒子层的厚度为30-100纳米，金属纳米粒子的粒径为10～80nm。The metal nanoparticle layer has a thickness of 30 to 100 nm, and the metal nanoparticle has a particle diameter of 10 to 80 nm.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments, and any other changes, modifications, substitutions, and combinations may be made without departing from the spirit and scope of the present invention. And simplifications, all of which are equivalent replacement means, are included in the scope of protection of the present invention.

Claims (8)

  1. 一种等离子激元复合减反射膜增强太阳电池，其特征在于：由下至上依次包括太阳电池，金属纳米粒子层以及减反射膜层。A plasmon-activated composite anti-reflection film reinforced solar cell characterized by comprising a solar cell, a metal nanoparticle layer and an anti-reflection film layer in order from bottom to top.
  2. 根据权利要求1所述等离子激元复合减反射膜增强太阳电池，其特征在于：所述金属纳米粒子层中金属纳米粒子为银纳米粒子、金纳米粒子或铂金属纳米粒子；The plasmon-activated composite anti-reflection film-enhancing solar cell according to claim 1, wherein the metal nanoparticles in the metal nano-particle layer are silver nanoparticles, gold nanoparticles or platinum metal nanoparticles;
    所述减反射膜层为二氧化钛。The anti-reflection film layer is titanium dioxide.
  3. 根据权利要求2所述等离子激元复合减反射膜增强太阳电池，其特征在于：所述金属纳米粒子层中金属纳米粒子为银纳米粒子。The plasmon-activated composite anti-reflection film-enhancing solar cell according to claim 2, wherein the metal nanoparticles in the metal nanoparticle layer are silver nanoparticles.
  4. 根据权利要求1所述等离子激元复合减反射膜增强太阳电池，其特征在于：所述太阳电池为肖特基结太阳电池。The plasmon-activated composite anti-reflection film-enhancing solar cell according to claim 1, wherein the solar cell is a Schottky junction solar cell.
  5. 根据权利要求4所述等离子激元复合减反射膜增强太阳电池，其特征在于：所述肖特基结太阳电池，从下到上依次包括底电极、GaAs衬底、石墨烯层和顶电极。A plasmon-activated composite anti-reflection film-enhancing solar cell according to claim 4, wherein said Schottky junction solar cell comprises, in order from bottom to top, a bottom electrode, a GaAs substrate, a graphene layer and a top electrode.
  6. 根据权利要求1～5任一项所述等离子激元复合减反射膜增强太阳电池的制备方法，其特征在于：包括以下步骤：The method for preparing a plasmon-activated composite anti-reflection film reinforced solar cell according to any one of claims 1 to 5, comprising the steps of:
    (1)配置金属纳米粒子的溶胶溶液；(1) Configuring a sol solution of metal nanoparticles;
    (2)配置减反射膜层材料的溶胶溶液；(2) locating the sol solution of the anti-reflection coating material;
    (3)将金属纳米粒子的溶胶溶液和减反射膜层材料的溶胶溶液依次旋涂在太阳电池的表面，获得等离子激元复合减反射膜太阳电池。(3) The sol solution of the metal nanoparticles and the sol solution of the anti-reflection film layer material are sequentially spin-coated on the surface of the solar cell to obtain a plasmon-activated composite anti-reflection film solar cell.
  7. 根据权利要求6所述等离子激元复合减反射膜增强太阳电池的制备方法，其特征在于：所述太阳电池为肖特基结太阳电池，金属纳米粒子的溶胶溶液为纳米银溶胶；The method for preparing a plasmon-activated composite anti-reflection film reinforced solar cell according to claim 6, wherein the solar cell is a Schottky junction solar cell, and the sol solution of the metal nanoparticle is a nanosilver sol;
    所述减反射膜层材料的溶胶溶液为二氧化钛溶胶。The sol solution of the anti-reflection film layer material is a titania sol.
  8. 根据权利要求6所述等离子激元复合减反射膜增强太阳电池的制备方法，其特征在于：金属纳米粒子的溶胶溶液在进行旋涂时，旋涂的转速为2500～4500r/min，旋涂的时间为20～100秒；减反射膜层材料的溶胶溶液在进行旋涂时，旋涂的转速为2500～4500r/min，旋涂的时间为50～100秒。The method for preparing a plasmon-activated composite anti-reflection film reinforced solar cell according to claim 6, wherein the sol solution of the metal nanoparticles is spin-coated at a rotational speed of 2500 to 4500 r/min, and is spin-coated. The time is 20 to 100 seconds; when the sol solution of the antireflection film material is spin-coated, the rotational speed of the spin coating is 2500 to 4500 r/min, and the spin coating time is 50 to 100 seconds.
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