WO2019127765A1 - Methods for preparing rare-earth-complex-doped silica microsphere solution and modified solar cell - Google Patents

Methods for preparing rare-earth-complex-doped silica microsphere solution and modified solar cell Download PDF

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WO2019127765A1
WO2019127765A1 PCT/CN2018/073548 CN2018073548W WO2019127765A1 WO 2019127765 A1 WO2019127765 A1 WO 2019127765A1 CN 2018073548 W CN2018073548 W CN 2018073548W WO 2019127765 A1 WO2019127765 A1 WO 2019127765A1
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rare earth
doped silica
earth complex
solar cell
silica microsphere
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French (fr)
Chinese (zh)
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王薇
李磊
唐建国
王瑶
黄林军
沈文飞
刘继宪
焦吉庆
王彦欣
王久兴
杜中林
王世超
李国鹏
李付霞
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青岛大学
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • 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
    • Y02E10/549—Organic 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 relates to the field of hybrid material technology and solar cell preparation technology, and particularly relates to a rare earth complex doped silica microsphere solution and a preparation method of the modified solar cell.
  • rare earth materials As a material with excellent and unique optical, electrical and magnetic properties, rare earth materials have important application value. Its unique electronic layer structure is unmatched by general materials. The advantages of high fluorescence intensity and narrow luminescence range make rare earths have unparalleled natural advantages in the field of luminescence. As a result, rare earth materials are widely used in the three fields of lighting, display and inspection. With the maturity of rare earth materials technology, the scale of industrial production and consumption related to rare earths is growing. The research on the function and application technology of rare earth compounds is an important topic in the development of materials in the 21st century. Luminescence is the most prominent advantage of rare earth compounds. Rare earth luminescent materials are an important development direction for rare earth materials.
  • the synthesis process is simple and the cost is low.
  • the combination with the flexible polymer substrate can produce higher flexibility, which makes the application field more extensive, but its stability is poor, it is easy to aging, and the low photoelectric conversion efficiency becomes a hindrance to its large scale. A huge obstacle to production and application. Improving solar cell stability and improving photoelectric conversion efficiency have become the key to researching solar cells.
  • the special optical properties of rare earth complexes provide a feasible solution to this critical problem. Due to the unique fluorescent properties of rare earths, it is possible to convert light from the wavelength range of the ultraviolet region that is not used by the active layer of the original solar cell. Rare earth can absorb light of wavelength, and can increase light absorption without increasing the thickness of the photoactive layer of the solar cell, thereby increasing the photoelectric conversion efficiency of the solar cell. At present, how to use the fluorescent properties of rare earth complexes to improve the photoelectric conversion efficiency of solar cells has important research value, and has opened up new fields for the application of rare earth complexes.
  • the object of the present invention is to improve the disadvantage of low efficiency of a solar cell, and to spin-coat a rare earth complex doped silica microsphere solution having a fluorescent property on a PET substrate of a solar cell, thereby utilizing the fluorescent property of the rare earth complex and
  • the characteristic of increasing the scattering of silicon dioxide increases the light absorption intensity of the solar cell and improves the photoelectric conversion efficiency of the solar cell.
  • the present invention provides a method for preparing a rare earth complex doped silica microsphere solution, the method comprising the steps of:
  • the two organic conjugated small molecules are respectively used as a first ligand and a second ligand, and the first ligand and the second ligand are mixed with a rare earth chloride solution to obtain a rare earth complex solution. ;
  • the invention also provides a preparation method of a modified solar cell, wherein the rare earth complex doped silica microsphere solution is spin-coated on a PET substrate of a solar cell to prepare a rare earth complex doping Modified solar cell of silica microspheres.
  • the present invention provides a rare earth complex doped silica microsphere solution and a modified solar cell preparation method, the rare earth complex doping
  • the preparation method of the silica microsphere solution comprises the following steps: (1) treating two organic conjugated small molecules as a first ligand and a second ligand, respectively, the first ligand and the second ligand and the rare earth
  • the chloride solution is mixed and reacted to obtain a rare earth complex solution
  • the silicate is added dropwise to the rare earth complex solution to obtain a rare earth complex doped silica microsphere solution.
  • the preparation method of the modified solar cell comprises spin-coating the rare earth complex doped silica microsphere solution on a PET substrate of a solar cell to prepare a modified rare earth complex doped silica microsphere.
  • Solar cells Advantages and positive effects include: (1)
  • the present invention combines a rare earth complex with silica to improve the photoelectric conversion efficiency of a solar cell.
  • the rare earth complex has excellent fluorescent properties, can absorb light in the ultraviolet range and convert it into visible light, so that the solar cell can obtain more visible light and improve its photoelectric conversion efficiency, and the ligand is added. Enhanced its ability to absorb ultraviolet light.
  • the rare earth complex of the present invention can absorb the ultraviolet spectrum in sunlight, on the one hand, can reduce the irradiation of the ultraviolet active layer to the photoactive layer, prolong the life of the photoactive layer, and improve the stability of the battery;
  • the narrow band polymer in the active layer is mixed with the acceptor material to form an interpenetrating network structure.
  • the addition of the rare earth complex can increase the light absorption intensity of the battery, and the polymer donor material absorbs a large amount of light energy to generate excitons.
  • Excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported in the donor material, eventually reaching the cathode and the anode, respectively, forming current and voltage. .
  • the silica and rare earth complex layer is used for utilizing solar cells in the ultraviolet absorption and emission of red light, and since the size of the silicon dioxide is large, direct addition to the solar cell affects itself. The structure in turn affects the efficiency of use, and spin coating on the PET substrate not only maximizes the external light but maximizes its use efficiency, but also maintains the structural integrity of the solar cell.
  • FIG. 1 is a schematic view showing the structure of a rare earth complex of the present invention, comprising a central ion Eu 3+ , 2-thiophene trifluoroacetone and 1-10 phenanthroline;
  • FIG. 3 is a schematic view showing the structure of a modified solar cell of the present invention, comprising: 1. a rare earth silicon dioxide layer, 2. a PET substrate, 3. an anode electrode ITO, 4. a hole transport layer, 5. a photoactive layer, 6. electron transport Layer, 7. cathode electrode; wherein the direction of the arrow indicates the direction of illumination;
  • Example 4 is a graph showing voltage and current density of the modified solar cell of Example 1 and the solar cell of Comparative Example 1.
  • the preparation method of the rare earth complex doped silica microsphere solution comprises the following steps:
  • the two organic conjugated small molecules are respectively used as a first ligand and a second ligand, and the first ligand and the second ligand are mixed with a rare earth chloride solution to obtain a rare earth complex solution. ;
  • the rare earth chloride solution is one of a barium chloride solution, a barium chloride solution, a barium chloride solution and a barium chloride solution, preferably a barium chloride solution, and the barium chloride has excellent properties.
  • Luminescent property embodied as red light; the first ligand is 2-thiophene trifluoroacetone, the second ligand is 1-10 phenanthroline; the first ligand and the second ligand are typical
  • a ligand having an antenna effect transfers energy to a central rare earth ion to increase the luminous efficiency of the rare earth ion, and acetylacetone and dibenzoylmethane have the same effects.
  • the molar ratio of the rare earth chloride, the first ligand, and the second ligand is 1:3:1, and the molar ratio is an optimal synthesis ratio, and the obtained rare earth complex
  • the fluorescence intensity of the object is the best.
  • the reaction temperature is room temperature
  • the reaction time is 1-3 hours.
  • the ultraviolet absorption range of the rare earth complex solution is in the range of 200-500 nm, and the rare earth complex solution absorbs in the ultraviolet range, and the ultraviolet portion can be converted into visible light to be applied to the solar cell to improve photoelectric conversion. effectiveness.
  • the silicate is ethyl orthosilicate.
  • the ultraviolet absorption range of the rare earth complex doped silica microsphere solution is in the range of 200-400 nm.
  • the silica microspheres have a diameter of 350-450 nm.
  • the rare earth complex doped silica microsphere solution absorbs in the ultraviolet range, and can convert the ultraviolet portion into visible light to be applied to a solar cell to improve photoelectric conversion efficiency.
  • the reaction time is 6 to 9 hours.
  • a method for preparing a modified solar cell wherein a rare earth complex doped silica microsphere solution is spin-coated on a PET substrate of a solar cell to prepare a modified solar cell having rare earth complex doped silica microspheres .
  • the preparation method of the modified solar cell specifically includes the following steps:
  • the PET transparent substrate with anode electrode ITO is ultrasonically cleaned with detergent, deionized water, acetone, deionized water, absolute ethanol and isopropanol, washed, dried with dry high-purity nitrogen or dried at high temperature. Drying, forming a clean PET substrate; then transferring the PET substrate to a plasma surface treatment apparatus, plasma treating the PET substrate for 5-15 minutes under a pressure of 25 Pa, oxygen and nitrogen, and then cooling to room temperature;
  • step 3 forming a discontinuously dispersed uniform rare earth silica layer on the plasma treated PET substrate (without the ITO surface) in step 1) by spin coating;
  • step 5) forming a photoactive layer on the hole transport layer of step 4) by spin coating the active layer material
  • An electron transport layer and a cathode electrode layer are sequentially deposited by vapor deposition on the photoactive layer of the step 5) to prepare a modified solar cell having rare earth complex doped silica microspheres.
  • the anode electrode of the solar cell of the present invention is transparent conductive bismuth tin oxide (ITO), and the anode electrode is formed by vapor deposition or magnetron sputtering.
  • the material of the anode electrode has a high transmittance in the visible light wavelength range.
  • the invention spin-coats the rare earth complex doped silica microsphere solution on the PET substrate of the solar cell instead of the anode electrode ITO layer because the anode electrode ITO layer is the inside of the battery and is suspended on the ITO layer.
  • a hole transport layer such as PEDOT:PSS, if the rare earth complex doped silica microsphere solution is spin coated on the anodic electrode ITO layer, the rare earth complex layer is adjacent to the hole transport layer, which will not cause battery efficiency.
  • the hole transport layer is a PEDOT:PSS polymer conductive film (PEDOT is a polymer of 3,4-ethylenedioxyphene monomer, PSS is polystyrene sulfonate), hole transport layer
  • PEDOT is a polymer of 3,4-ethylenedioxyphene monomer
  • PSS is polystyrene sulfonate
  • hole transport layer The material has electrical conductivity and work function and has a transmittance in the visible wavelength range.
  • the photoactive layer material comprises a polymer donor material and an acceptor material, and the two materials are mixed to form an interpenetrating network structure, wherein the donor material absorbs light energy to generate excitons, and the LUMO energy level of the donor material Above the LUMO level of the acceptor material, excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported into the material, ultimately The cathode and anode are reached to form a current and a voltage.
  • Polymer donor materials include polybenzazoles (such as P3HT, PEOPT and P30T, etc.), polyparaphenylene vinylene derivatives (such as MDMO-PPV and MEH-PPV, etc.) and DA-type narrow bandgap conjugated donor polymer materials. (such as PBDTTT-CT, PCPDTBT, PBDTTPD, PNDT-BT, PBDFDTBT and PDTSTPD), the polymer donor material has a conjugated structure that absorbs light energy in visible light and undergoes electronic transitions to form excitons.
  • the acceptor material includes fullerene derivatives such as PC 61 BM, PC 71 BM, ICBA and ICMA.
  • the acceptor material can form a nano-interpenetrating network structure with the polymer donor material in the photoactive layer material, with the polymer Different absorption ranges for donor materials.
  • the material of the cathode material comprises aluminum and calcium
  • the material of the cathode electrode of the battery is electrically conductive, and the work function is low, and an internal electric field can be formed with the anode electrode having a high work function, which is favorable for the transfer of electrons and holes.
  • the present invention combines a rare earth complex with silica to improve the photoelectric conversion efficiency of a solar cell.
  • the rare earth complex has excellent fluorescent properties, can absorb light in the ultraviolet range and convert it into visible light, so that the solar cell can obtain more visible light and improve its photoelectric conversion efficiency, and the ligand is added. Enhanced its ability to absorb ultraviolet light.
  • the silicon dioxide can also Improve the stability of the rare earth complex.
  • the rare earth complex of the present invention can absorb the ultraviolet spectrum in sunlight, on the one hand, can reduce the irradiation of the ultraviolet active layer to the photoactive layer, prolong the life of the photoactive layer, and improve the stability of the battery;
  • the narrow band polymer in the active layer is mixed with the acceptor material to form an interpenetrating network structure.
  • the addition of the rare earth complex can increase the light absorption intensity of the battery, and the polymer donor material absorbs a large amount of light energy to generate excitons.
  • Excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported in the donor material, eventually reaching the cathode and the anode, respectively, forming current and voltage. .
  • the silica and rare earth complex layer is used for utilizing solar cells in the ultraviolet absorption and emission of red light, and since the size of the silicon dioxide is large, direct addition to the solar cell affects itself.
  • the structure in turn affects the efficiency of use, and spin coating on the PET substrate not only maximizes the external light but maximizes its use efficiency, but also maintains the structural integrity of the solar cell.
  • the preparation process of the ruthenium chloride solution a certain amount of ruthenium oxide and an excess of aqueous hydrogen chloride are reacted under stirring for a period of time to fully dissolve the solution, and the solution is transferred to a 70 ° C oil bath to evaporate the excess solvent until the solvent Disappeared, the remaining reactants were crystals, dried to obtain EuCl 3 ⁇ H 2 O, and then the crystals were dissolved with an appropriate amount of ethanol to prepare a cerium chloride solution having a concentration of 0.1 mol/L;
  • the modified solar cell main structure of the present embodiment comprises: a rare earth silicon dioxide layer having a thickness of 400 nm; a PET substrate having a thickness of 180 nm; an anode electrode ITO having a thickness of 180 nm; and a hole transport layer being a PEDOT:PSS polymerization.
  • the PET transparent substrate with anode electrode ITO is ultrasonically cleaned with detergent, deionized water, acetone, deionized water, absolute ethanol and isopropanol, washed, dried with dry high-purity nitrogen or dried at high temperature. Dry to form a clean PET substrate; then transfer the PET substrate to a plasma surface treatment apparatus, plasma-treat the PET substrate for 6 minutes under a pressure of 25 Pa, oxygen and nitrogen, and then cool to room temperature;
  • step 1) the plasma-treated PET substrate is placed in a homogenizer, and the step 2) spin-coating the uniform rare earth complex-doped silica microsphere solution on the PET substrate at a rotation speed of 2000 rpm for a time of 40s, finally forming a rare earth silicon dioxide layer having a thickness of 400 nm on the PET substrate;
  • step 1) of the anode electrode ITO obtained in the step 3) repeating the operation of the step 1) of the anode electrode ITO obtained in the step 3) to obtain the plasma-treated anode electrode ITO; the plasma-treated anode electrode ITO is placed in the homogenizer, and the polyelectrolyte is spin-coated on the anode electrode ITO.
  • Conductive material PEDOT:PSS rotating at 4000 rpm for 40 s, finally forming a hole transport layer (polymer conductive film) having a thickness of 30 nm on the anode electrode ITO, followed by heat treatment at 100 ° C for 20 minutes;
  • the hole transport layer obtained in the step 4) is placed in a homomixer, and a solution of PBDTT-CT and PC71BM having a mass ratio of 1:1.5 and a total concentration of 25 mg/mL in an o-dichlorobenzene solution is spin-coated at 800 rpm.
  • the photoactive layer is formed on the hole transport layer at a time of 60 s; and the heat treatment is performed in step 4) to increase the surface roughness of the photoactive layer, thereby causing phase separation between the acceptor and the donor material, thereby increasing the crystallinity of the active layer, thereby Allowing the acceptor and donor materials to form an interpenetrating network structure;
  • step 6) sequentially forming an electron transport layer and a cathode electrode layer by vapor deposition on the photoactive layer of step 5) to obtain a modified solar cell; applying a vacuum evaporation apparatus having a degree of vacuum greater than 5 ⁇ 10 ⁇ 4 Pa Evaporation, the electron transport layer material is Ca, the evaporation rate is 0.01 nm/s, the thickness is 10 nm; the cathode electrode material is Al, the evaporation rate is 0.5 nm/s, the thickness is 100 nm, and the evaporation rate and thickness are installed by the probe. Monitoring of the crystal film thickness gauge near the substrate.
  • the solar cell of the present comparative example was substantially the same as the solar cell prepared in Example 1, except that the PET substrate of the solar cell of Comparative Example 1 was not spin-coated with a rare earth complex doped silica microsphere layer.
  • the solar cell of the solar cell of Example 1 has a rare earth complex doped silica microsphere layer on the PET substrate, and the solar cell of the solar cell of Comparative Example 1 has no rare earth complex doped silica microsphere layer on the PET substrate. 4, the photovoltaic conversion efficiency of the solar cell of Example 1 was greater than that of the solar cell of Comparative Example 1.
  • the small molecule ligand in the complex absorbs the energy of the ultraviolet portion and then transfers the energy when the sunlight passes through the rare earth silica layer without affecting the light transmittance.
  • the solar cell of Embodiment 1 corresponds to an increase in the ratio of visible light, so that the photoelectric conversion efficiency is increased; meanwhile, when the light passes through the rare earth silicon dioxide layer, the light is scattered and angled. Deflection occurs, resulting in a longer optical path and increased photoelectric conversion efficiency.
  • the energy conversion efficiency of the solar cell coated with the rare earth doped silica microsphere layer prepared in Example 1 was 7.85%, and the solar cell efficiency of Comparative Example 1 was 7.05%; compared with Comparative Example 1, the example 1
  • the photoelectric conversion efficiency of the solar cell is improved by about 11.3%.

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Abstract

Disclosed are methods for preparing a rare-earth-complex-doped silica microsphere solution and a modified solar cell, wherein the method for preparing a rare-earth-complex-doped silica microsphere solution comprises the following steps: (1) two types of organic conjugated small molecules are respectively used as a first ligand and a second ligand, the first ligand and the second ligand are mixed and reacted with a rare-earth chloride solution so as to obtain a rare-earth complex solution; and (2) a silicate ester is added dropwise to the rare-earth complex solution for reaction to obtain the rare-earth-complex-doped silica microsphere solution. The method for preparing a modified solar cell comprises spin-coating the rare-earth-complex-doped silica microsphere solution on a PET substrate of a solar cell so as to obtain a modified solar cell having rare-earth-complex-doped silica microspheres. The fluorescence properties of a rare-earth complex and the increase in scattering by silica are used to improve the light absorption intensity of a solar cell, and to improve the photoelectric conversion efficiency of the solar cell.

Description

稀土络合物掺杂二氧化硅微球溶液和改性太阳能电池的制备方法Rare earth complex doped silica microsphere solution and preparation method of modified solar cell 技术领域Technical field
本发明涉及杂化材料技术和太阳能电池制备技术的交叉领域，特别涉及一种稀土络合物掺杂二氧化硅微球溶液和改性太阳能电池的制备方法。The invention relates to the field of hybrid material technology and solar cell preparation technology, and particularly relates to a rare earth complex doped silica microsphere solution and a preparation method of the modified solar cell.
背景技术Background technique
作为一种具有优异且独特的光、电、磁性能的材料，稀土材料具有十分重要的应用价值。其独特的电子层结构，是一般材料所无法比拟的。而其荧光强度高、发光范围窄的优势使得稀土在发光领域拥有者无可比拟的天然优势。由此，稀土材料被广泛应用于照明、显示和检测三大领域，伴随着稀土材料技术的日臻成熟，与稀土有关的工业生产和消费市场规模日益庞大。稀土化合物功能和应用技术的研究是21世纪材料发展的重要课题。发光是稀土化合物最突出的优势功能，稀土发光材料是稀土材料研究重要的发展方向。As a material with excellent and unique optical, electrical and magnetic properties, rare earth materials have important application value. Its unique electronic layer structure is unmatched by general materials. The advantages of high fluorescence intensity and narrow luminescence range make rare earths have unparalleled natural advantages in the field of luminescence. As a result, rare earth materials are widely used in the three fields of lighting, display and inspection. With the maturity of rare earth materials technology, the scale of industrial production and consumption related to rare earths is growing. The research on the function and application technology of rare earth compounds is an important topic in the development of materials in the 21st century. Luminescence is the most prominent advantage of rare earth compounds. Rare earth luminescent materials are an important development direction for rare earth materials.
而随着人类世界的不断发展，能源问题成为制约人类发展的一个主要因素。如何合理的利用自然资源成为一个亟待解决的问题。太阳能是取之不尽、用之不竭的清洁能源，在化石能源日益枯竭、环境污染日益严重的今天，将太阳能转化为电能被视为是一个可以实现人类可持续发展的一条出路。而其中以无机半导体材料作为核心的太阳能电池发展迅速，占据了90%左右的太阳能电池市场，但由于其生产工艺复杂、成本高、制作耗能高等不足，制约了其大规模的使用和发展。而对于太阳能电池而言，则其制备工艺简单、成本较低、可弯曲度高，成为了新能源发展的又一热点。With the continuous development of the human world, the energy issue has become a major factor constraining human development. How to make rational use of natural resources has become an urgent problem to be solved. Solar energy is an inexhaustible source of clean energy. In today's increasingly depleted fossil energy and increasingly polluted environment, converting solar energy into electricity is regarded as a way to achieve sustainable human development. Among them, solar cells with inorganic semiconductor materials as the core have developed rapidly, occupying about 90% of the solar cell market. However, due to its complicated production process, high cost and high energy consumption, it has restricted its large-scale use and development. For solar cells, the preparation process is simple, the cost is low, and the flexibility is high, which has become another hot spot in the development of new energy.
对于太阳能电池而言，合成工艺简单，成本较低，与柔性聚合物基底结合生产可以获得柔性较高使得其应用领域更加广泛，但其稳定性差，容易老化，光电转换效率低下成为阻碍其大规模生产与应用的一个巨大障碍。改善太阳能电池稳定性，提高光电转化效率成为研究太阳能电池的关键。For solar cells, the synthesis process is simple and the cost is low. The combination with the flexible polymer substrate can produce higher flexibility, which makes the application field more extensive, but its stability is poor, it is easy to aging, and the low photoelectric conversion efficiency becomes a hindrance to its large scale. A huge obstacle to production and application. Improving solar cell stability and improving photoelectric conversion efficiency have become the key to researching solar cells.
稀土络合物特殊的光学性能则为解决这一关键问题提供了一条可行的解决方法，由于稀土自身独特的荧光特性，可以将原来太阳能电池活性层利用不到的如紫外区波长范围的光转换成稀土可吸收波长的光，可以在不增加太阳能电池光活性层厚度的情况下增加光吸收，从而增加太阳能电池的光电转化效率。目前，如何利用稀土络合物的荧光性能来提高太阳能电池的光电转化效率具有重要的研究价值，也为稀土络合物的应用开拓了新领域。The special optical properties of rare earth complexes provide a feasible solution to this critical problem. Due to the unique fluorescent properties of rare earths, it is possible to convert light from the wavelength range of the ultraviolet region that is not used by the active layer of the original solar cell. Rare earth can absorb light of wavelength, and can increase light absorption without increasing the thickness of the photoactive layer of the solar cell, thereby increasing the photoelectric conversion efficiency of the solar cell. At present, how to use the fluorescent properties of rare earth complexes to improve the photoelectric conversion efficiency of solar cells has important research value, and has opened up new fields for the application of rare earth complexes.
技术问题technical problem
本发明的目的在于改善太阳能电池效率低的缺点，通过将具有荧光特性的稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，利用稀土络合物的荧光特性以及二氧化硅增加散射的特点增大太阳能电池的光吸收强度，提高太阳能电池的光电转化效率。The object of the present invention is to improve the disadvantage of low efficiency of a solar cell, and to spin-coat a rare earth complex doped silica microsphere solution having a fluorescent property on a PET substrate of a solar cell, thereby utilizing the fluorescent property of the rare earth complex and The characteristic of increasing the scattering of silicon dioxide increases the light absorption intensity of the solar cell and improves the photoelectric conversion efficiency of the solar cell.
技术解决方案Technical solution
为此，本发明提供了一种稀土络合物掺杂二氧化硅微球溶液的制备方法，所述方法包括以下步骤：To this end, the present invention provides a method for preparing a rare earth complex doped silica microsphere solution, the method comprising the steps of:
（1）将两种有机共轭小分子分别作为第一配体和第二配体，所述第一配体和所述第二配体与稀土氯化物溶液混合反应，得到稀土络合物溶液；(1) The two organic conjugated small molecules are respectively used as a first ligand and a second ligand, and the first ligand and the second ligand are mixed with a rare earth chloride solution to obtain a rare earth complex solution. ;
（2）在所述稀土络合物溶液中滴加硅酸酯进行反应，得到稀土络合物掺杂二氧化硅微球溶液。(2) A silicate is added dropwise to the rare earth complex solution to carry out a reaction to obtain a rare earth complex-doped silica microsphere solution.
本发明还提供了一种改性太阳能电池的制备方法，将所述的稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。The invention also provides a preparation method of a modified solar cell, wherein the rare earth complex doped silica microsphere solution is spin-coated on a PET substrate of a solar cell to prepare a rare earth complex doping Modified solar cell of silica microspheres.
有益效果Beneficial effect
与现有技术相比，本发明的优点和积极效果是：本发明提供了一种稀土络合物掺杂二氧化硅微球溶液和改性太阳能电池的制备方法，稀土络合物掺杂二氧化硅微球溶液的制备方法包括以下步骤：（1）将两种有机共轭小分子分别作为第一配体和第二配体，所述第一配体和所述第二配体与稀土氯化物溶液混合反应，得到稀土络合物溶液；（2）在所述稀土络合物溶液中滴加硅酸酯进行反应，得到稀土络合物掺杂二氧化硅微球溶液。改性太阳能电池的制备方法包括将所述的稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。优点和积极效果包括：（1）本发明将稀土络合物和二氧化硅相结合，以提高太阳能电池的光电转化效率。其中，稀土络合物具有优异的荧光性能，可以吸收紫外范围的光并将其转化成可见光发射出来，从而使得太阳能电池可以得到更多的可见光，提高其光电转化效率，而配体的加入则增强了其吸收紫外光的能力。当光线经过二氧化硅时，会发生散射，使得原先入射的光线角度发生变化，在太阳能电池内部的光程得以延长，也可以在一定程度上增加太阳能电池的光电转化效率；二氧化硅还可以提高稀土络合物的稳定性。（2）本发明的稀土络合物能够吸收太阳光中的紫外光谱，一方面可以减少紫外光对光活性层的照射，延长光活性层的寿命，提高电池的稳定性；另一方面，光活性层中的窄带系聚合物给体材料和受体材料混合能够形成互穿网络结构，稀土络合物的加入能够增加电池的光吸收强度，聚合物给体材料吸收大量的光能产生激子，激子在给体材料与受体材料界面处产生分离，形成电子和空穴，电子在受体材料中传输，空穴在给体材料中传输，最终分别到达阴极和阳极，形成电流和电压。（3）二氧化硅与稀土络合物层是为了利用其在紫外吸收发射出红光而被太阳能电池利用的这一特性，而由于二氧化硅尺寸较大，直接加入太阳能电池中会影响本身的结构进而影响使用效率，而旋涂在PET基底上上不仅可以最大程度上的接受到外界光线而使其使用效率最大化，还可以保持太阳能电池结构的完整性。Compared with the prior art, the advantages and positive effects of the present invention are: the present invention provides a rare earth complex doped silica microsphere solution and a modified solar cell preparation method, the rare earth complex doping The preparation method of the silica microsphere solution comprises the following steps: (1) treating two organic conjugated small molecules as a first ligand and a second ligand, respectively, the first ligand and the second ligand and the rare earth The chloride solution is mixed and reacted to obtain a rare earth complex solution; (2) the silicate is added dropwise to the rare earth complex solution to obtain a rare earth complex doped silica microsphere solution. The preparation method of the modified solar cell comprises spin-coating the rare earth complex doped silica microsphere solution on a PET substrate of a solar cell to prepare a modified rare earth complex doped silica microsphere. Solar cells. Advantages and positive effects include: (1) The present invention combines a rare earth complex with silica to improve the photoelectric conversion efficiency of a solar cell. Among them, the rare earth complex has excellent fluorescent properties, can absorb light in the ultraviolet range and convert it into visible light, so that the solar cell can obtain more visible light and improve its photoelectric conversion efficiency, and the ligand is added. Enhanced its ability to absorb ultraviolet light. When the light passes through the silica, scattering occurs, so that the angle of the originally incident light changes, the optical path inside the solar cell is prolonged, and the photoelectric conversion efficiency of the solar cell can be increased to some extent; the silicon dioxide can also Improve the stability of the rare earth complex. (2) The rare earth complex of the present invention can absorb the ultraviolet spectrum in sunlight, on the one hand, can reduce the irradiation of the ultraviolet active layer to the photoactive layer, prolong the life of the photoactive layer, and improve the stability of the battery; The narrow band polymer in the active layer is mixed with the acceptor material to form an interpenetrating network structure. The addition of the rare earth complex can increase the light absorption intensity of the battery, and the polymer donor material absorbs a large amount of light energy to generate excitons. Excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported in the donor material, eventually reaching the cathode and the anode, respectively, forming current and voltage. . (3) The silica and rare earth complex layer is used for utilizing solar cells in the ultraviolet absorption and emission of red light, and since the size of the silicon dioxide is large, direct addition to the solar cell affects itself. The structure in turn affects the efficiency of use, and spin coating on the PET substrate not only maximizes the external light but maximizes its use efficiency, but also maintains the structural integrity of the solar cell.
结合附图阅读本发明的具体实施方式后，本发明的其他特点和优点将变得更加清楚。Other features and advantages of the present invention will become apparent from the Detailed Description of the Drawing.
附图说明DRAWINGS
图1为本发明稀土络合物结构示意图，包括中心离子Eu 3+、2-噻吩甲酰三氟丙酮和1-10菲罗啉； 1 is a schematic view showing the structure of a rare earth complex of the present invention, comprising a central ion Eu 3+ , 2-thiophene trifluoroacetone and 1-10 phenanthroline;
图2为本发明稀土络合物掺杂二氧化硅微球的透射电镜照片；2 is a transmission electron micrograph of a rare earth complex doped silica microsphere of the present invention;
图3为本发明改性太阳能电池结构原理示意图，包括1.稀土二氧化硅层，2.PET基底，3.阳极电极ITO，4.空穴传输层，5.光活性层，6.电子传输层，7.阴极电极；其中箭头方向表示光照方向；3 is a schematic view showing the structure of a modified solar cell of the present invention, comprising: 1. a rare earth silicon dioxide layer, 2. a PET substrate, 3. an anode electrode ITO, 4. a hole transport layer, 5. a photoactive layer, 6. electron transport Layer, 7. cathode electrode; wherein the direction of the arrow indicates the direction of illumination;
图4为实施例1的改性太阳能电池和对比例1的太阳能电池的电压与电流密度的曲线图。4 is a graph showing voltage and current density of the modified solar cell of Example 1 and the solar cell of Comparative Example 1.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
以下对本发明的具体实施方式进行详细说明，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。The detailed description of the embodiments of the present invention is intended to be understood as
稀土络合物掺杂二氧化硅微球溶液的制备方法包括以下步骤：The preparation method of the rare earth complex doped silica microsphere solution comprises the following steps:
（1）将两种有机共轭小分子分别作为第一配体和第二配体，所述第一配体和所述第二配体与稀土氯化物溶液混合反应，得到稀土络合物溶液；(1) The two organic conjugated small molecules are respectively used as a first ligand and a second ligand, and the first ligand and the second ligand are mixed with a rare earth chloride solution to obtain a rare earth complex solution. ;
（2）在所述稀土络合物溶液中滴加硅酸酯进行反应，得到稀土络合物掺杂二氧化硅微球溶液。(2) A silicate is added dropwise to the rare earth complex solution to carry out a reaction to obtain a rare earth complex-doped silica microsphere solution.
步骤（1）中，所述稀土氯化物溶液为氯化铕溶液、氯化铽溶液、氯化铥溶液和氯化钆溶液中的一种，优选为氯化铕溶液，氯化铕具有优异的发光性能，体现为红光；所述第一配体为2-噻吩甲酰三氟丙酮，所述第二配体为1-10菲罗啉；第一配体和第二配体是典型的具有天线效应的配体，将能量转移给中心稀土离子以提高稀土离子的发光效率，具有相同作用的还有乙酰丙酮和二苯甲酰甲烷等。In the step (1), the rare earth chloride solution is one of a barium chloride solution, a barium chloride solution, a barium chloride solution and a barium chloride solution, preferably a barium chloride solution, and the barium chloride has excellent properties. Luminescent property, embodied as red light; the first ligand is 2-thiophene trifluoroacetone, the second ligand is 1-10 phenanthroline; the first ligand and the second ligand are typical A ligand having an antenna effect transfers energy to a central rare earth ion to increase the luminous efficiency of the rare earth ion, and acetylacetone and dibenzoylmethane have the same effects.
步骤（1）中，所述稀土氯化物、所述第一配体、所述第二配体的摩尔比为1：3：1，此摩尔比是最优的合成比例，所得的稀土络合物荧光强度最好。In the step (1), the molar ratio of the rare earth chloride, the first ligand, and the second ligand is 1:3:1, and the molar ratio is an optimal synthesis ratio, and the obtained rare earth complex The fluorescence intensity of the object is the best.
步骤（1）中，反应温度为室温，反应时间为1-3h。In the step (1), the reaction temperature is room temperature, and the reaction time is 1-3 hours.
步骤（1）中，所述稀土络合物溶液的紫外吸收范围处于200-500nm，稀土络合物溶液在紫外范围有吸收，可以将紫外部分转化成可见光从而应用于太阳能电池中以提高光电转化效率。In the step (1), the ultraviolet absorption range of the rare earth complex solution is in the range of 200-500 nm, and the rare earth complex solution absorbs in the ultraviolet range, and the ultraviolet portion can be converted into visible light to be applied to the solar cell to improve photoelectric conversion. effectiveness.
步骤（2）中，所述硅酸酯为正硅酸乙酯。In the step (2), the silicate is ethyl orthosilicate.
步骤（2）中，稀土络合物掺杂二氧化硅微球溶液的紫外吸收范围处于200-400nm，In the step (2), the ultraviolet absorption range of the rare earth complex doped silica microsphere solution is in the range of 200-400 nm.
二氧化硅微球直径为350-450nm。稀土络合物掺杂二氧化硅微球溶液在紫外范围有吸收，可以将紫外部分转化成可见光从而应用于太阳能电池中以提高光电转化效率。The silica microspheres have a diameter of 350-450 nm. The rare earth complex doped silica microsphere solution absorbs in the ultraviolet range, and can convert the ultraviolet portion into visible light to be applied to a solar cell to improve photoelectric conversion efficiency.
步骤（2）中，反应时间为6-9h。In the step (2), the reaction time is 6 to 9 hours.
改性太阳能电池的制备方法，将稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。A method for preparing a modified solar cell, wherein a rare earth complex doped silica microsphere solution is spin-coated on a PET substrate of a solar cell to prepare a modified solar cell having rare earth complex doped silica microspheres .
改性太阳能电池的制备方法具体包括如下步骤：The preparation method of the modified solar cell specifically includes the following steps:
1）将带有阳极电极ITO的PET透明基底依次用洗涤剂、去离子水、丙酮、去离子水、无水乙醇和异丙醇超声清洗，清洗后用干燥的高纯氮气吹干或高温烘干，形成洁净的PET基底；然后将所述PET基底转入等离子体表面处理仪，在25Pa气压，氧气和氮气环境下对所述PET基底等离子处理5-15min后冷却至室温；1) The PET transparent substrate with anode electrode ITO is ultrasonically cleaned with detergent, deionized water, acetone, deionized water, absolute ethanol and isopropanol, washed, dried with dry high-purity nitrogen or dried at high temperature. Drying, forming a clean PET substrate; then transferring the PET substrate to a plasma surface treatment apparatus, plasma treating the PET substrate for 5-15 minutes under a pressure of 25 Pa, oxygen and nitrogen, and then cooling to room temperature;
2）用有机溶剂对所述稀土络合物掺杂二氧化硅微球溶液进行稀释，然后经超声分散，得到分散均匀的稀土络合物掺杂二氧化硅微球溶液；2) diluting the rare earth complex doped silica microsphere solution with an organic solvent, and then dispersing by ultrasonication to obtain a uniformly dispersed rare earth complex doped silica microsphere solution;
3）在步骤1）等离子处理过的PET基底上（不含ITO面）通过旋涂的方法形成不连续分散均匀的稀土二氧化硅层；3) forming a discontinuously dispersed uniform rare earth silica layer on the plasma treated PET substrate (without the ITO surface) in step 1) by spin coating;
4）在步骤3）形成的阳极电极ITO面上通过旋涂的方法形成带有一层空穴传输层的导电基底；4) forming a conductive substrate with a hole transport layer by spin coating on the ITO surface of the anode electrode formed in the step 3);
5）将活性层材料通过旋涂的方法在步骤4）的空穴传输层上形成光活性层；5) forming a photoactive layer on the hole transport layer of step 4) by spin coating the active layer material;
6）在步骤5）的光活性层上通过蒸镀的方法依次蒸镀形成电子传输层和阴极电极层，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。6) An electron transport layer and a cathode electrode layer are sequentially deposited by vapor deposition on the photoactive layer of the step 5) to prepare a modified solar cell having rare earth complex doped silica microspheres.
本发明的太阳能电池的阳极电极为透明导电的氧化锢锡(ITO)，阳极电极通过气相沉积、磁控溅射的方法形成，阳极电极的材质在可见光波长范围内有较高的透过率。The anode electrode of the solar cell of the present invention is transparent conductive bismuth tin oxide (ITO), and the anode electrode is formed by vapor deposition or magnetron sputtering. The material of the anode electrode has a high transmittance in the visible light wavelength range.
本发明将稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，而非阳极电极ITO层上，是因为阳极电极ITO层是电池内部，在ITO层上悬涂空穴传输层，如PEDOT:PSS，如果将稀土络合物掺杂二氧化硅微球溶液旋涂在阳极电极ITO层上的话，稀土络合物层紧邻空穴传输层，会对电池效率产生不好的影响：（1）影响空穴传输层性能，（2）PEDOT:PSS是酸性的，会对稀土络合物的荧光性能产生负面影响。The invention spin-coats the rare earth complex doped silica microsphere solution on the PET substrate of the solar cell instead of the anode electrode ITO layer because the anode electrode ITO layer is the inside of the battery and is suspended on the ITO layer. A hole transport layer, such as PEDOT:PSS, if the rare earth complex doped silica microsphere solution is spin coated on the anodic electrode ITO layer, the rare earth complex layer is adjacent to the hole transport layer, which will not cause battery efficiency. Good effects: (1) affect the performance of the hole transport layer, (2) PEDOT: PSS is acidic, which will have a negative impact on the fluorescent properties of the rare earth complex.
步骤4）中，空穴传输层为PEDOT:PSS聚合物导电薄膜 (PEDOT是3,4-乙撑二氧曝吩单体的聚合物，PSS是聚苯乙烯磺酸盐)，空穴传输层的材质具有导电率和功函数，在可见光波长范围内有透过率。In step 4), the hole transport layer is a PEDOT:PSS polymer conductive film (PEDOT is a polymer of 3,4-ethylenedioxyphene monomer, PSS is polystyrene sulfonate), hole transport layer The material has electrical conductivity and work function and has a transmittance in the visible wavelength range.
步骤5）中，光活性层材料包括聚合物给体材料和受体材料，这两种材料会混合形成互穿网络结构，其中给体材料吸收光能产生激子，给体材料的LUMO能级高于受体材料的LUMO能级，激子在给体材料与受体材料界面处产生分离，形成电子和空穴，电子在受体材料中传输，空穴存给体材料中传输，最终分别到达阴极和阳极，从而形成电流和电压。In step 5), the photoactive layer material comprises a polymer donor material and an acceptor material, and the two materials are mixed to form an interpenetrating network structure, wherein the donor material absorbs light energy to generate excitons, and the LUMO energy level of the donor material Above the LUMO level of the acceptor material, excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported into the material, ultimately The cathode and anode are reached to form a current and a voltage.
聚合物给体材料包括聚唆吩类(如P3HT,PEOPT和P30T等)、聚对苯亚乙烯衍生物(如MDMO-PPV和MEH-PPV等)和D-A型窄带隙共扼给体聚合物材料(如PBDTTT-C-T,PCPDTBT,PBDTTPD,PNDT-BT,PBDFDTBT和PDTSTPD)，聚合物给体材料具有共扼结构，能够吸收可见光中的光能并发生电子跃迁形成激子。受体材料包括富勒烯衍生物，如PC 61BM, PC 71BM、ICBA和ICMA，受体材料能在光活性层材料中与聚合物给体材料形成纳米互穿网络结构，有着与聚合物给体材料不同的吸光范围。 Polymer donor materials include polybenzazoles (such as P3HT, PEOPT and P30T, etc.), polyparaphenylene vinylene derivatives (such as MDMO-PPV and MEH-PPV, etc.) and DA-type narrow bandgap conjugated donor polymer materials. (such as PBDTTT-CT, PCPDTBT, PBDTTPD, PNDT-BT, PBDFDTBT and PDTSTPD), the polymer donor material has a conjugated structure that absorbs light energy in visible light and undergoes electronic transitions to form excitons. The acceptor material includes fullerene derivatives such as PC 61 BM, PC 71 BM, ICBA and ICMA. The acceptor material can form a nano-interpenetrating network structure with the polymer donor material in the photoactive layer material, with the polymer Different absorption ranges for donor materials.
步骤6）中，阴极材料的材质包括铝和钙，电池的阴极电极的材质有导电性，功函数低，能够和功函数高的阳极电极形成内电场，有利于电子和空穴的转移。In the step 6), the material of the cathode material comprises aluminum and calcium, and the material of the cathode electrode of the battery is electrically conductive, and the work function is low, and an internal electric field can be formed with the anode electrode having a high work function, which is favorable for the transfer of electrons and holes.
本发明的优点和积极效果包括；Advantages and positive effects of the present invention include;
（1）本发明将稀土络合物和二氧化硅相结合，以提高太阳能电池的光电转化效率。其中，稀土络合物具有优异的荧光性能，可以吸收紫外范围的光并将其转化成可见光发射出来，从而使得太阳能电池可以得到更多的可见光，提高其光电转化效率，而配体的加入则增强了其吸收紫外光的能力。当光线经过二氧化硅时，会发生散射，使得原先入射的光线角度发生变化，在太阳能电池内部的光程得以延长，也可以在一定程度上增加太阳能电池的光电转化效率；二氧化硅还可以提高稀土络合物的稳定性。(1) The present invention combines a rare earth complex with silica to improve the photoelectric conversion efficiency of a solar cell. Among them, the rare earth complex has excellent fluorescent properties, can absorb light in the ultraviolet range and convert it into visible light, so that the solar cell can obtain more visible light and improve its photoelectric conversion efficiency, and the ligand is added. Enhanced its ability to absorb ultraviolet light. When the light passes through the silica, scattering occurs, so that the angle of the originally incident light changes, the optical path inside the solar cell is prolonged, and the photoelectric conversion efficiency of the solar cell can be increased to some extent; the silicon dioxide can also Improve the stability of the rare earth complex.
（2）本发明的稀土络合物能够吸收太阳光中的紫外光谱，一方面可以减少紫外光对光活性层的照射，延长光活性层的寿命，提高电池的稳定性；另一方面，光活性层中的窄带系聚合物给体材料和受体材料混合能够形成互穿网络结构，稀土络合物的加入能够增加电池的光吸收强度，聚合物给体材料吸收大量的光能产生激子，激子在给体材料与受体材料界面处产生分离，形成电子和空穴，电子在受体材料中传输，空穴在给体材料中传输，最终分别到达阴极和阳极，形成电流和电压。(2) The rare earth complex of the present invention can absorb the ultraviolet spectrum in sunlight, on the one hand, can reduce the irradiation of the ultraviolet active layer to the photoactive layer, prolong the life of the photoactive layer, and improve the stability of the battery; The narrow band polymer in the active layer is mixed with the acceptor material to form an interpenetrating network structure. The addition of the rare earth complex can increase the light absorption intensity of the battery, and the polymer donor material absorbs a large amount of light energy to generate excitons. Excitons separate at the interface between the donor material and the acceptor material, forming electrons and holes, electrons are transported in the acceptor material, and holes are transported in the donor material, eventually reaching the cathode and the anode, respectively, forming current and voltage. .
（3）二氧化硅与稀土络合物层是为了利用其在紫外吸收发射出红光而被太阳能电池利用的这一特性，而由于二氧化硅尺寸较大，直接加入太阳能电池中会影响本身的结构进而影响使用效率，而旋涂在PET基底上上不仅可以最大程度上的接受到外界光线而使其使用效率最大化，还可以保持太阳能电池结构的完整性。(3) The silica and rare earth complex layer is used for utilizing solar cells in the ultraviolet absorption and emission of red light, and since the size of the silicon dioxide is large, direct addition to the solar cell affects itself. The structure in turn affects the efficiency of use, and spin coating on the PET substrate not only maximizes the external light but maximizes its use efficiency, but also maintains the structural integrity of the solar cell.
实施例1Example 1
本实施例的稀土络合物掺杂二氧化硅微球溶液的制备方法包括以下步骤：The preparation method of the rare earth complex doped silica microsphere solution of the present embodiment comprises the following steps:
（1）将2-噻吩甲酰三氟丙酮作为第一配体，将1-10菲罗啉作为第二配体，第一配体和第二配体与氯化铕溶液混合，氯化铕、2-噻吩甲酰三氟丙酮、1-10菲罗啉的摩尔比为1：3：1，在室温下反应2h，得到稀土络合物溶液；(1) 2-thiophene trifluoroacetone as a first ligand, 1-10 phenanthroline as a second ligand, first ligand and second ligand mixed with a ruthenium chloride solution, ruthenium chloride , the molar ratio of 2-thiophene trifluoroacetone and 1-10 phenanthroline is 1:3:1, and reacted at room temperature for 2 hours to obtain a rare earth complex solution;
其中，氯化铕溶液的制备过程：一定量的氧化铕与过量氯化氢水溶液在搅拌的条件下反应一段时间，使其充分溶解，将溶液在移至70℃油浴锅中将多余溶剂蒸发直至溶剂消失，剩余反应物呈晶体，干燥得到EuCl 3∙H 2O，然后将晶体用适量的乙醇进行溶解，配制成浓度为0.1mol/L的氯化铕溶液； Wherein, the preparation process of the ruthenium chloride solution: a certain amount of ruthenium oxide and an excess of aqueous hydrogen chloride are reacted under stirring for a period of time to fully dissolve the solution, and the solution is transferred to a 70 ° C oil bath to evaporate the excess solvent until the solvent Disappeared, the remaining reactants were crystals, dried to obtain EuCl 3 ∙H 2 O, and then the crystals were dissolved with an appropriate amount of ethanol to prepare a cerium chloride solution having a concentration of 0.1 mol/L;
（2）向稀土络合物溶液加入适量乙醇和水，搅拌半小时使其溶解均匀，用氨水调节溶液的pH为7，然后逐滴加入正硅酸乙酯，反应7小时，对所得溶液进行离心，并用乙醇进行洗涤，最终得到稀土络合物掺杂二氧化硅微球溶液；溶液为中性环境时，制备得到的稀土络合物掺杂二氧化硅微球溶液的性能最佳。(2) adding an appropriate amount of ethanol and water to the rare earth complex solution, stirring for half an hour to dissolve it uniformly, adjusting the pH of the solution to 7 with ammonia water, then adding tetraethyl orthosilicate dropwise, reacting for 7 hours, and performing the solution for 7 hours. After centrifugation and washing with ethanol, the rare earth complex doped silica microsphere solution is finally obtained; when the solution is in a neutral environment, the prepared rare earth complex doped silica microsphere solution has the best performance.
如图3所示，本实施例的改性太阳能电池主体结构包括：稀土二氧化硅层，厚度400nm；PET基底，厚度180nm；阳极电极ITO，厚度180nm；空穴传输层，为PEDOT:PSS聚合物导电薄膜，厚度为200nm；光活性层，给体材料为基于BDT的窄带隙聚合物PBDTTT-C-T，受体材料为富勒烯衍生物（PC 71BM），厚度为100nm；电子传输层，厚度为10nm；阴极电极，为铝，厚度为100nm。 As shown in FIG. 3, the modified solar cell main structure of the present embodiment comprises: a rare earth silicon dioxide layer having a thickness of 400 nm; a PET substrate having a thickness of 180 nm; an anode electrode ITO having a thickness of 180 nm; and a hole transport layer being a PEDOT:PSS polymerization. Conductive film, thickness 200nm; photoactive layer, donor material is BDT-based narrow band gap polymer PBDTTT-CT, acceptor material is fullerene derivative (PC 71 BM), thickness is 100nm; electron transport layer, The thickness is 10 nm; the cathode electrode is aluminum and has a thickness of 100 nm.
本实施例的改性太阳能电池的制备方法包括如下步骤：The method for preparing the modified solar cell of the embodiment includes the following steps:
1）将带有阳极电极ITO的PET透明基底依次用洗涤剂、去离子水、丙酮、去离子水、无水乙醇和异丙醇超声清洗，清洗后用干燥的高纯氮气吹干或高温烘干，形成洁净的PET基底；然后将PET基底转入等离子体表面处理仪，在25Pa气压，氧气和氮气环境下对PET基底等离子处理6min后冷却至室温；1) The PET transparent substrate with anode electrode ITO is ultrasonically cleaned with detergent, deionized water, acetone, deionized water, absolute ethanol and isopropanol, washed, dried with dry high-purity nitrogen or dried at high temperature. Dry to form a clean PET substrate; then transfer the PET substrate to a plasma surface treatment apparatus, plasma-treat the PET substrate for 6 minutes under a pressure of 25 Pa, oxygen and nitrogen, and then cool to room temperature;
2）用乙醇对稀土络合物掺杂二氧化硅微球溶液进行稀释，然后经超声分散，得到分散均匀的稀土络合物掺杂二氧化硅微球溶液；2) diluting the rare earth complex doped silica microsphere solution with ethanol, and then dispersing by ultrasonication to obtain a uniformly dispersed rare earth complex doped silica microsphere solution;
3）在步骤1）等离子处理过的PET基底置于匀胶机中，在PET基底上旋涂步骤2）分散均匀的稀土络合物掺杂二氧化硅微球溶液，转速为2000rpm，时间为40s，最终在PET基底上形成厚度为400nm的稀土二氧化硅层；3) In step 1) the plasma-treated PET substrate is placed in a homogenizer, and the step 2) spin-coating the uniform rare earth complex-doped silica microsphere solution on the PET substrate at a rotation speed of 2000 rpm for a time of 40s, finally forming a rare earth silicon dioxide layer having a thickness of 400 nm on the PET substrate;
4）将步骤3）得到的阳极电极ITO重复步骤1）的操作，得到等离子处理过的阳极电极ITO；等离子处理过的阳极电极ITO置于匀胶机中，在阳极电极ITO上旋涂聚电解质导电材料PEDOT:PSS，转速为4000rpm，时间为40s，最终在阳极电极ITO上形成厚度为30nm的空穴传输层（聚合物导电薄膜），随后在100℃下热处理20分钟；4) repeating the operation of the step 1) of the anode electrode ITO obtained in the step 3) to obtain the plasma-treated anode electrode ITO; the plasma-treated anode electrode ITO is placed in the homogenizer, and the polyelectrolyte is spin-coated on the anode electrode ITO. Conductive material PEDOT:PSS, rotating at 4000 rpm for 40 s, finally forming a hole transport layer (polymer conductive film) having a thickness of 30 nm on the anode electrode ITO, followed by heat treatment at 100 ° C for 20 minutes;
5）将步骤4）得到的空穴传输层置于匀胶机中，旋涂PBDTT-C-T与PC71BM质量比为1：1.5、总浓度为25mg/mL的邻二氯苯溶液，转速为800rpm，时间为60s，在空穴传输层上形成光活性层；步骤4）进行热处理，可以增加光活性层的表面粗糙度，使得受体与给体材料出现相分离，提高活性层的结晶度，从而使受体和给体材料能形成互穿网络结构；5) The hole transport layer obtained in the step 4) is placed in a homomixer, and a solution of PBDTT-CT and PC71BM having a mass ratio of 1:1.5 and a total concentration of 25 mg/mL in an o-dichlorobenzene solution is spin-coated at 800 rpm. The photoactive layer is formed on the hole transport layer at a time of 60 s; and the heat treatment is performed in step 4) to increase the surface roughness of the photoactive layer, thereby causing phase separation between the acceptor and the donor material, thereby increasing the crystallinity of the active layer, thereby Allowing the acceptor and donor materials to form an interpenetrating network structure;
6）在步骤5）的光活性层上通过蒸镀的方法依次蒸镀形成电子传输层和阴极电极层，得到改性太阳能电池；应用真空度大于5×10 -4Pa的真空蒸镀仪进行蒸镀，电子传输层材料为Ca，蒸镀速率为0.01nm/s，厚度为10nm；阴极电极材料为Al，蒸镀速率为0.5nm/s，厚度为100nm，蒸镀速率及厚度由探头安装在基片附近的晶振膜厚仪监控。 6) sequentially forming an electron transport layer and a cathode electrode layer by vapor deposition on the photoactive layer of step 5) to obtain a modified solar cell; applying a vacuum evaporation apparatus having a degree of vacuum greater than 5×10 −4 Pa Evaporation, the electron transport layer material is Ca, the evaporation rate is 0.01 nm/s, the thickness is 10 nm; the cathode electrode material is Al, the evaporation rate is 0.5 nm/s, the thickness is 100 nm, and the evaporation rate and thickness are installed by the probe. Monitoring of the crystal film thickness gauge near the substrate.
对比例1Comparative example 1
本对比例的太阳能电池与实施例1制备得到的太阳能电池基本相同，区别点在于，对比例1的太阳能电池的PET基底上没有旋涂稀土络合物掺杂二氧化硅微球层。The solar cell of the present comparative example was substantially the same as the solar cell prepared in Example 1, except that the PET substrate of the solar cell of Comparative Example 1 was not spin-coated with a rare earth complex doped silica microsphere layer.
实施例1的太阳能电池的PET基底上具有稀土络合物掺杂二氧化硅微球层，而对比例1的太阳能电池的PET基底上没有稀土络合物掺杂二氧化硅微球层，由图4可知，实施例1的太阳能电池的光电转化效率大于对比例1的太阳能电池的光电转化效率。对于实施例1的太阳能电池而言，在不影响透光率的前提下，当阳光穿过稀土二氧化硅层时，络合物中的小分子配体吸收紫外部分的能量，然后将能量转移给稀土离子发射出红光，实施例1的太阳能电池相当于增加了可见光的比例，使得光电转化效率得以增加；同时，当光线穿过稀土二氧化硅层时，光线会发生散射而使其角度发生偏转，从而得到了更长的光程，也可以增加光电转化效率。The solar cell of the solar cell of Example 1 has a rare earth complex doped silica microsphere layer on the PET substrate, and the solar cell of the solar cell of Comparative Example 1 has no rare earth complex doped silica microsphere layer on the PET substrate. 4, the photovoltaic conversion efficiency of the solar cell of Example 1 was greater than that of the solar cell of Comparative Example 1. For the solar cell of Example 1, the small molecule ligand in the complex absorbs the energy of the ultraviolet portion and then transfers the energy when the sunlight passes through the rare earth silica layer without affecting the light transmittance. For the rare earth ions to emit red light, the solar cell of Embodiment 1 corresponds to an increase in the ratio of visible light, so that the photoelectric conversion efficiency is increased; meanwhile, when the light passes through the rare earth silicon dioxide layer, the light is scattered and angled. Deflection occurs, resulting in a longer optical path and increased photoelectric conversion efficiency.
实施例1制备的涂覆有稀土掺杂二氧化硅微球层的太阳能电池的能量转换效率为7.85%，对比例1的太阳能电池效率的7.05%；以对比例1相比，实施例1的太阳能电池的光电转换效率提高了约11.3%。The energy conversion efficiency of the solar cell coated with the rare earth doped silica microsphere layer prepared in Example 1 was 7.85%, and the solar cell efficiency of Comparative Example 1 was 7.05%; compared with Comparative Example 1, the example 1 The photoelectric conversion efficiency of the solar cell is improved by about 11.3%.
以上实施例仅用以说明本发明的技术方案，而非对其进行限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。The above embodiments are only used to illustrate the technical solutions of the present invention, and are not limited thereto; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still The technical solutions are described as being modified, or equivalents are replaced by some of the technical features; and such modifications or substitutions do not depart from the spirit and scope of the technical solutions claimed in the present invention.

Claims (10)

  1. 一种稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， Method for preparing rare earth complex doped silica microsphere solution, characterized in that
    所述方法包括以下步骤：The method includes the following steps:
    （1）将两种有机共轭小分子分别作为第一配体和第二配体，所述第一配体和所述第二配体与稀土氯化物溶液混合反应，得到稀土络合物溶液；(1) The two organic conjugated small molecules are respectively used as a first ligand and a second ligand, and the first ligand and the second ligand are mixed with a rare earth chloride solution to obtain a rare earth complex solution. ;
    （2）在所述稀土络合物溶液中滴加硅酸酯进行反应，得到稀土络合物掺杂二氧化硅微球溶液。(2) A silicate is added dropwise to the rare earth complex solution to carry out a reaction to obtain a rare earth complex-doped silica microsphere solution.
  2. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（1）中，所述稀土氯化物溶液为氯化铕溶液、氯化铽溶液、氯化铥溶液和氯化钆溶液中的一种，所述第一配体为2-噻吩甲酰三氟丙酮，所述第二配体为1-10菲罗啉。In the step (1), the rare earth chloride solution is one of a barium chloride solution, a barium chloride solution, a barium chloride solution and a barium chloride solution, and the first ligand is 2-thiophene. Acyl trifluoroacetone, the second ligand is 1-10 phenanthroline.
  3. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（1）中，所述稀土氯化物、所述第一配体、所述第二配体的摩尔比为1：3：1。In the step (1), the molar ratio of the rare earth chloride, the first ligand, and the second ligand is 1:3:1.
  4. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（1）中，反应温度为室温，反应时间为1-3h。In the step (1), the reaction temperature is room temperature, and the reaction time is 1-3 h.
  5. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（1）中，所述稀土络合物溶液的紫外吸收范围处于200-500nm。In the step (1), the ultraviolet absorption range of the rare earth complex solution is in the range of 200 to 500 nm.
  6. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（2）中，所述硅酸酯为正硅酸乙酯。In the step (2), the silicate is ethyl orthosilicate.
  7. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（2）中，所述稀土络合物掺杂二氧化硅微球溶液的紫外吸收范围处于200-400nm，In the step (2), the ultraviolet absorption range of the rare earth complex doped silica microsphere solution is in the range of 200-400 nm.
    二氧化硅微球直径为350-450nm。The silica microspheres have a diameter of 350-450 nm.
  8. 如权利要求1所述的稀土络合物掺杂二氧化硅微球溶液的制备方法，其特征在于， The method for preparing a rare earth complex doped silica microsphere solution according to claim 1, wherein
    所述步骤（2）中，反应时间为6-9h。In the step (2), the reaction time is 6-9 h.
  9. 一种改性太阳能电池的制备方法，其特征在于，A method for preparing a modified solar cell, characterized in that
    将权利要求1-8中任一项所述的稀土络合物掺杂二氧化硅微球溶液旋涂在太阳能电池的PET基底上，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。The rare earth complex doped silica microsphere solution according to any one of claims 1-8 is spin-coated on a PET substrate of a solar cell to prepare a rare earth complex doped silica microsphere. Modified solar cells.
  10. 如权利要求9所述的改性太阳能电池的制备方法，其特征在于，A method of producing a modified solar cell according to claim 9, wherein
    所述方法包括如下步骤：The method includes the following steps:
    1）将带有阳极电极ITO的PET透明基底依次用洗涤剂、去离子水、丙酮、去离子水、无水乙醇和异丙醇超声清洗，清洗后用干燥的高纯氮气吹干或高温烘干，形成洁净的PET基底；然后将所述PET基底转入等离子体表面处理仪，在25Pa气压，氧气和氮气环境下对所述PET基底等离子处理5-15min后冷却至室温；1) The PET transparent substrate with anode electrode ITO is ultrasonically cleaned with detergent, deionized water, acetone, deionized water, absolute ethanol and isopropanol, washed, dried with dry high-purity nitrogen or dried at high temperature. Drying, forming a clean PET substrate; then transferring the PET substrate to a plasma surface treatment apparatus, plasma treating the PET substrate for 5-15 minutes under a pressure of 25 Pa, oxygen and nitrogen, and then cooling to room temperature;
    2）用有机溶剂对所述稀土络合物掺杂二氧化硅微球溶液进行稀释，然后经超声分散，得到分散均匀的稀土络合物掺杂二氧化硅微球溶液；2) diluting the rare earth complex doped silica microsphere solution with an organic solvent, and then dispersing by ultrasonication to obtain a uniformly dispersed rare earth complex doped silica microsphere solution;
    3）在步骤1）等离子处理过的PET基底上（不含ITO面）通过旋涂的方法形成不连续分散均匀的稀土二氧化硅层；3) forming a discontinuously dispersed uniform rare earth silica layer on the plasma treated PET substrate (without the ITO surface) in step 1) by spin coating;
    4）在步骤3）形成的阳极电极ITO面上通过旋涂的方法形成带有一层空穴传输层的导电基底；4) forming a conductive substrate with a hole transport layer by spin coating on the ITO surface of the anode electrode formed in the step 3);
    5）将活性层材料通过旋涂的方法在步骤4）的空穴传输层上形成光活性层；5) forming a photoactive layer on the hole transport layer of step 4) by spin coating the active layer material;
    6）在步骤5）的光活性层上通过蒸镀的方法依次蒸镀形成电子传输层和阴极电极层，制备成具有稀土络合物掺杂二氧化硅微球的改性太阳能电池。6) An electron transport layer and a cathode electrode layer are sequentially deposited by vapor deposition on the photoactive layer of the step 5) to prepare a modified solar cell having rare earth complex doped silica microspheres.
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