WO2021027373A1 - Crystal seed and method for manufacturing perovskite solar cell thereby - Google Patents

Crystal seed and method for manufacturing perovskite solar cell thereby Download PDF

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WO2021027373A1
WO2021027373A1 PCT/CN2020/093815 CN2020093815W WO2021027373A1 WO 2021027373 A1 WO2021027373 A1 WO 2021027373A1 CN 2020093815 W CN2020093815 W CN 2020093815W WO 2021027373 A1 WO2021027373 A1 WO 2021027373A1
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perovskite
precursor
film
metal halide
solar cell
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Chinese (zh)
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顾楠楠
盛睿
颜步一
姚冀众
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杭州纤纳光电科技有限公司
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
    • 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 belongs to the technical field of perovskite solar cell preparation, and particularly relates to a seed crystal and a method for preparing the perovskite solar cell.
  • Perovskite solar cells have received widespread attention, which use organometallic halides as the light absorption layer.
  • the perovskite has a cubic octahedral structure of ABX 3 type, as shown in Figure 1.
  • Thin-film solar cells made of this material have simple process, low production cost, stability and high conversion rate. Since 2009, the photoelectric conversion efficiency has increased from 3.8% to more than 23%, which is higher than that of commercial crystalline silicon solar cells. Larger cost advantage.
  • additives can assist the formation of perovskite crystal nuclei more uniformly, and affect the crystallization process of the perovskite material, thereby improving the quality of the perovskite film, accurately controlling its crystal growth, and improving the stability of the crystal.
  • the benefits of applying additives include the ability to prepare a flat film surface, increase the surface coverage, and control the grain size, thereby increasing the parallel resistance of the perovskite battery, thereby achieving the purpose of increasing battery efficiency.
  • the existing perovskite film additives mainly include polymers, fullerenes, metal halide salts, inorganic acids, solvents, organic halide salts, nanoparticles and other types of additives. These additives regulate the crystallization process of perovskite to stabilize Alpha-phase perovskite crystals.
  • Perovskite materials may exhibit different phases under different temperatures or environments, and different phases will lead to completely different photoelectric properties.
  • formamidine lead iodide perovskite is usually a black phase at high temperature, but at room temperature.
  • the yellow ⁇ -phase perovskite crystal form exists, and this ⁇ -phase perovskite crystal has no photoactivity, which affects the stability and efficiency of the device.
  • a similar phase transition is one of the important factors for the poor stability of perovskite solar cells.
  • the technical problem to be solved by the present invention is to provide a seed crystal and a method for preparing a perovskite solar cell. Aiming at the problem of poor stability of the perovskite black phase which is easy to form delta phase crystals at room temperature, it is designed from a chemical point of view The structure of perovskite crystals, adding "seeds" to the precursor solution, perovskite crystals use this as a growth "template", making it easier to form black phase crystals with photoelectric effect during the growth of perovskite crystals. Non-yellow phase crystal.
  • the present invention is achieved in this way, providing a seed crystal, the seed crystal is a compound, the general chemical formula of which is: E x F y G z Pb(I a Br b Cl c ) 3 , where E, F, G is cesium, rubidium, amine, amidine or any one of the monovalent cations in the alkali family, 0 ⁇ x ⁇ 1.1, 0 ⁇ y ⁇ 1.1, 0 ⁇ z ⁇ 1.1, 0.8 ⁇ x+y+z ⁇ 1.1, 0.9 ⁇ a+b+c ⁇ 1.1, Pb is lead ion, I is iodide ion, Br is bromide ion, and Cl is chloride ion.
  • the seed crystal is used in the preparation of the perovskite film.
  • the present invention is achieved in this way and provides a method for preparing a perovskite solar cell.
  • the seed crystal as described above is used in the process of preparing the perovskite solar cell.
  • the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
  • Step 1 Prepare a perovskite precursor containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor;
  • Step 2 Coat the perovskite precursor BX 2 precursor prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
  • Step 3 Dissolve the perovskite precursor AX in a solvent to obtain a solution containing the perovskite precursor AX.
  • the calcium-containing solution can be processed by any of spin coating, blade coating, slit continuous coating, and spray coating.
  • the solution of the titanium ore precursor AX is coated on the surface of the metal halide BX 2 film containing the seed crystals, so that the perovskite precursor AX molecules and the metal halide BX 2 molecules react to form a perovskite film layer containing the seed crystals.
  • the method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
  • Step 1 Prepare a perovskite precursor liquid containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor liquid;
  • Step 2 Coat the perovskite precursor BX 2 precursor solution prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
  • Step 3 Place the film in the film forming cavity, and place the perovskite precursor AX in the evaporation source of the cavity for heating and evaporation, so that the film is placed in the vapor atmosphere of the perovskite precursor AX.
  • Titanium ore precursor AX gas molecules react with metal halide BX 2 molecules to form a perovskite film containing seed crystals;
  • Step 4 Rinse the perovskite film with isopropanol (IPA), dry it with nitrogen N 2 and then anneal to obtain a perovskite film layer containing seed crystals.
  • IPA isopropanol
  • B is lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, At least one divalent metal cation of cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, and polonium, and X is at least one of iodine, bromine, chlorine, astatine, thiocyanate, and acetate
  • a negative monovalent anion A is at least one positive monovalent cation in the metal, amidino group or alkali family.
  • the concentration of the metal halide BX 2 of the perovskite precursor is 0.5 mol/L to 2 mol/L, and the amount of seed crystal blended is the molar amount of the metal halide BX 2 of the perovskite precursor 0 ⁇ 30%.
  • the air pressure of the film forming cavity ranges from 10 -5 Pa to 10 5 Pa
  • the heating temperature of the perovskite precursor AX is controlled at 30°C to 250°C
  • the heating temperature of the substrate is controlled at 30°C ⁇ 250°C
  • the reaction time between the perovskite precursor AX molecule and the metal halide BX 2 molecule of the perovskite precursor is controlled within 10min ⁇ 120min; in step 4, the prepared perovskite containing seed crystals
  • the thickness of the mineral film layer is 200nm ⁇ 800nm.
  • the seed crystal of the present invention and the method for preparing the perovskite solar cell add the perovskite seed crystal to the lead halide to control the growth of the perovskite crystal in a specific direction so that it is in the crystallization process.
  • Figure 1 is a schematic diagram of the molecular structure in a perovskite film
  • Figure 2 is an XRD comparison diagram of perovskite films prepared without seed crystals and seed crystals
  • Fig. 3 is a J-V curve diagram of a perovskite solar cell containing seed crystals prepared in Example 1 of the present invention.
  • the seed crystal is a compound whose general chemical formula is: E x F y G z Pb(I a Br b Cl c ) 3 , where E, F, and G are respectively Cesium, rubidium, amine group, amidine group or any one of the monovalent cations in the alkali family, 0 ⁇ x ⁇ 1.1, 0 ⁇ y ⁇ 1.1, 0 ⁇ z ⁇ 1.1, 0.8 ⁇ x+y+z ⁇ 1.1, 0.9 ⁇ a+b+c ⁇ 1.1, Pb is lead ion, I is iodide ion, Br is bromide ion, and Cl is chloride ion.
  • the seed crystals are used in the preparation of perovskite films.
  • the invention also discloses a method for preparing the perovskite solar cell.
  • the seed crystal as described above is used in the process of preparing the perovskite solar cell.
  • the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
  • Step 1 Prepare a perovskite precursor liquid containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor liquid.
  • Step 2 Coat the perovskite precursor BX 2 precursor prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , A film containing a metal halide BX 2 precursor solution is obtained, and then the film is annealed to obtain a metal halide BX 2 film containing a seed crystal.
  • Step 3 Dissolve the perovskite precursor AX in a solvent to obtain a solution containing the perovskite precursor AX.
  • the calcium-containing solution can be processed by any of spin coating, blade coating, slit continuous coating, and spray coating.
  • the solution of the titanium ore precursor AX is coated on the surface of the metal halide BX 2 film containing the seed crystals, so that the perovskite precursor AX molecules and the metal halide BX 2 molecules react to form a perovskite film layer containing the seed crystals.
  • the thickness of the prepared perovskite thin film layer containing seed crystals is 200 nm to 800 nm.
  • the method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
  • Step 1 Prepare a perovskite precursor containing seed crystals, and dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor.
  • Step 2 Coat the perovskite precursor BX 2 precursor solution prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , A film containing a metal halide BX 2 precursor solution is obtained, and then the film is annealed to obtain a metal halide BX 2 film containing a seed crystal.
  • Step 3 Place the film in the film forming cavity, use a vacuum pump to control the air pressure within a certain range, place the perovskite precursor AX in the evaporation source of the cavity for heating and evaporation, so that the film is placed in the perovskite In the vapor atmosphere of the precursor AX, the perovskite precursor AX gas molecules react with the metal halide BX 2 molecules to form a perovskite film containing seed crystals.
  • Step 4 Rinse the perovskite film with isopropanol (IPA), dry it with nitrogen N 2 and then anneal to obtain a perovskite film layer containing seed crystals.
  • IPA isopropanol
  • B is lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium , Antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium at least one divalent metal cation, X is at least one of iodine, bromine, chlorine, astatine, thiocyanate, acetate A monovalent anion, A is at least one positive monovalent cation in the metal, amidino group, or alkali family.
  • the concentration of the metal halide BX 2 of the perovskite precursor is 0.5 mol/L to 2 mol/L, and the doping amount of the seed crystal is 0-30 of the molar amount of the metal halide BX 2 of the perovskite precursor %.
  • the air pressure of the film forming cavity ranges from 10 -5 Pa to 10 5 Pa
  • the heating temperature of the perovskite precursor AX is controlled at 30°C to 250°C
  • the heating temperature of the substrate is controlled at 30°C ⁇
  • the reaction time between AX molecules of the perovskite precursor and the metal halide BX 2 molecules of the perovskite precursor is controlled within 10min ⁇ 120min; in step 4, the prepared perovskite film layer containing seed crystals
  • the thickness is 200nm ⁇ 800nm.
  • the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
  • the Cu electrode of the metal conductive layer is evaporated to prepare the perovskite solar cell containing the seed crystal.
  • the method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
  • a metal conductive layer Ag electrode is evaporated to prepare a perovskite solar cell containing seed crystals.
  • the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
  • the 5 ⁇ 5 cm ITO glass plate was ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol for 30 minutes, then dried with N 2 and treated with UV O-zone for 10 minutes.
  • a metal conductive layer Au electrode is evaporated to prepare a perovskite solar cell containing a seed crystal.
  • Fig. 2 shows the comparison of XRD patterns between doped perovskite seed crystals and undoped seed crystals in Example 2.
  • the undoped phase is stable for three days, FA perovskite It is converted into a yellow phase, which has low photoactivity and affects the stability of the perovskite solar cell device.
  • the perovskite doped with seed crystals remains in the black phase after being placed for a week and has photoactivity.
  • the efficiency of perovskite solar cells doped with FA 0.83 Cs 0.17 PbI 3 perovskite seeds is significantly higher than that of perovskite solar cells without doped seeds, and its efficiency is increased from 8.63% to 17.31 %.

Abstract

The present invention relates to a crystal seed, which is a compound. The chemical general formula thereof is: E xF yG zPb(I aBr bCl c) 3. In the formula, E, F, and G respectively represent monovalent cations of any one of cesium, rubidium, amine, amidine or alkali, 0≤x≤1.1, 0≤y≤1.1, 0≤z≤1.1, 0.8≤x+y+z≤1.1, 0.9≤a+b+c≤1.1, Pb represents lead ion, I represents iodide ion, Br represents bromide ion, and Cl represents chloride ion. Also disclosed in the present invention is a method for manufacturing perovskite solar cell by the crystal seed. According to the present invention, perovskite crystal seeds are added to lead halide, and the perovskite crystal is controlled to grow in a specific direction, so that black alpha-phase perovskite crystal, rather than yellow-phase crystal, is formed in a crystallization process, the crystalline phase of perovskite is stabilized under various conditions, a long-term stable perovskite thin film layer is manufactured, and the efficiency and stability of solar cells are improved.

Description

一种晶种及其制备钙钛矿太阳能电池的方法Seed crystal and method for preparing perovskite solar cell 技术领域Technical field
本发明属于钙钛矿太阳能电池制备技术领域，特别涉及一种晶种及其制备钙钛矿太阳能电池的方法。The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a seed crystal and a method for preparing the perovskite solar cell.
背景技术Background technique
钙钛矿太阳能电池受到广泛关注，它以有机金属卤化物为光吸收层。钙钛矿为ABX 3型的立方八面体结构，如图1所示。此种材料制备的薄膜太阳能电池工艺简便、生产成本低、稳定且转化率高，自2009年至今，光电转换效率从3.8%提升至23%以上，已高于商业化的晶硅太阳能电池且具有较大的成本优势。 Perovskite solar cells have received widespread attention, which use organometallic halides as the light absorption layer. The perovskite has a cubic octahedral structure of ABX 3 type, as shown in Figure 1. Thin-film solar cells made of this material have simple process, low production cost, stability and high conversion rate. Since 2009, the photoelectric conversion efficiency has increased from 3.8% to more than 23%, which is higher than that of commercial crystalline silicon solar cells. Larger cost advantage.
为了进一步提高钙钛矿电池效率及稳定性，除了最常见的甲胺铅碘钙钛矿，研究者也会使用甲脒铅碘钙钛矿或纯无机钙钛矿，此类钙钛矿具有更高的效率及更优的热稳定性。同时，添加剂的应用可以辅助钙钛矿晶核更均匀的形成，并且影响钙钛矿材料的结晶过程，从而提高钙钛矿薄膜质量，精确控制其晶体生长，提高晶体的稳定性。应用添加剂的好处包括可制备平整的薄膜表面，提高表面覆盖率，控制晶粒大小，从而增大钙钛矿电池的并联电阻，进而达到增加电池效率的目的。In order to further improve the efficiency and stability of the perovskite battery, in addition to the most common methylamine lead iodine perovskite, researchers will also use formamidine lead iodine perovskite or pure inorganic perovskite, which has more High efficiency and better thermal stability. At the same time, the application of additives can assist the formation of perovskite crystal nuclei more uniformly, and affect the crystallization process of the perovskite material, thereby improving the quality of the perovskite film, accurately controlling its crystal growth, and improving the stability of the crystal. The benefits of applying additives include the ability to prepare a flat film surface, increase the surface coverage, and control the grain size, thereby increasing the parallel resistance of the perovskite battery, thereby achieving the purpose of increasing battery efficiency.
现有的钙钛矿薄膜添加剂主要有聚合物、富勒烯、金属卤素盐、无机酸、溶剂、有机卤素盐、纳米粒子和其他种类添加剂，这些添加剂通过调控钙钛矿的结晶过程，以稳定α相钙钛矿晶体。The existing perovskite film additives mainly include polymers, fullerenes, metal halide salts, inorganic acids, solvents, organic halide salts, nanoparticles and other types of additives. These additives regulate the crystallization process of perovskite to stabilize Alpha-phase perovskite crystals.
钙钛矿材料在不同温度或环境下可能会呈现不一样的相，而不同的相会导致完全不同的光电性质，如甲脒铅碘钙钛矿通常在高温为黑相，而在常温下以黄色的δ相钙钛矿晶体形式存在，此种δ相钙钛矿晶体不具有光活性，从而影响器件的稳定性及效率。类似的相转变是钙钛矿太阳能电池稳定性差的重要因素之一。Perovskite materials may exhibit different phases under different temperatures or environments, and different phases will lead to completely different photoelectric properties. For example, formamidine lead iodide perovskite is usually a black phase at high temperature, but at room temperature. The yellow δ-phase perovskite crystal form exists, and this δ-phase perovskite crystal has no photoactivity, which affects the stability and efficiency of the device. A similar phase transition is one of the important factors for the poor stability of perovskite solar cells.
技术问题technical problem
本发明所要解决的技术问题在于，提供一种晶种及其制备钙钛矿太阳能电池的方法，针对一些常温下易于形成δ相晶体的钙钛矿黑相稳定性差的问题，从化学的角度设计钙钛矿晶体的结构，在前驱体溶液中加入“晶种”，钙钛矿晶体以此为生长“模板”，使钙钛矿晶体的生长过程中更易于形成有光电效应的黑相晶体而非黄相晶体。The technical problem to be solved by the present invention is to provide a seed crystal and a method for preparing a perovskite solar cell. Aiming at the problem of poor stability of the perovskite black phase which is easy to form delta phase crystals at room temperature, it is designed from a chemical point of view The structure of perovskite crystals, adding "seeds" to the precursor solution, perovskite crystals use this as a growth "template", making it easier to form black phase crystals with photoelectric effect during the growth of perovskite crystals. Non-yellow phase crystal.
技术解决方案Technical solutions
本发明是这样实现的，提供一种晶种，所述晶种为化合物，其化学通式为：E xF yG zPb(I aBr bCl c) 3，式中，E、F、G分别是铯、铷、胺基、脒基或者碱族中的任意一种一价阳离子，0≤x≤1.1，0≤y≤1.1，0≤z≤1.1，0.8≤x+y+z≤1.1，0.9≤a+b+c≤1.1，Pb为铅离子，I为碘离子，Br为溴离子，Cl为氯离子。 The present invention is achieved in this way, providing a seed crystal, the seed crystal is a compound, the general chemical formula of which is: E x F y G z Pb(I a Br b Cl c ) 3 , where E, F, G is cesium, rubidium, amine, amidine or any one of the monovalent cations in the alkali family, 0≤x≤1.1, 0≤y≤1.1, 0≤z≤1.1, 0.8≤x+y+z≤ 1.1, 0.9≤a+b+c≤1.1, Pb is lead ion, I is iodide ion, Br is bromide ion, and Cl is chloride ion.
进一步地，所述晶种被用于制备钙钛矿薄膜中。Further, the seed crystal is used in the preparation of the perovskite film.
本发明是这样实现的，提供一种制备钙钛矿太阳能电池的方法，在制备钙钛矿太阳能电池的过程中使用了如前所述的晶种。The present invention is achieved in this way and provides a method for preparing a perovskite solar cell. The seed crystal as described above is used in the process of preparing the perovskite solar cell.
进一步地，所述制备钙钛矿太阳能电池的方法为溶液法，其包括如下步骤：Further, the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
步骤1. 制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液； Step 1. Prepare a perovskite precursor containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor;
步骤2. 通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤1制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜； Step 2. Coat the perovskite precursor BX 2 precursor prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
步骤3. 将钙钛矿前驱体AX溶解于溶剂中，得到含钙钛矿前驱体AX的溶液，通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将含钙钛矿前驱体AX的溶液涂覆在含有晶种的金属卤化物BX 2薄膜表面，使钙钛矿前驱体AX分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜层。 Step 3. Dissolve the perovskite precursor AX in a solvent to obtain a solution containing the perovskite precursor AX. The calcium-containing solution can be processed by any of spin coating, blade coating, slit continuous coating, and spray coating. The solution of the titanium ore precursor AX is coated on the surface of the metal halide BX 2 film containing the seed crystals, so that the perovskite precursor AX molecules and the metal halide BX 2 molecules react to form a perovskite film layer containing the seed crystals.
进一步地，所述制备钙钛矿太阳能电池的方法为气相溶液辅助法，其包括如下步骤：Further, the method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
步骤一、制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液； Step 1. Prepare a perovskite precursor liquid containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor liquid;
步骤二、通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤一制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜； Step 2: Coat the perovskite precursor BX 2 precursor solution prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
步骤三、将该薄膜置于薄膜成型腔体中，将钙钛矿前驱体AX放置于腔体的蒸发源中进行加热蒸发，使得该薄膜置于钙钛矿前驱体AX的蒸汽氛围中，钙钛矿前驱体AX气体分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜； Step 3. Place the film in the film forming cavity, and place the perovskite precursor AX in the evaporation source of the cavity for heating and evaporation, so that the film is placed in the vapor atmosphere of the perovskite precursor AX. Titanium ore precursor AX gas molecules react with metal halide BX 2 molecules to form a perovskite film containing seed crystals;
步骤四、利用异丙醇（IPA）冲洗该钙钛矿薄膜，再用氮气N 2吹干后退火处理得到含有晶种的钙钛矿薄膜层。 Step 4: Rinse the perovskite film with isopropanol (IPA), dry it with nitrogen N 2 and then anneal to obtain a perovskite film layer containing seed crystals.
进一步地，在钙钛矿前驱体的金属卤化物BX 2和钙钛矿前驱体AX中，B为铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的至少一种二价金属阳离子，X 为碘、溴、氯、砹、硫氰根、醋酸根中的至少一种负一价阴离子，A为金属、脒基或者碱族中的至少一种正一价阳离子。 Further, in the metal halide BX 2 of the perovskite precursor and the perovskite precursor AX, B is lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, At least one divalent metal cation of cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, and polonium, and X is at least one of iodine, bromine, chlorine, astatine, thiocyanate, and acetate A negative monovalent anion, A is at least one positive monovalent cation in the metal, amidino group or alkali family.
进一步地，所述钙钛矿前驱体的金属卤化物BX 2浓度为0.5mol/L~2mol/L，所述晶种的掺入量是钙钛矿前驱体的金属卤化物BX 2摩尔量的0~30%。 Further, the concentration of the metal halide BX 2 of the perovskite precursor is 0.5 mol/L to 2 mol/L, and the amount of seed crystal blended is the molar amount of the metal halide BX 2 of the perovskite precursor 0~30%.
进一步地，所述薄膜成型腔体的气压范围为10 -5Pa~10 5Pa，所述钙钛矿前驱体AX的加热温度控制在30℃~250℃，所述基片的加热温度控制在30℃~250℃，钙钛矿前驱体AX分子与钙钛矿前驱体的金属卤化物BX 2分子的反应时间控制在10min~120min；在步骤4中，所制得的含有晶种的钙钛矿薄膜层厚度为200nm~800nm。 Further, the air pressure of the film forming cavity ranges from 10 -5 Pa to 10 5 Pa, the heating temperature of the perovskite precursor AX is controlled at 30°C to 250°C, and the heating temperature of the substrate is controlled at 30℃~250℃, the reaction time between the perovskite precursor AX molecule and the metal halide BX 2 molecule of the perovskite precursor is controlled within 10min~120min; in step 4, the prepared perovskite containing seed crystals The thickness of the mineral film layer is 200nm~800nm.
有益效果Beneficial effect
与现有技术相比，本发明的晶种及其制备钙钛矿太阳能电池的方法，在卤化铅中加入钙钛矿晶种，控制钙钛矿晶体在特定的方向生长，使其在结晶过程中形成黑色的α相钙钛矿晶体而非黄相晶体，并在各种条件下稳定钙钛矿的晶相，可制备得到长期稳定的钙钛矿薄膜层，提高太阳能电池的效率及稳定性。Compared with the prior art, the seed crystal of the present invention and the method for preparing the perovskite solar cell add the perovskite seed crystal to the lead halide to control the growth of the perovskite crystal in a specific direction so that it is in the crystallization process. Forms black α-phase perovskite crystals instead of yellow-phase crystals, and stabilizes the perovskite crystal phase under various conditions, which can prepare long-term stable perovskite thin film layers and improve the efficiency and stability of solar cells .
附图说明Description of the drawings
图1为钙钛矿薄膜中分子结构示意图；Figure 1 is a schematic diagram of the molecular structure in a perovskite film;
图2为不添加晶种与添加晶种制备的钙钛矿薄膜的XRD对比图；Figure 2 is an XRD comparison diagram of perovskite films prepared without seed crystals and seed crystals;
图3为本发明的实施例1制备的含有晶种的钙钛矿太阳能电池的J-V曲线图。Fig. 3 is a J-V curve diagram of a perovskite solar cell containing seed crystals prepared in Example 1 of the present invention.
本发明的最佳实施方式The best mode of the invention
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the following further describes the present invention in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
本发明晶种的较佳实施例，所述晶种为化合物，其化学通式为：E xF yG zPb(I aBr bCl c) 3，式中，E、F、G分别是铯、铷、胺基、脒基或者碱族中的任意一种一价阳离子，0≤x≤1.1，0≤y≤1.1，0≤z≤1.1，0.8≤x+y+z≤1.1，0.9≤a+b+c≤1.1，Pb为铅离子，I为碘离子，Br为溴离子，Cl为氯离子。 In a preferred embodiment of the seed crystal of the present invention, the seed crystal is a compound whose general chemical formula is: E x F y G z Pb(I a Br b Cl c ) 3 , where E, F, and G are respectively Cesium, rubidium, amine group, amidine group or any one of the monovalent cations in the alkali family, 0≤x≤1.1, 0≤y≤1.1, 0≤z≤1.1, 0.8≤x+y+z≤1.1, 0.9 ≤a+b+c≤1.1, Pb is lead ion, I is iodide ion, Br is bromide ion, and Cl is chloride ion.
所述晶种被用于制备钙钛矿薄膜中。The seed crystals are used in the preparation of perovskite films.
本发明还公开一种制备钙钛矿太阳能电池的方法，在制备钙钛矿太阳能电池的过程中使用了如前所述的晶种。The invention also discloses a method for preparing the perovskite solar cell. The seed crystal as described above is used in the process of preparing the perovskite solar cell.
所述制备钙钛矿太阳能电池的方法为溶液法，其包括如下步骤：The method for preparing a perovskite solar cell is a solution method, which includes the following steps:
步骤1. 制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液。 Step 1. Prepare a perovskite precursor liquid containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor liquid.
步骤2. 通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤1制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜。 Step 2. Coat the perovskite precursor BX 2 precursor prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , A film containing a metal halide BX 2 precursor solution is obtained, and then the film is annealed to obtain a metal halide BX 2 film containing a seed crystal.
步骤3. 将钙钛矿前驱体AX溶解于溶剂中，得到含钙钛矿前驱体AX的溶液，通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将含钙钛矿前驱体AX的溶液涂覆在含有晶种的金属卤化物BX 2薄膜表面，使钙钛矿前驱体AX分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜层。所制得的含有晶种的钙钛矿薄膜层厚度为200nm~800nm。 Step 3. Dissolve the perovskite precursor AX in a solvent to obtain a solution containing the perovskite precursor AX. The calcium-containing solution can be processed by any of spin coating, blade coating, slit continuous coating, and spray coating. The solution of the titanium ore precursor AX is coated on the surface of the metal halide BX 2 film containing the seed crystals, so that the perovskite precursor AX molecules and the metal halide BX 2 molecules react to form a perovskite film layer containing the seed crystals. The thickness of the prepared perovskite thin film layer containing seed crystals is 200 nm to 800 nm.
所述制备钙钛矿太阳能电池的方法为气相溶液辅助法，其包括如下步骤：The method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
步骤一、制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液。 Step 1: Prepare a perovskite precursor containing seed crystals, and dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor.
步骤二、通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤一制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜。 Step 2: Coat the perovskite precursor BX 2 precursor solution prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , A film containing a metal halide BX 2 precursor solution is obtained, and then the film is annealed to obtain a metal halide BX 2 film containing a seed crystal.
步骤三、将该薄膜置于薄膜成型腔体中，利用真空泵控制气压在一定范围内，将钙钛矿前驱体AX放置于腔体的蒸发源中进行加热蒸发，使得该薄膜置于钙钛矿前驱体AX的蒸汽氛围中，钙钛矿前驱体AX气体分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜。 Step 3. Place the film in the film forming cavity, use a vacuum pump to control the air pressure within a certain range, place the perovskite precursor AX in the evaporation source of the cavity for heating and evaporation, so that the film is placed in the perovskite In the vapor atmosphere of the precursor AX, the perovskite precursor AX gas molecules react with the metal halide BX 2 molecules to form a perovskite film containing seed crystals.
步骤四、利用异丙醇（IPA）冲洗该钙钛矿薄膜，再用氮气N 2吹干后退火处理得到含有晶种的钙钛矿薄膜层。 Step 4: Rinse the perovskite film with isopropanol (IPA), dry it with nitrogen N 2 and then anneal to obtain a perovskite film layer containing seed crystals.
在钙钛矿前驱体的金属卤化物BX 2和钙钛矿前驱体AX中，B为铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的至少一种二价金属阳离子，X为碘、溴、氯、砹、硫氰根、醋酸根中的至少一种负一价阴离子，A为金属、脒基或者碱族中的至少一种正一价阳离子。 In the metal halide BX 2 of the perovskite precursor and the perovskite precursor AX, B is lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium , Antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium at least one divalent metal cation, X is at least one of iodine, bromine, chlorine, astatine, thiocyanate, acetate A monovalent anion, A is at least one positive monovalent cation in the metal, amidino group, or alkali family.
所述钙钛矿前驱体的金属卤化物BX 2浓度为0.5mol/L~2mol/L，所述晶种的掺入量是钙钛矿前驱体的金属卤化物BX 2摩尔量的0~30%。 The concentration of the metal halide BX 2 of the perovskite precursor is 0.5 mol/L to 2 mol/L, and the doping amount of the seed crystal is 0-30 of the molar amount of the metal halide BX 2 of the perovskite precursor %.
所述薄膜成型腔体的气压范围为10 -5Pa~10 5Pa，所述钙钛矿前驱体AX的加热温度控制在30℃~250℃，所述基片的加热温度控制在30℃~250℃，钙钛矿前驱体AX分子与钙钛矿前驱体的金属卤化物BX 2分子的反应时间控制在10min~120min；在步骤4中，所制得的含有晶种的钙钛矿薄膜层厚度为200nm~800nm。 The air pressure of the film forming cavity ranges from 10 -5 Pa to 10 5 Pa, the heating temperature of the perovskite precursor AX is controlled at 30°C to 250°C, and the heating temperature of the substrate is controlled at 30°C~ At 250°C, the reaction time between AX molecules of the perovskite precursor and the metal halide BX 2 molecules of the perovskite precursor is controlled within 10min~120min; in step 4, the prepared perovskite film layer containing seed crystals The thickness is 200nm~800nm.
本发明的实施方式Embodiments of the invention
下面结合具体实施例来进一步说明本发明的制备钙钛矿太阳能电池的方法。The method for preparing a perovskite solar cell of the present invention will be further described below with reference to specific examples.
实施例1Example 1
作为本发明的制备钙钛矿太阳能电池的方法的第一实施例，所述制备钙钛矿太阳能电池的方法为溶液法，其包括如下步骤：As a first embodiment of the method for preparing a perovskite solar cell of the present invention, the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
（11）将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min。 (11) The 5×5 cm ITO glass plate was ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol for 30 minutes, then dried with N 2 and treated with UV O-zone for 10 minutes.
（12）制备PEDOT:PSS薄膜作为空穴传输层。(12) Prepare PEDOT:PSS film as the hole transport layer.
（13）制备掺杂有晶种的的金属卤化物前驱液：将461mg的PbI 2（1mmol）溶解于1mL的DMF溶液中，添加70.9uL的无水DMSO，并添加62.00mg的MAPbI 3（0.10mmol）作为晶种，60℃加热搅拌2h，混合完全后待用。 (13) Preparation of metal halide precursor doped with seed crystals: Dissolve 461 mg of PbI 2 (1 mmol) in 1 mL of DMF solution, add 70.9 uL of anhydrous DMSO, and add 62.00 mg of MAPbI 3 (0.10 mmol) as seed crystals, heat and stir at 60°C for 2h, and set aside after mixing.
（14）使用旋涂法制备掺杂有钙钛矿晶种的PbI 2层。 (14) Use spin coating to prepare PbI 2 layer doped with perovskite seeds.
（15）将FAI溶液溶于异丙醇中，旋涂滴加FAI的异丙醇溶液，100℃退火10min。(15) Dissolve the FAI solution in isopropanol, spin-coat and drop the FAI isopropanol solution, and anneal at 100°C for 10 min.
（16）在基片上沉积电子传输层C60，厚20nm~50nm。(16) Deposit the electron transport layer C60 on the substrate with a thickness of 20nm~50nm.
（17）蒸镀金属导电层Cu电极，制得含有晶种的钙钛矿太阳能电池。(17) The Cu electrode of the metal conductive layer is evaporated to prepare the perovskite solar cell containing the seed crystal.
实施例2Example 2
作为本发明的制备钙钛矿太阳能电池的方法的第二实施例，所述制备钙钛矿太阳能电池的方法为气相溶液辅助法，其包括如下步骤：As a second embodiment of the method for preparing a perovskite solar cell of the present invention, the method for preparing a perovskite solar cell is a gas phase solution assisted method, which includes the following steps:
（21）将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min。 (21) The 5×5 cm ITO glass plate was ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol for 30 minutes, then dried with N 2 and treated with UV O-zone for 10 minutes.
（22）制备PTAA薄膜作为空穴传输层。(22) Prepare PTAA film as the hole transport layer.
（23）制备掺杂有晶种的的金属卤化物前驱液：将461mg的PbI 2（1mmol）溶解于1mL的DMF溶液中，添加70.9uL的无水DMSO，并添加97.19mg的FA 0.83Cs 0.17PbI 3（0.15mmol）作为晶种，60℃加热搅拌2h，混合完全后待用。 (23) Preparation of metal halide precursor doped with seed crystals: Dissolve 461 mg of PbI 2 (1 mmol) in 1 mL of DMF solution, add 70.9 uL of anhydrous DMSO, and add 97.19 mg of FA 0.83 Cs 0.17 PbI 3 (0.15mmol) was used as seed crystals, heated at 60°C and stirred for 2h, and set aside after mixing.
（24）使用旋涂法制备掺杂有钙钛矿晶种的PbI 2层。 (24) Use spin coating to prepare PbI 2 layer doped with perovskite seeds.
（25）将基片放置于薄膜成型腔内，控制气压在10 -8Pa~10 5Pa，加热FAI，使FAI蒸汽与卤化铅进行反应，生成有晶种的、且具有光活性和稳定的钙钛矿薄膜层。 (25) Place the substrate in the film forming cavity, control the air pressure at 10 -8 Pa~10 5 Pa, and heat the FAI to make the FAI steam react with the lead halide to generate a seeded, photoactive and stable Perovskite film layer.
（26）在基片上沉积电子传输层PCBM，厚20nm~50nm。(26) Deposit the electron transport layer PCBM on the substrate with a thickness of 20nm~50nm.
（27）蒸镀金属导电层Ag电极，制得含有晶种的钙钛矿太阳能电池。(27) A metal conductive layer Ag electrode is evaporated to prepare a perovskite solar cell containing seed crystals.
实施例3Example 3
作为本发明的制备钙钛矿太阳能电池的方法的第三实施例，所述制备钙钛矿太阳能电池的方法为溶液法，其包括如下步骤：As a third embodiment of the method for preparing a perovskite solar cell of the present invention, the method for preparing a perovskite solar cell is a solution method, which includes the following steps:
（31）将5×5cm的ITO玻璃板依次经洗洁精、去离子水、丙酮、异丙醇超声各清洗30min，再用N 2吹干后经UV O-zone处理10min。 (31) The 5×5 cm ITO glass plate was ultrasonically cleaned with detergent, deionized water, acetone, and isopropanol for 30 minutes, then dried with N 2 and treated with UV O-zone for 10 minutes.
（32）制备SnO 2薄膜作为电子传输层。 (32) Prepare SnO 2 thin film as the electron transport layer.
（33）制备掺杂有晶种的的钙钛矿前驱液：将461mg的PbI 2（1mmol）、172mg的FAI溶解于1mL的DMF溶液中，添加70.9uL的无水DMSO，并添加62.00mg的MAPbI 3（0.10mmol）作为晶种，60℃加热搅拌2h，混合完全后待用。 (33) Preparation of perovskite precursor doped with seed crystals: Dissolve 461 mg of PbI 2 (1 mmol) and 172 mg of FAI in 1 mL of DMF solution, add 70.9 uL of anhydrous DMSO, and add 62.00 mg of MAPbI 3 (0.10mmol) was used as a seed crystal, heated and stirred at 60°C for 2h, and set aside after mixing.
（34）使用旋涂法制备掺杂有晶种的钙钛矿层。(34) Use spin coating to prepare perovskite layer doped with seed crystals.
（35）在基片上沉积空穴传输层Spiro-OMeTAD，厚10nm~30nm。(35) Deposit the hole transport layer Spiro-OMeTAD on the substrate with a thickness of 10nm~30nm.
（36）蒸镀金属导电层Au电极，制得含有晶种的钙钛矿太阳能电池。(36) A metal conductive layer Au electrode is evaporated to prepare a perovskite solar cell containing a seed crystal.
请同时参照图2以及图3所示，图2为实施例2为掺杂有钙钛矿晶种与未掺杂晶种的XRD图对比，未掺杂相稳定的放置三天后FA钙钛矿转化为黄相，此相光活性低、影响钙钛矿太阳能电池器件的稳定性，而掺杂有晶种的钙钛矿放置一周后仍然为黒相，具有光活性。另一方面，掺杂有FA 0.83Cs 0.17PbI 3钙钛矿晶种的钙钛矿太阳能电池较无掺杂晶种的钙钛矿太阳能电池的效率有明显提升，其效率从8.63%提升至17.31%。 Please refer to Fig. 2 and Fig. 3 at the same time. Fig. 2 shows the comparison of XRD patterns between doped perovskite seed crystals and undoped seed crystals in Example 2. After the undoped phase is stable for three days, FA perovskite It is converted into a yellow phase, which has low photoactivity and affects the stability of the perovskite solar cell device. However, the perovskite doped with seed crystals remains in the black phase after being placed for a week and has photoactivity. On the other hand, the efficiency of perovskite solar cells doped with FA 0.83 Cs 0.17 PbI 3 perovskite seeds is significantly higher than that of perovskite solar cells without doped seeds, and its efficiency is increased from 8.63% to 17.31 %.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included in the protection of the present invention. Within range.
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Claims (8)

  1. 一种晶种，其特征在于，所述晶种为化合物，其化学通式为：E xF yG zPb(I aBr bCl c) 3，式中，E、F、G分别是铯、铷、胺基、脒基或者碱族中的任意一种一价阳离子，0≤x≤1.1，0≤y≤1.1，0≤z≤1.1，0.8≤x+y+z≤1.1，0.9≤a+b+c≤1.1，Pb为铅离子，I为碘离子，Br为溴离子，Cl为氯离子。 A seed crystal, characterized in that the seed crystal is a compound, and its general chemical formula is: E x F y G z Pb(I a Br b Cl c ) 3 , where E, F, and G are respectively cesium , Rubidium, amine group, amidine group or any one of the monovalent cations in the alkali family, 0≤x≤1.1, 0≤y≤1.1, 0≤z≤1.1, 0.8≤x+y+z≤1.1, 0.9≤ a+b+c≤1.1, Pb is lead ion, I is iodide ion, Br is bromide ion, and Cl is chloride ion.
  2. 如权利要求1所述的晶种，其特征在于，所述晶种被用于制备钙钛矿薄膜中。3. The seed crystal of claim 1, wherein the seed crystal is used for preparing a perovskite film.
  3. 一种制备钙钛矿太阳能电池的方法，其特征在于，在制备钙钛矿太阳能电池的过程中使用了所述如权利要求1所述的晶种。A method for preparing a perovskite solar cell, characterized in that the seed crystal according to claim 1 is used in the process of preparing the perovskite solar cell.
  4. 如权利要求3所述的制备钙钛矿太阳能电池的方法，其特征在于，所述制备钙钛矿太阳能电池的方法为溶液法，其包括如下步骤：The method for preparing a perovskite solar cell according to claim 3, wherein the method for preparing a perovskite solar cell is a solution method, which comprises the following steps:
    步骤1. 制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液； Step 1. Prepare a perovskite precursor containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor;
    步骤2. 通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤1制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜； Step 2. Coat the perovskite precursor BX 2 precursor prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
    步骤3. 将钙钛矿前驱体AX溶解于溶剂中，得到含钙钛矿前驱体AX的溶液，通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将含钙钛矿前驱体AX的溶液涂覆在含有晶种的金属卤化物BX 2薄膜表面，使钙钛矿前驱体AX分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜层。 Step 3. Dissolve the perovskite precursor AX in a solvent to obtain a solution containing the perovskite precursor AX. The calcium-containing solution can be processed by any of spin coating, blade coating, slit continuous coating, and spray coating. The solution of the titanium ore precursor AX is coated on the surface of the metal halide BX 2 film containing the seed crystals, so that the perovskite precursor AX molecules and the metal halide BX 2 molecules react to form a perovskite film layer containing the seed crystals.
  5. 如权利要求3所述的制备钙钛矿太阳能电池的方法，其特征在于，所述制备钙钛矿太阳能电池的方法为气相溶液辅助法，其包括如下步骤：The method for preparing a perovskite solar cell according to claim 3, wherein the method for preparing a perovskite solar cell is a gas phase solution assisted method, which comprises the following steps:
    步骤一、制备含有晶种的钙钛矿前驱液，将钙钛矿前驱体的金属卤化物BX 2以及晶种溶解于有机溶剂中，得到混合晶种的钙钛矿前驱体BX 2前驱液； Step 1. Prepare a perovskite precursor liquid containing seed crystals, dissolve the metal halide BX 2 of the perovskite precursor and the seed crystals in an organic solvent to obtain a mixed seed perovskite precursor BX 2 precursor liquid;
    步骤二、通过旋涂、刮涂、狭缝式连续涂布、喷涂中任意一种加工方式将步骤一制备的钙钛矿前驱体BX 2前驱液涂覆在已经制备有传输层的基片表面，得到含金属卤化物BX 2前驱液的薄膜，再对该薄膜进行退火处理，得到含有晶种的金属卤化物BX 2薄膜； Step 2: Coat the perovskite precursor BX 2 precursor solution prepared in step 1 on the surface of the substrate with the transmission layer prepared by any one of spin coating, knife coating, slit continuous coating, and spraying. , Obtaining a film containing a metal halide BX 2 precursor, and then annealing the film to obtain a metal halide BX 2 film containing a seed crystal;
    步骤三、将该薄膜置于薄膜成型腔体中，将钙钛矿前驱体AX放置于腔体的蒸发源中进行加热蒸发，使得该薄膜置于钙钛矿前驱体AX的蒸汽氛围中，钙钛矿前驱体AX气体分子与金属卤化物BX 2分子反应生成含有晶种的钙钛矿薄膜； Step 3. Place the film in the film forming cavity, and place the perovskite precursor AX in the evaporation source of the cavity for heating and evaporation, so that the film is placed in the vapor atmosphere of the perovskite precursor AX. Titanium ore precursor AX gas molecules react with metal halide BX 2 molecules to form a perovskite film containing seed crystals;
    步骤四、利用异丙醇（IPA）冲洗该钙钛矿薄膜，再用氮气N 2吹干后退火处理得到含有晶种的钙钛矿薄膜层。 Step 4: Rinse the perovskite film with isopropanol (IPA), dry it with nitrogen N 2 and then anneal to obtain a perovskite film layer containing seed crystals.
  6. 如权利要求4或5所述的制备钙钛矿太阳能电池的方法，其特征在于，在钙钛矿前驱体的金属卤化物BX 2和钙钛矿前驱体AX中，B为铅、锡、钨、铜、锌、镓、锗、砷、硒、铑、钯、银、镉、铟、锑、锇、铱、铂、金、汞、铊、铋、钋中的至少一种二价金属阳离子，X 为碘、溴、氯、砹、硫氰根、醋酸根中的至少一种负一价阴离子，A为金属、脒基或者碱族中的至少一种正一价阳离子。 The method for preparing a perovskite solar cell according to claim 4 or 5, wherein, in the metal halide BX 2 of the perovskite precursor and the perovskite precursor AX, B is lead, tin, tungsten , Copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, at least one divalent metal cation, X is at least one negative monovalent anion of iodine, bromine, chlorine, astatine, thiocyanate, and acetate, and A is at least one positive monovalent cation of metal, amidino or alkali.
  7. 如权利要求4或5所述的制备钙钛矿太阳能电池的方法，其特征在于，所述钙钛矿前驱体的金属卤化物BX 2浓度为0.5mol/L~2mol/L，所述晶种的掺入量是钙钛矿前驱体的金属卤化物BX 2摩尔量的0~30%。 The method for preparing a perovskite solar cell according to claim 4 or 5, wherein the metal halide BX 2 concentration of the perovskite precursor is 0.5 mol/L~2 mol/L, and the seed crystal The doping amount is 0-30% of the molar amount of the metal halide BX 2 of the perovskite precursor.
  8. 如权利要求5所述的制备钙钛矿太阳能电池的方法，其特征在于，所述薄膜成型腔体的气压范围为10 -5Pa~10 5Pa，所述钙钛矿前驱体AX的加热温度控制在30℃~250℃，所述基片的加热温度控制在30℃~250℃，钙钛矿前驱体AX分子与钙钛矿前驱体的金属卤化物BX 2分子的反应时间控制在10min~120min；在步骤4中，所制得的含有晶种的钙钛矿薄膜层厚度为200nm~800nm。 The method for preparing a perovskite solar cell according to claim 5, wherein the air pressure of the film forming cavity ranges from 10 -5 Pa to 10 5 Pa, and the heating temperature of the perovskite precursor AX Controlled at 30℃~250℃, the heating temperature of the substrate is controlled at 30℃~250℃, the reaction time of the perovskite precursor AX molecule and the metal halide BX 2 molecule of the perovskite precursor is controlled at 10min~ 120min; In step 4, the thickness of the prepared perovskite film layer containing seed crystals is 200nm~800nm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114920282A (en) * 2022-06-30 2022-08-19 齐鲁工业大学 Perovskite nanocrystalline growing on GaN monocrystal substrate and preparation method thereof
CN115843189A (en) * 2022-12-22 2023-03-24 浙江科鼐尔机电制造有限公司 Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782685B (en) * 2021-09-10 2022-10-21 华能新能源股份有限公司 Preparation method of perovskite thin film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890816B2 (en) * 2003-02-07 2005-05-10 Freescale Semiconductor, Inc. Compound semiconductor structure including an epitaxial perovskite layer and method for fabricating semiconductor structures and devices
CN108321300A (en) * 2018-02-06 2018-07-24 杭州纤纳光电科技有限公司 A kind of perovskite thin film of admixed with additives and its preparation method and application
CN108950689A (en) * 2017-05-19 2018-12-07 卫子健 The preparation method of perovskite crystal
CN110120455A (en) * 2019-04-25 2019-08-13 武汉大学 A kind of perovskite photovoltaic film preparation method based on economic benefits and social benefits seed mediated growth method
CN111313238A (en) * 2020-02-29 2020-06-19 华南理工大学 Tapered perovskite micro-nano crystal laser and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6890816B2 (en) * 2003-02-07 2005-05-10 Freescale Semiconductor, Inc. Compound semiconductor structure including an epitaxial perovskite layer and method for fabricating semiconductor structures and devices
CN108950689A (en) * 2017-05-19 2018-12-07 卫子健 The preparation method of perovskite crystal
CN108321300A (en) * 2018-02-06 2018-07-24 杭州纤纳光电科技有限公司 A kind of perovskite thin film of admixed with additives and its preparation method and application
CN110120455A (en) * 2019-04-25 2019-08-13 武汉大学 A kind of perovskite photovoltaic film preparation method based on economic benefits and social benefits seed mediated growth method
CN111313238A (en) * 2020-02-29 2020-06-19 华南理工大学 Tapered perovskite micro-nano crystal laser and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHAO YICHENG, TAN HAIREN, YUAN HAIFENG, YANG ZHENYU, FAN JAMES Z., KIM JUNGHWAN, VOZNYY OLEKSANDR, GONG XIWEN, QUAN LI NA, TAN CHI: "Perovskite seeding growth of formamidinium-lead-iodide-based perovskites for efficient and stable solar cells", NATURE COMMUNICATIONS, vol. 9, no. 1, 1 December 2018 (2018-12-01), XP055780840, DOI: 10.1038/s41467-018-04029-7 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114920282A (en) * 2022-06-30 2022-08-19 齐鲁工业大学 Perovskite nanocrystalline growing on GaN monocrystal substrate and preparation method thereof
CN115843189A (en) * 2022-12-22 2023-03-24 浙江科鼐尔机电制造有限公司 Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains
CN115843189B (en) * 2022-12-22 2023-07-25 浙江科鼐尔机电制造有限公司 Method for improving performance of perovskite solar cell through secondary growth of perovskite crystal grains

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