WO2024109424A1 - Additive and use method therefor - Google Patents

Additive and use method therefor Download PDF

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Publication number
WO2024109424A1
WO2024109424A1 PCT/CN2023/126229 CN2023126229W WO2024109424A1 WO 2024109424 A1 WO2024109424 A1 WO 2024109424A1 CN 2023126229 W CN2023126229 W CN 2023126229W WO 2024109424 A1 WO2024109424 A1 WO 2024109424A1
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Prior art keywords
ferrocene
perovskite
hole transport
transport layer
additive
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PCT/CN2023/126229
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French (fr)
Chinese (zh)
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李静
常青
尹君
吴炳辉
郑南峰
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嘉庚创新实验室
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Publication of WO2024109424A1 publication Critical patent/WO2024109424A1/en

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50Photovoltaic [PV] devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80Constructional details
    • H10K30/88Passivation; Containers; Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Definitions

  • the invention relates to an additive used in perovskite, in particular to a perovskite hole transport layer.
  • the photoelectric conversion efficiency (PCE) of perovskite solar cells (PSCs) based on organic-inorganic hybrid metal halide perovskites has increased from nearly 3.8% to about 25.7% in just over a decade, becoming one of the most promising new generation photovoltaic materials recognized worldwide.
  • the hole transport layer is set between the perovskite light absorption layer and the metal electrode. It serves as a hole extraction functional layer and also a protective umbrella for the perovskite. It is one of the key factors that determine the photoelectric conversion efficiency and stability of perovskite solar cells.
  • organic hole transport layer materials include 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), poly(3-hexylthiophene) (P3HT) and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS), etc.
  • inorganic hole transport layer materials include CuSCN, NiO x , MoS 2 , MoO x , etc.
  • doped organic hole materials are often used as hole transport layers, but their own conductivity and mobility are very low, so they need to be additionally doped with dopants such as lithium trifluoromethanesulfonyl imide (Li-TFSI) to improve the electrical properties of the material.
  • dopants such as lithium trifluoromethanesulfonyl imide (Li-TFSI) to improve the electrical properties of the material.
  • Li-TFSI lithium trifluoromethanesulfonyl imide
  • Iodine vacancy defects are generated, which are not conducive to the stability of the perovskite structure. The large-scale generation of defects will lead to the failure of the perovskite active layer.
  • the performance of the hole transport layer is also affected by ion migration in the perovskite structure.
  • High-efficiency perovskite solar cells are mainly composed of perovskites containing mixed cations of cesium (Cs) and formamidine (FA) and a high proportion of iodide.
  • Cs cesium
  • FA formamidine
  • iodide a high proportion of iodide.
  • the instability of iodine makes it easy for perovskites to produce related defects in the film.
  • these defects including iodine vacancies and iodine interstitial defects, will cause interfacial charge recombination, resulting in a decrease in the efficiency and long-term operation stability of PSCs.
  • the further migration of iodine will affect the conductivity, Fermi level and structural stability of the hole transport layer.
  • the main purpose of the present invention is to provide an additive that can inhibit ion migration in the hole transport layer and improve the problem of decreased device working stability caused by the generation of vacancy defects in the perovskite active layer.
  • the technical solution adopted by the present invention to solve its technical problem is:
  • An additive characterized in that it comprises a first component, wherein the first component comprises at least one of ferrocene and ferrocene compounds, and a polar solvent for dissolving the ferrocene and ferrocene compounds.
  • the concentration of ferrocene and ferrocene-based compounds is 1-20 mg/mL.
  • the ferrocene and ferrocene-based compounds include at least one of ferrocene hexafluorophosphate, ferrocene tetrafluoroborate, ferrocene trifluorosulfonate, ferrocene iodide and ferrocene.
  • the polar solvent includes acetonitrile, DMF (N,N-dimethylformamide), DMSO (dimethylformamide), Sulfoxide), NMP (N-methylpyrrolidone) or at least one of the following.
  • the present invention also provides a surface modification method for a metal electrode, wherein the additive is coated on the metal electrode or between the metal electrode and an adjacent contact layer to modify the surface of the metal electrode.
  • the present invention also provides a method for passivating the surface of perovskite, which adopts the additive to be coated on the surface of organic halide perovskite or inorganic halide perovskite to passivate the surface of the perovskite.
  • the present invention also provides a perovskite photoelectric device, wherein the perovskite light absorbing layer is modified by the additive, and/or the metal electrode is modified by the additive.
  • the additive provided by the present invention further comprises a second component, wherein the second component comprises an aprotic non-polar solvent.
  • the volume ratio of the first component to the second component is (1-10):100.
  • the aprotic non-polar solvent comprises at least one of diethyl ether, ethyl acetate, chlorobenzene, toluene or chloroform.
  • the present invention also provides a hole transport layer, which is prepared by using the additive.
  • the present invention also provides a method for preparing a hole transport layer, which is prepared by adding hole transport layer materials into the additives to react to obtain a mixed solution, and coating the mixed solution on a substrate.
  • the mass ratio of the ferrocene and ferrocene-based compounds to the hole transport layer material is 1:10-1:90.
  • the hole transport layer material includes at least one of Spiro-OMeTAD, PTAA, P3HT, phthalocyanine, and NiO x .
  • the present invention also provides another perovskite photoelectric device, comprising the hole transport layer or the hole transport layer prepared by the preparation method.
  • the additive provided by the present invention can improve the oxidation potential of the metal electrode on the upper layer of the hole transport layer, inhibit ion migration in the hole transport layer, and improve the problem of decreased device working stability caused by the generation of vacancy defects in the perovskite active layer. Therefore, after being used in the hole transport layer material, it can inhibit ion migration and improve the photoelectric conversion efficiency and stability of the overall device, and is particularly suitable for the doping of high-efficiency hole transport layer materials of ortho-perovskite solar cells; for perovskite surface modification, it can effectively inhibit ion migration in perovskite films; for metal electrode surface modification, it can enhance antioxidant capacity and stability, and improve the flatness of the metal electrode surface.
  • the ferrocene and ferrocene compounds of the present invention are not polymers, nor are they used as terminal groups, and can exert an oxidizing effect on hole transport layer materials.
  • the additives of the present invention can be used not only in the hole transport layer, but also can be used alone on the surface modification of perovskite or on metal electrodes.
  • FIG. 1 shows different usages of additives in Examples 1-11 (implementation route 3), Example 12 (implementation route 1), and Examples 13-14 (implementation route 2).
  • FIG2 is an X-ray photoelectron spectrum of the gold electrode layer of the perovskite solar cell prepared by Example 1 and Comparative Example 1 after aging.
  • FIG2a and FIG2b are X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Example 1
  • FIG2c and FIG2d are X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Comparative Example 1, respectively.
  • FIG3 is an X-ray photoelectron spectrum of the hole transport layer of the perovskite solar cell prepared by Example 1 and Comparative Example 1 after aging.
  • FIG3a and FIG3b are X-ray photoelectron spectra of lead (Pb) and iodine (I) measured in Example 1
  • FIG3c and FIG3d are X-ray photoelectron spectra of lead (Pb) and iodine (I) measured in Comparative Example 1. Photoelectron spectrum.
  • FIG5 is a graph showing the photoelectric conversion efficiency test results of the perovskite solar cells prepared using Example 1 and Comparative Example 1.
  • FIG. 7 is a graph showing the light stability test results of the perovskite films prepared using Example 12 and Comparative Example 2.
  • FIG8 is a graph showing the test results of the oxidation potential of the gold electrode layer obtained after annealing the metal-deposited perovskite film prepared in Example 13 and Comparative Example 3.
  • FIG9 is a scanning electron microscope image of the upper metal layer of the metal-deposited perovskite film prepared by Example 13 and Comparative Example 3.
  • the preparation of a normal structure perovskite solar cell includes the following steps:
  • Substrate cleaning Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
  • FTO F-doped Tin Oxide
  • tin oxide electron transport layer also known as n-type semiconductor
  • the tin oxide nanoparticle aqueous solution was diluted with ultrapure water at a volume ratio of 1:2, and the target solution was obtained after ultrasonication for 30 seconds. The solution was then heated at 3000 rpm/s.
  • the electron transport layer was obtained by spin coating on the cleaned FTO substrate at a rotation speed of 1000 nm and annealing at 120°C for 40 min.
  • perovskite light absorbing layer Lead iodide, iodoformamide, methylamine bromide and lead bromide were dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, and shaken for 2 h to obtain a perovskite precursor solution. The precursor solution was then spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain a perovskite light absorbing layer.
  • the ratio of lead iodide, iodomethane, methylammonium bromide, lead bromide, N,N-dimethylformamide, and dimethyl sulfoxide is 353 mg:120 mg:4 mg:13 mg:400 ⁇ L:100 ⁇ L.
  • Metal electrode layer deposition vacuum thermal evaporation deposition 80nm of metal was evaporated at a rate of 1.5 times that of the original material to obtain a complete upright structure perovskite solar cell.
  • the method for using the additives is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • S2 The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
  • Li-TFSI lithium bis(trifluoromethane)sulfonyl imide
  • a normal structure perovskite solar cell was prepared using the same preparation method as in Example 1.
  • the method is different in that the hole transport layer is prepared in step (4), and the preparation of the hole transport layer specifically includes the following steps:
  • Li-TFSI lithium bis(trifluoromethane)sulfonyl imide
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • S2 The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • S2 The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), and the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • S2 The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 73 mg/mL, shaken well, dissolved by ultrasonication and filtered;
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • S2 The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 73 mg/mL, shaken well, dissolved by ultrasonication and filtered;
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 .
  • the preparation of the hole transport layer specifically includes the following steps:
  • the perovskite film is prepared, including the following steps:
  • Substrate cleaning Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
  • FTO F-doped Tin Oxide
  • the ratio of lead iodide, iodomethane, methylammonium bromide, lead bromide, N,N-dimethylformamide, and dimethyl sulfoxide is 353 mg:120 mg:4 mg:13 mg:400 ⁇ L:100 ⁇ L.
  • the method of using the additives is shown in the implementation route 1 in FIG. 1 .
  • the steps include:
  • S2 Take 20 ⁇ L of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
  • the perovskite film is prepared by the same preparation method as in Example 12, except that after the perovskite light absorbing layer is prepared, the following steps are included:
  • the perovskite film deposited with metal is prepared, including the following steps, wherein the method of using the additive is as shown in the implementation route 2 in FIG. 1 :
  • Substrate cleaning Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
  • FTO F-doped Tin Oxide
  • perovskite light-absorbing layer Dissolve lead iodide, iodoformamidine, methylamine bromide, and lead bromide in N,N-dichloromethane.
  • the perovskite precursor solution was obtained by shaking in a mixed solvent of methylformamide and dimethyl sulfoxide for 2 h, and then the precursor solution was spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain the perovskite light absorbing layer.
  • S2 Take 20 ⁇ L of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
  • S4 The modified optoelectronic device film is subjected to metal deposition to deposit 80 nm of gold on the perovskite surface.
  • the preparation of a metal-deposited perovskite film includes the following steps:
  • Substrate cleaning Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
  • FTO F-doped Tin Oxide
  • a perovskite film with metal deposited thereon is prepared by the same preparation method as in Example 13, except that an additive is used in step (3), specifically comprising the following steps:
  • S2 Take 20 ⁇ L of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
  • S4 The modified optoelectronic device film is subjected to metal deposition to deposit 80 nm of silver (Ag) on the surface of the perovskite.
  • the perovskite solar cells prepared using Example 1 and Comparative Example 1 were photoaged in a nitrogen environment at 85°C for 7 days, and the X-ray photoelectron spectrum of the gold electrode layer was tested. The measured results are shown in Figure 2.
  • the X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Example 1 and the X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Comparative Example 1 correspond to Figures 2a, 2b and 2c, 2d, respectively.
  • the perovskite solar cells prepared in Example 1 and Comparative Example 1 were light aged for 7 days in a nitrogen environment at 85°C, and the X-ray photoelectron spectrum of the hole transport layer was tested. The measured results are shown in Figure 3.
  • the X-ray photoelectron spectrum of lead (Pb) and iodine (I) measured in Example 1 and the X-ray photoelectron spectrum of lead (Pb) and iodine (I) measured in Comparative Example 1 correspond to Figures 3a, 3b and 3c, 3d, respectively.
  • the perovskite solar cells prepared in Examples 1-4 and Comparative Example 1 were subjected to photoelectric tests, and the test results are shown in Table 1. As can be seen from Table 1, the perovskite solar cells prepared in Examples 1-4 have good open circuit voltage, short circuit voltage, and In terms of the four core performance indicators of flux density, filling factor, and efficiency, they are all better than the perovskite solar cell prepared in Comparative Example 1, indicating that the perovskite solar cell prepared using additives has better photoelectric performance.
  • the iodine/lead ratio of the perovskite film prepared in Example 12 after aging is closer to 3 (perovskite has an ABX 3 structure, and the iodine/lead ratio is close to 3, which indicates that the ion migration is low), indicating that the ion migration of the perovskite film prepared using the additive is
  • the migration of ions can be slowed down and ion migration can be more effectively suppressed.
  • the metal-deposited perovskite film prepared in Example 13 and Comparative Example 3 was subjected to thermal annealing treatment to remove the perovskite light-absorbing layer on the film, and the gold electrode layer to be tested was obtained, and then the redox potential was tested by a three-electrode system cyclic voltammetry (the electrolyte was a 0.4 mol/L Na 2 SO 4 aqueous solution, the reference electrode was an Ag/AgCl electrode immersed in a saturated potassium chloride solution, the counter electrode was a Pt electrode, and the metal electrode layer was fixed with an electrode clamp as a working electrode, and the cyclic voltammetry test method was used, the scanning speed was 5 mV/s, and a stable spectrum was obtained after multiple scans), and the test results are shown in Figure 8.
  • the oxidation potential test diagrams of the gold electrode layer to be tested obtained in Comparative Example 3 and the gold electrode layer to be tested obtained in Example 13 are shown in Figures 8a and 8b, respectively.
  • the gold electrode layer to be tested (modified with additives) obtained in Example 13 has a higher oxidation potential (1.34 V) and enhanced antioxidant capacity.
  • the metal-deposited perovskite films prepared in Example 13 and Comparative Example 3 were aged for 3 days under indoor ambient light, and the surface morphology of the perovskite films was observed by scanning electron microscopy, and the corrosion of the gold electrode was detected by direct comparison.
  • the scanning electron microscope image obtained by the test is shown in Figure 9, and the surface morphologies of Comparative Example 3 treated with light, Comparative Example 3 treated with light, and Example 13 treated with light are shown in Figures 9a, 9b, and 9c, respectively.
  • the present invention discloses an additive, comprising a first component, wherein the first component comprises at least one of ferrocene and ferrocene compounds, and a polar solvent for dissolving the ferrocene and ferrocene compounds.
  • the additive provided by the present invention can be used for surface modification of metal electrodes, surface passivation of perovskite materials, and hole transport layer materials, can inhibit ion migration, and can improve the photoelectric conversion efficiency and stability of the overall device, and is particularly suitable for doping of high-efficiency hole transport layer materials of ortho-structure perovskite solar cells, and has industrial practicability.

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Abstract

An additive, comprising a first component, wherein the first component comprises at least one of ferrocene and a ferrocene compound, and a polar solvent used for dissolving the ferrocene and the ferrocene compound. The provided additive can be used for surface modification of a metal electrode, surface passivation of a perovskite material and doping of a hole transport layer material, can inhibit ion migration, and can improve the photoelectric conversion efficiency and stability of a device; and the additive is particularly suitable for efficient doping of a hole transport layer material in perovskite solar cell of a normal structure.

Description

一种添加剂及其使用方法Additive and method of using the same
本申请要求申请日2022年11月22日向中国国家知识产权局,申请号为:202211464849.5,发明创造名称是:“一种添加剂及其使用方法”的中国专利申请为基础,并主张其优先权,该中国专利申请的公开内容在此作为整体引入本申请文本中。This application claims a Chinese patent application filed on November 22, 2022 with the State Intellectual Property Office of China, with application number: 202211464849.5, and the name of the invention is: "An additive and its method of use" as the basis, and claims its priority. The disclosed content of the Chinese patent application is hereby introduced as a whole into the text of this application.
技术领域Technical Field
本发明涉及一种钙钛矿使用的添加剂,尤其涉及钙钛矿空穴传输层。The invention relates to an additive used in perovskite, in particular to a perovskite hole transport layer.
背景技术Background technique
在钙钛矿光伏领域,基于有机-无机杂化金属卤化物钙钛矿的钙钛矿太阳能电池(PSCs)的光电转换效率(PCE)在短短十余年内从近3.8%提高到约25.7%,成为全球公认最具前景的新一代光伏材料之一。空穴传输层设置于钙钛矿吸光层与金属电极中,作为空穴提取功能层的同时,也是钙钛矿的一层保护伞,是决定钙钛矿太阳能电池光电转换效率和稳定性的关键因素之一。In the field of perovskite photovoltaics, the photoelectric conversion efficiency (PCE) of perovskite solar cells (PSCs) based on organic-inorganic hybrid metal halide perovskites has increased from nearly 3.8% to about 25.7% in just over a decade, becoming one of the most promising new generation photovoltaic materials recognized worldwide. The hole transport layer is set between the perovskite light absorption layer and the metal electrode. It serves as a hole extraction functional layer and also a protective umbrella for the perovskite. It is one of the key factors that determine the photoelectric conversion efficiency and stability of perovskite solar cells.
目前常用的有机空穴传输层材料有2,2',7,7'-四[N,N-二(4-甲氧基苯基)氨基]-9,9'-螺二芴(Spiro-OMeTAD),聚三芳基胺(PTAA),聚(3-己基噻吩)(P3HT)和聚(3,4-乙二氧噻吩):聚苯乙烯磺酸酯(PEDOT:PSS)等,无机空穴传输层材料有CuSCN,NiOx,MoS2,MoOx等。无机空穴传输层材料虽然稳定性较好,但是器件效率处于劣势,在正置器件结构中,为了得到高效的光电转化效率常使用掺杂的有机空穴材料用作空穴传输层,但是它本身的电导率和迁移率都很低,就需要额外掺杂三氟甲磺酰亚胺锂(Li-TFSI)等掺杂剂来提高材料的电学性能。这些掺杂剂虽然可以提高有机材料等的空穴传输性能,但是常因为掺杂剂本身容易团聚导致吸水,或扩散到其他功能层从而影响整体到器件稳定性。钙钛矿薄膜中由于钙钛矿在高温高湿等环境下的分解,会 产生不利于钙钛矿结构稳定的碘空位缺陷,缺陷的大量产生会导致钙钛矿活性层的失效,它们常常会向上迁移并使得钙钛矿晶体产生分解,随时间缓慢的扩散甚至能迁移至金属电极并与其发生反应导致整体器件的不稳定。因此,如何在空穴传输层中选用适合的添加剂以平衡钙钛矿器件的性能与稳定性至关重要。往往添加剂的选择只能针对一个功能层的特定对象作用,无法兼顾多功能层的稳定性问题。At present, commonly used organic hole transport layer materials include 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), poly(3-hexylthiophene) (P3HT) and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS), etc., and inorganic hole transport layer materials include CuSCN, NiO x , MoS 2 , MoO x , etc. Although inorganic hole transport layer materials have good stability, the device efficiency is at a disadvantage. In the normal device structure, in order to obtain high photoelectric conversion efficiency, doped organic hole materials are often used as hole transport layers, but their own conductivity and mobility are very low, so they need to be additionally doped with dopants such as lithium trifluoromethanesulfonyl imide (Li-TFSI) to improve the electrical properties of the material. Although these dopants can improve the hole transport performance of organic materials, they often tend to aggregate and absorb water, or diffuse into other functional layers, thus affecting the overall stability of the device. Iodine vacancy defects are generated, which are not conducive to the stability of the perovskite structure. The large-scale generation of defects will lead to the failure of the perovskite active layer. They often migrate upward and cause the perovskite crystal to decompose. Over time, they slowly diffuse and can even migrate to the metal electrode and react with it, causing the overall device to be unstable. Therefore, it is crucial to select suitable additives in the hole transport layer to balance the performance and stability of the perovskite device. Often, the selection of additives can only act on a specific object of a functional layer, and cannot take into account the stability of the multifunctional layer.
此外,空穴传输层性能也会受钙钛矿结构中的离子迁移影响。高效的钙钛矿太阳能电池主要由含有混合阳离子铯(Cs)和甲脒(FA)的钙钛矿以及高比例的碘化物组成。碘的不稳定性使得钙钛矿在薄膜容易产生相关的缺陷。同时,这些缺陷包括碘空位和碘间质缺陷会引起界面电荷重组,导致PSCs效率和长期运行稳定性下降。并且碘的进一步迁移会影响空穴传输层的导电性、费米能级以及结构稳定性。目前有通过使用许多化合物后处理钙钛矿表面,以抑制与碘相关的表面缺陷的形成以及离子迁移的方案。In addition, the performance of the hole transport layer is also affected by ion migration in the perovskite structure. High-efficiency perovskite solar cells are mainly composed of perovskites containing mixed cations of cesium (Cs) and formamidine (FA) and a high proportion of iodide. The instability of iodine makes it easy for perovskites to produce related defects in the film. At the same time, these defects, including iodine vacancies and iodine interstitial defects, will cause interfacial charge recombination, resulting in a decrease in the efficiency and long-term operation stability of PSCs. And the further migration of iodine will affect the conductivity, Fermi level and structural stability of the hole transport layer. There are currently schemes to suppress the formation of iodine-related surface defects and ion migration by post-treating the perovskite surface with many compounds.
发明内容Summary of the invention
本发明的主要目的,在于提供一种添加剂能够抑制空穴传输层中离子迁移及改善钙钛矿活性层中对空位缺陷的产生引起的器件工作稳定性下降问题。本发明解决其技术问题的所采用的技术方案是:The main purpose of the present invention is to provide an additive that can inhibit ion migration in the hole transport layer and improve the problem of decreased device working stability caused by the generation of vacancy defects in the perovskite active layer. The technical solution adopted by the present invention to solve its technical problem is:
一种添加剂,其特征在于:包括第一组分,所述第一组分包括二茂铁及二茂铁类化合物中的至少一种、及用于溶解所述二茂铁及二茂铁类化合物的极性溶剂。An additive, characterized in that it comprises a first component, wherein the first component comprises at least one of ferrocene and ferrocene compounds, and a polar solvent for dissolving the ferrocene and ferrocene compounds.
优选地,所述二茂铁及二茂铁类化合物的浓度为1-20mg/mL。Preferably, the concentration of ferrocene and ferrocene-based compounds is 1-20 mg/mL.
优选地,所述二茂铁及二茂铁类化合物包括六氟磷酸二茂铁、四氟硼酸二茂铁、三氟磺酸二茂铁、碘代二茂铁、二茂铁中的至少一种。Preferably, the ferrocene and ferrocene-based compounds include at least one of ferrocene hexafluorophosphate, ferrocene tetrafluoroborate, ferrocene trifluorosulfonate, ferrocene iodide and ferrocene.
优选地,所述极性溶剂包括乙腈,DMF(N,N-二甲基甲酰胺),DMSO(二甲基 亚砜),NMP(N-甲基吡咯烷酮)中的至少一种。Preferably, the polar solvent includes acetonitrile, DMF (N,N-dimethylformamide), DMSO (dimethylformamide), Sulfoxide), NMP (N-methylpyrrolidone) or at least one of the following.
本发明还提供一种金属电极的表面修饰方法,采用所述添加剂涂布在所述金属电极上或涂布在所述金属电极与相邻接触层之间以修饰所述金属电极的表面。The present invention also provides a surface modification method for a metal electrode, wherein the additive is coated on the metal electrode or between the metal electrode and an adjacent contact layer to modify the surface of the metal electrode.
本发明还提供一种钙钛矿表面钝化方法,采用所述的添加剂在有机卤化钙钛矿或无机卤化钙钛矿表面涂布以钝化所述钙钛矿表面。The present invention also provides a method for passivating the surface of perovskite, which adopts the additive to be coated on the surface of organic halide perovskite or inorganic halide perovskite to passivate the surface of the perovskite.
本发明还提供一种钙钛矿光电器件,钙钛矿吸光层经过所述的添加剂修饰,和/或金属电极经过所述的添加剂修饰。The present invention also provides a perovskite photoelectric device, wherein the perovskite light absorbing layer is modified by the additive, and/or the metal electrode is modified by the additive.
优选地,本发明提供的添加剂还包括第二组分,所述第二组分包括非质子非极性溶剂。Preferably, the additive provided by the present invention further comprises a second component, wherein the second component comprises an aprotic non-polar solvent.
优选地,所述第一组分与所述第二组分的体积比为(1-10):100。Preferably, the volume ratio of the first component to the second component is (1-10):100.
优选地,所述非质子非极性溶剂包含乙醚、乙酸乙酯、氯苯、甲苯或三氯甲烷中的至少一种。Preferably, the aprotic non-polar solvent comprises at least one of diethyl ether, ethyl acetate, chlorobenzene, toluene or chloroform.
本发明还提供一种空穴传输层,所述空穴传输层采用所述的添加剂制备而成。The present invention also provides a hole transport layer, which is prepared by using the additive.
本发明还提供一种空穴传输层的制备方法,通过将空穴传输层材料加入到所述的添加剂中反应,得到混合溶液,涂布至基底上方制备而成。The present invention also provides a method for preparing a hole transport layer, which is prepared by adding hole transport layer materials into the additives to react to obtain a mixed solution, and coating the mixed solution on a substrate.
优选地,所述二茂铁及二茂铁类化合物与所述空穴传输层材料的质量比为1:10-1:90。Preferably, the mass ratio of the ferrocene and ferrocene-based compounds to the hole transport layer material is 1:10-1:90.
优选地,所述空穴传输层材料包括Spiro-OMeTAD、PTAA、P3HT、钛菁、NiOx中的至少一种。Preferably, the hole transport layer material includes at least one of Spiro-OMeTAD, PTAA, P3HT, phthalocyanine, and NiO x .
本发明还提供另一种钙钛矿光电器件,包括所述空穴传输层或采用所述制备方法制备的空穴传输层。 The present invention also provides another perovskite photoelectric device, comprising the hole transport layer or the hole transport layer prepared by the preparation method.
本发明技术方案与背景技术相比,具有如下优点:Compared with the background technology, the technical solution of the present invention has the following advantages:
1、本发明提供的添加剂,能够提高空穴传输层上层的金属电极的氧化电势,以及抑制空穴传输层中离子迁移及改善钙钛矿活性层中对空位缺陷的产生引起的器件工作稳定性下降问题。因此,用于空穴传输层材料之后,能够抑制离子迁移,并能够提升整体器件的光电转换效率与稳定性,尤其适合正置钙钛矿太阳能电池的高效空穴传输层材料的掺杂;用于钙钛矿表面修饰,能够有效抑制钙钛矿薄膜中的离子迁移;用于金属电极表面修饰,可增强抗氧化能力和稳定性,提升金属电极表面的平整性。1. The additive provided by the present invention can improve the oxidation potential of the metal electrode on the upper layer of the hole transport layer, inhibit ion migration in the hole transport layer, and improve the problem of decreased device working stability caused by the generation of vacancy defects in the perovskite active layer. Therefore, after being used in the hole transport layer material, it can inhibit ion migration and improve the photoelectric conversion efficiency and stability of the overall device, and is particularly suitable for the doping of high-efficiency hole transport layer materials of ortho-perovskite solar cells; for perovskite surface modification, it can effectively inhibit ion migration in perovskite films; for metal electrode surface modification, it can enhance antioxidant capacity and stability, and improve the flatness of the metal electrode surface.
2、本发明的二茂铁及二茂铁类化合物并非聚合物,也不作为端位基团使用,且能够对空穴传输层材料发挥氧化作用。同时,本发明的添加剂不仅可以在空穴传输层中使用,也能够在钙钛矿表面修饰或者金属电极上单独使用。2. The ferrocene and ferrocene compounds of the present invention are not polymers, nor are they used as terminal groups, and can exert an oxidizing effect on hole transport layer materials. At the same time, the additives of the present invention can be used not only in the hole transport layer, but also can be used alone on the surface modification of perovskite or on metal electrodes.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
图1为实施例1-11(实施线路3)、实施例12(实施线路1)、实施例13-14(实施线路2)中添加剂的不同使用方式。FIG. 1 shows different usages of additives in Examples 1-11 (implementation route 3), Example 12 (implementation route 1), and Examples 13-14 (implementation route 2).
图2为采用实施例1与对比例1制备的钙钛矿太阳能电池经老化后的金电极层X-射线光电子能谱图。其中:图2a、图2b分别是实施例1测得的金(Au)与碘(I)的X-射线光电子能谱图和图2c、图2d是对比例1测得的金(Au)与碘(I)的X-射线光电子能谱图。FIG2 is an X-ray photoelectron spectrum of the gold electrode layer of the perovskite solar cell prepared by Example 1 and Comparative Example 1 after aging. Wherein: FIG2a and FIG2b are X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Example 1, and FIG2c and FIG2d are X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Comparative Example 1, respectively.
图3为采用实施例1与对比例1制备的钙钛矿太阳能电池经老化后的空穴传输层X-射线光电子能谱图。其中:图3a、图3b是实施例1测得的铅(Pb)与碘(I)的X-射线光电子能谱图,图3c、图3d是对比例1测得的铅(Pb)与碘(I)的X-射线 光电子能谱图。FIG3 is an X-ray photoelectron spectrum of the hole transport layer of the perovskite solar cell prepared by Example 1 and Comparative Example 1 after aging. Wherein: FIG3a and FIG3b are X-ray photoelectron spectra of lead (Pb) and iodine (I) measured in Example 1, and FIG3c and FIG3d are X-ray photoelectron spectra of lead (Pb) and iodine (I) measured in Comparative Example 1. Photoelectron spectrum.
图4为采用实施例1与对比例1制备的钙钛矿太阳能电池的光照稳定性测试结果图。FIG. 4 is a graph showing the light stability test results of the perovskite solar cells prepared using Example 1 and Comparative Example 1.
图5为采用实施例1与对比例1制备的钙钛矿太阳能电池的光电转换效率测试结果图。FIG5 is a graph showing the photoelectric conversion efficiency test results of the perovskite solar cells prepared using Example 1 and Comparative Example 1.
图6为采用实施例12与对比例2制备的钙钛矿薄膜的基于X-射线光电子能谱测得的薄膜表面碘/铅含量比例结果图。FIG6 is a graph showing the ratio of iodine/lead content on the surface of the perovskite films prepared in Example 12 and Comparative Example 2 measured based on X-ray photoelectron spectroscopy.
图7为采用实施例12与对比例2制备的钙钛矿薄膜的光照稳定性测试结果图。FIG. 7 is a graph showing the light stability test results of the perovskite films prepared using Example 12 and Comparative Example 2.
图8为采用实施例13与对比例3制备的沉积有金属的钙钛矿薄膜经退火后得到的金电极层的氧化电位测试结果图。FIG8 is a graph showing the test results of the oxidation potential of the gold electrode layer obtained after annealing the metal-deposited perovskite film prepared in Example 13 and Comparative Example 3.
图9为采用实施例13与对比例3制备的沉积有金属的钙钛矿薄膜的上层金属的扫描电子显微镜图。FIG9 is a scanning electron microscope image of the upper metal layer of the metal-deposited perovskite film prepared by Example 13 and Comparative Example 3.
具体实施方式Detailed ways
实施例1Example 1
本实施例中制备正置结构钙钛矿太阳能电池,包括如下步骤:In this embodiment, the preparation of a normal structure perovskite solar cell includes the following steps:
(1)基底清洗:将已刻蚀好的FTO(F-doped Tin Oxide,氟掺杂氧化锡)透明导电玻璃放置于清洗架上,使用水溶液、丙酮、乙醇、乙醇依次超声清洗四次,每次清洗时间15min,清洗完毕后取出用氮气吹干,放入紫外臭氧清洗机内清洗玻璃表面15min。(1) Substrate cleaning: Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
(2)氧化锡电子传输层(又称n型半导体)的制备:将氧化锡纳米分散颗粒水溶液加入超纯水以1:2体积比稀释,超声30s后得到目标溶液,将该溶液以3000rpm/s 的转速旋涂在清洗干净的FTO基底上并120℃退火40min得到电子传输层。(2) Preparation of tin oxide electron transport layer (also known as n-type semiconductor): The tin oxide nanoparticle aqueous solution was diluted with ultrapure water at a volume ratio of 1:2, and the target solution was obtained after ultrasonication for 30 seconds. The solution was then heated at 3000 rpm/s. The electron transport layer was obtained by spin coating on the cleaned FTO substrate at a rotation speed of 1000 nm and annealing at 120°C for 40 min.
(3)钙钛矿吸光层的制备:把碘化铅、碘甲脒、溴化甲胺、溴化铅溶于N,N-二甲基甲酰胺、二甲基亚砜的混合溶剂中,震荡2h得到钙钛矿前驱体溶液,然后旋涂前驱液于电子传输层上并100℃退火60min得到钙钛矿吸光层。(3) Preparation of perovskite light absorbing layer: Lead iodide, iodoformamide, methylamine bromide and lead bromide were dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, and shaken for 2 h to obtain a perovskite precursor solution. The precursor solution was then spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain a perovskite light absorbing layer.
其中,碘化铅、碘甲脒、溴化甲胺、溴化铅、N,N-二甲基甲酰胺、二甲基亚砜的比例为353mg:120mg:4mg:13mg:400μL:100μL。Among them, the ratio of lead iodide, iodomethane, methylammonium bromide, lead bromide, N,N-dimethylformamide, and dimethyl sulfoxide is 353 mg:120 mg:4 mg:13 mg:400 μL:100 μL.
(4)制备空穴传输层。(4) Preparation of hole transport layer.
(5)金属电极层沉积:用真空热蒸发蒸镀仪以的速率蒸镀金属80nm,得到完整的正置结构钙钛矿太阳能电池。(5) Metal electrode layer deposition: vacuum thermal evaporation deposition 80nm of metal was evaporated at a rate of 1.5 times that of the original material to obtain a complete upright structure perovskite solar cell.
其中,添加剂的使用方法参见图1中的实施线路3,空穴传输层的制备具体包括如下步骤:The method for using the additives is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以90mg/mL溶解于S1氯苯中,摇匀后,超声溶解后过滤;S2: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S3:添加叔丁基吡啶(tBP)39μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 39 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将双(三氟甲烷)磺酰亚胺锂(Li-TFSI)以520mg/mL溶解于乙腈溶液中,取用23μL加入S3中得到的溶液中摇匀;S4: Dissolve lithium bis(trifluoromethane)sulfonyl imide (Li-TFSI) at 520 mg/mL in acetonitrile solution, take 23 μL and add it to the solution obtained in S3 and shake well;
S5:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续30s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 30 seconds.
对比例1Comparative Example 1
本对比例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方 法,不同在于步骤(4)中空穴传输层的制备,空穴传输层的制备具体包括如下步骤:In this comparative example, a normal structure perovskite solar cell was prepared using the same preparation method as in Example 1. The method is different in that the hole transport layer is prepared in step (4), and the preparation of the hole transport layer specifically includes the following steps:
S1:空穴传输层材料Spiro-OMeTAD以90mg/mL溶解于氯苯中,摇匀后,超声溶解后过滤;S1: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S2:添加叔丁基吡啶(tBP)39μL于1mL的S1中得到的澄清溶液中,摇匀;S2: Add 39 μL of tert-butylpyridine (tBP) to 1 mL of the clear solution obtained in S1 and shake well;
S3:将双(三氟甲烷)磺酰亚胺锂(Li-TFSI)以520mg/mL溶解于乙腈溶液中,取用23μL加入S2中得到的溶液中摇匀;S3: Dissolve lithium bis(trifluoromethane)sulfonyl imide (Li-TFSI) at 520 mg/mL in acetonitrile solution, take 23 μL and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续30s。S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 30 seconds.
实施例2Example 2
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将碘代二茂铁称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of iodoferrocene and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以90mg/mL溶解于S1氯苯中,摇匀后,超声溶解后过滤;S2: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S3:添加叔丁基吡啶(tBP)39μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 39 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将Li-TFSI以520mg/mL溶解于乙腈溶液中,取用23μL加入S3中得到的溶液中摇匀;S4: Dissolve Li-TFSI at 520 mg/mL in acetonitrile solution, take 23 μL and add it to the solution obtained in S3 and shake well;
S5:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续30s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 30 seconds.
实施例3 Example 3
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of ferrocene hexafluorophosphate and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以90mg/mL溶解于S1氯苯中,摇匀后,超声溶解后过滤;S2: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 90 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S3:添加叔丁基吡啶(tBP)39μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 39 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将Li-TFSI以520mg/mL溶解于乙腈溶液中,取用23μL加入S3中得到的溶液中摇匀;S4: Dissolve Li-TFSI at 520 mg/mL in acetonitrile solution, take 23 μL and add it to the solution obtained in S3 and shake well;
S5:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续30s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 30 seconds.
实施例4Example 4
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), and the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将四氟硼酸二茂铁(FcBF4)称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of ferrocene tetrafluoroborate (FcBF 4 ) and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以90mg/mL溶解于S1氯苯中,摇匀得到紫红色澄清溶液;S2: The hole transport layer material Spiro-OMeTAD was dissolved in S1 chlorobenzene at 90 mg/mL and shaken to obtain a purple-red clear solution;
S3:添加叔丁基吡啶(tBP)39μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 39 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将Li-TFSI以520mg/mL溶解于乙腈溶液中,取用23μL加入S3中得到的溶液中摇匀; S4: Dissolve Li-TFSI at 520 mg/mL in acetonitrile solution, take 23 μL and add it to the solution obtained in S3 and shake well;
S5:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续25s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 25 seconds.
实施例5Example 5
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将二茂铁称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of ferrocene and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以73mg/mL溶解于S1氯苯中,摇匀后,超声溶解后过滤;S2: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 73 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S3:添加叔丁基吡啶(tBP)29μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 29 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将Li-TFSI以520mg/mL溶解于乙腈溶液中,取用18μL加入S3中得到的溶液中摇匀;S4: Dissolve Li-TFSI at 520 mg/mL in acetonitrile solution, take 18 μL and add it to the solution obtained in S3 and shake well;
S5:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续30s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 30 seconds.
实施例6Example 6
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将碘代二茂铁称量1mg溶解于1mL氯苯溶液中;S1: Weigh 1 mg of iodoferrocene and dissolve it in 1 mL of chlorobenzene solution;
S2:空穴传输层材料Spiro-OMeTAD以73mg/mL溶解于S1氯苯中,摇匀后,超声溶解后过滤; S2: The hole transport layer material Spiro-OMeTAD was dissolved in chlorobenzene in S1 at 73 mg/mL, shaken well, dissolved by ultrasonication and filtered;
S3:添加叔丁基吡啶(tBP)29μL于1mL的S2中得到的澄清溶液中,摇匀;S3: Add 29 μL of tert-butylpyridine (tBP) to the clear solution obtained in 1 mL of S2 and shake well;
S4:将Li-TFSI以520mg/mL溶解于乙腈溶液中,取用18μL加入S2中得到的溶液中摇匀;S4: Dissolve Li-TFSI at 520 mg/mL in acetonitrile solution, take 18 μL and add it to the solution obtained in S2 and shake well;
S5:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续25s。S5: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 25 seconds.
实施例7Example 7
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution and shake well;
S2:空穴传输层材料PTAA以10mg/mL溶解于氯苯中,摇匀;S2: Dissolve the hole transport layer material PTAA in chlorobenzene at 10 mg/mL and shake well;
S3:取用S1中40μL加入S2中得到的溶液中振荡摇匀;S3: Take 40 μL of S1 and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续30s。S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 30 seconds.
实施例8Example 8
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL N,N-二甲基甲酰胺溶液中摇匀;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of N,N-dimethylformamide solution and shake well;
S2:空穴传输层材料PTAA以10mg/mL溶解于氯苯中,摇匀; S2: Dissolve the hole transport layer material PTAA in chlorobenzene at 10 mg/mL and shake well;
S3:取用S1中40μL加入S2中得到的溶液中振荡摇匀;S3: Take 40 μL of S1 and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续30s。S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 30 seconds.
实施例9Example 9
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution and shake well;
S2:空穴传输层材料P3HT以12mg/mL溶解于氯仿中,摇匀;S2: Dissolve the hole transport layer material P3HT in chloroform at 12 mg/mL and shake well;
S3:取用S1中40μL加入S2中得到的溶液中振荡摇匀;S3: Take 40 μL of S1 and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续30s。S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 30 seconds.
实施例10Example 10
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution and shake well;
S2:空穴传输层材料钛菁以10mg/mL溶解于氯仿中,摇匀;S2: Dissolve the hole transport layer material phthalocyanine in chloroform at 10 mg/mL and shake well;
S3:取用S1中40μL加入S2中得到的溶液中振荡摇匀;S3: Take 40 μL of S1 and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以4000rpm/s转速,滴加于钙钛矿吸光层上持续30s。 S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 4000 rpm/s for 30 seconds.
实施例11Embodiment 11
本实施例中制备正置结构钙钛矿太阳能电池,采用与实施例1中相同的制备方法,不同在于步骤(4)中空穴传输层的制备,其中添加剂的使用方法参见图1中的实施线路3。空穴传输层的制备具体包括如下步骤:In this embodiment, a normal structure perovskite solar cell is prepared by the same preparation method as in Example 1, except that the hole transport layer is prepared in step (4), wherein the method for using the additive is shown in the implementation route 3 in FIG1 . The preparation of the hole transport layer specifically includes the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution and shake well;
S2:空穴传输层材料NiOx以10mg/mL溶解于氯仿中,摇匀;S2: Dissolve the hole transport layer material NiO x in chloroform at 10 mg/mL and shake well;
S3:取用S1中40μL加入S2中得到的溶液中振荡摇匀;S3: Take 40 μL of S1 and add it to the solution obtained in S2 and shake well;
S4:将配好的溶液以3500rpm/s转速,滴加于钙钛矿吸光层上持续30s。S4: Add the prepared solution dropwise onto the perovskite light absorbing layer at a speed of 3500 rpm/s for 30 seconds.
实施例12Example 12
本实施例中制备钙钛矿薄膜,包括如下步骤:In this embodiment, the perovskite film is prepared, including the following steps:
(1)基底清洗:将已刻蚀好的FTO(F-doped Tin Oxide,氟掺杂氧化锡)透明导电玻璃放置于清洗架上,使用水溶液、丙酮、乙醇、乙醇依次超声清洗四次,每次清洗时间15min,清洗完毕后取出用氮气吹干,放入紫外臭氧清洗机内清洗玻璃表面15min。(1) Substrate cleaning: Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
(2)钙钛矿吸光层的制备:把碘化铅、碘甲脒、溴化甲胺、溴化铅溶于N,N-二甲基甲酰胺、二甲基亚砜的混合溶剂中,震荡2h得到钙钛矿前驱体溶液,然后旋涂前驱液于电子传输层上并100℃退火60min得到钙钛矿吸光层。(2) Preparation of perovskite light absorbing layer: Lead iodide, iodoformamide, methylamine bromide and lead bromide were dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, and shaken for 2 h to obtain a perovskite precursor solution. The precursor solution was then spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain a perovskite light absorbing layer.
其中,碘化铅、碘甲脒、溴化甲胺、溴化铅、N,N-二甲基甲酰胺、二甲基亚砜的比例为353mg:120mg:4mg:13mg:400μL:100μL。Among them, the ratio of lead iodide, iodomethane, methylammonium bromide, lead bromide, N,N-dimethylformamide, and dimethyl sulfoxide is 353 mg:120 mg:4 mg:13 mg:400 μL:100 μL.
其中,添加剂的使用方法参见图1中的实施线路1,在完成钙钛矿吸光层制备后, 包括如下步骤:The method of using the additives is shown in the implementation route 1 in FIG. 1 . After the perovskite light absorbing layer is prepared, The steps include:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀,过滤;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution, shake well, and filter;
S2:取用S1中20μL以动态3500rpm/s旋涂置钙钛矿光电器件中钙钛矿吸光层表面;S2: Take 20 μL of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
S3:在800℃下低温退火5min。S3: Low temperature annealing at 800°C for 5 minutes.
对比例2Comparative Example 2
本对比例中制备钙钛矿薄膜,采用与实施例12中相同的制备方法,不同在于在完成钙钛矿吸光层制备后,包括如下步骤:In this comparative example, the perovskite film is prepared by the same preparation method as in Example 12, except that after the perovskite light absorbing layer is prepared, the following steps are included:
S1:取用20μL乙腈溶液以动态3500rpm/s旋涂置钙钛矿光电器件中钙钛矿吸光层表面;S1: Take 20 μL of acetonitrile solution and spin coat it on the surface of the perovskite light absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
S2:在800℃下低温退火5min。S2: Low temperature annealing at 800°C for 5 min.
实施例13Example 13
本实施例中制备沉积有金属的钙钛矿薄膜,包括如下步骤,其中添加剂的使用方法参见图1中的实施线路2:In this embodiment, the perovskite film deposited with metal is prepared, including the following steps, wherein the method of using the additive is as shown in the implementation route 2 in FIG. 1 :
(1)基底清洗:将已刻蚀好的FTO(F-doped Tin Oxide,氟掺杂氧化锡)透明导电玻璃放置于清洗架上,使用水溶液、丙酮、乙醇、乙醇依次超声清洗四次,每次清洗时间15min,清洗完毕后取出用氮气吹干,放入紫外臭氧清洗机内清洗玻璃表面15min。(1) Substrate cleaning: Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
(2)钙钛矿吸光层的制备:把碘化铅、碘甲脒、溴化甲胺、溴化铅溶于N,N-二 甲基甲酰胺、二甲基亚砜的混合溶剂中,震荡2h得到钙钛矿前驱体溶液,然后旋涂前驱液于电子传输层上并100℃退火60min得到钙钛矿吸光层。(2) Preparation of perovskite light-absorbing layer: Dissolve lead iodide, iodoformamidine, methylamine bromide, and lead bromide in N,N-dichloromethane. The perovskite precursor solution was obtained by shaking in a mixed solvent of methylformamide and dimethyl sulfoxide for 2 h, and then the precursor solution was spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain the perovskite light absorbing layer.
(3)添加剂的使用:(3) Use of additives:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀,过滤;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution, shake well, and filter;
S2:取用S1中20μL以动态3500rpm/s旋涂置钙钛矿光电器件中钙钛矿吸光层表面;S2: Take 20 μL of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
S3:在800℃下低温退火5min;S3: low temperature annealing at 800°C for 5 min;
S4:将修饰后的光电器件薄膜进行金属沉积,使金在钙钛矿表面沉积80nm。S4: The modified optoelectronic device film is subjected to metal deposition to deposit 80 nm of gold on the perovskite surface.
对比例3Comparative Example 3
本实施例中制备沉积有金属的钙钛矿薄膜,包括如下步骤:In this embodiment, the preparation of a metal-deposited perovskite film includes the following steps:
(1)基底清洗:将已刻蚀好的FTO(F-doped Tin Oxide,氟掺杂氧化锡)透明导电玻璃放置于清洗架上,使用水溶液、丙酮、乙醇、乙醇依次超声清洗四次,每次清洗时间15min,清洗完毕后取出用氮气吹干,放入紫外臭氧清洗机内清洗玻璃表面15min。(1) Substrate cleaning: Place the etched FTO (F-doped Tin Oxide) transparent conductive glass on a cleaning rack and ultrasonically clean it four times with aqueous solution, acetone, ethanol, and ethanol in sequence. Each cleaning time is 15 min. After cleaning, take out the glass and blow dry it with nitrogen. Place the glass in a UV ozone cleaning machine and clean the glass surface for 15 min.
(2)钙钛矿吸光层的制备:把碘化铅、碘甲脒、溴化甲胺、溴化铅溶于N,N-二甲基甲酰胺、二甲基亚砜的混合溶剂中,震荡2h得到钙钛矿前驱体溶液,然后旋涂前驱液于电子传输层上并100℃退火60min得到钙钛矿吸光层。(2) Preparation of perovskite light absorbing layer: Lead iodide, iodoformamide, methylamine bromide and lead bromide were dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide, and shaken for 2 h to obtain a perovskite precursor solution. The precursor solution was then spin-coated on the electron transport layer and annealed at 100°C for 60 min to obtain a perovskite light absorbing layer.
(3)金属沉积:(3) Metal deposition:
S1:取用20μL乙腈溶液以动态3500rpm/s旋涂置钙钛矿光电器件中钙钛矿吸光层表面; S1: Take 20 μL of acetonitrile solution and spin coat it on the surface of the perovskite light absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
S2:在800℃下低温退火5min;S2: low temperature annealing at 800°C for 5 min;
S3:将光电器件薄膜进行金属沉积,使金(Au)在钙钛矿表面沉积80nm。S3: Perform metal deposition on the optoelectronic device film to deposit 80 nm of gold (Au) on the surface of the perovskite.
实施例14Embodiment 14
本实施例中制备沉积有金属的钙钛矿薄膜,采用与实施例13中相同的制备方法,不同在于步骤(3)中添加剂的使用,具体包括如下步骤:In this embodiment, a perovskite film with metal deposited thereon is prepared by the same preparation method as in Example 13, except that an additive is used in step (3), specifically comprising the following steps:
S1:将六氟磷酸二茂铁(FcPF6)称量20mg溶解于1mL乙腈溶液中摇匀,过滤;S1: Weigh 20 mg of ferrocene hexafluorophosphate (FcPF 6 ) and dissolve it in 1 mL of acetonitrile solution, shake well, and filter;
S2:取用S1中20μL以动态3500rpm/s旋涂置钙钛矿光电器件中钙钛矿吸光层表面;S2: Take 20 μL of S1 and spin-coat it on the surface of the perovskite light-absorbing layer in the perovskite photoelectric device at a dynamic speed of 3500 rpm/s;
S3:在800℃下低温退火5min;S3: low temperature annealing at 800°C for 5 min;
S4:将修饰后的光电器件薄膜进行金属沉积,使银(Ag)在钙钛矿表面沉积80nm。S4: The modified optoelectronic device film is subjected to metal deposition to deposit 80 nm of silver (Ag) on the surface of the perovskite.
性能测试Performance Testing
1、钙钛矿太阳能电池1. Perovskite solar cells
(1)金属电极层的X-射线光电子能谱测试(1) X-ray photoelectron spectroscopy test of metal electrode layer
采用实施例1与对比例1制备的钙钛矿太阳能电池在85℃的氮气环境下光老化7天,测试金电极层的X-射线光电子能谱,测得结果参见图2。采用实施例1测得的金(Au)与碘(I)的X-射线光电子能谱图和对比例1测得的金(Au)与碘(I)的X-射线光电子能谱图分别对应图2a、图2b与图2c、图2d。从图2中可以看出,相对于实施例1,采用对比例1制备的钙钛矿太阳能电池的金电极层的结合能向更高的能量偏移,且对应标准的AuI峰位(88.1eV),也检出了明显的I信号。而采用实施例1制备的钙钛矿太阳能电池的金电极层,其Au无偏移与标准的峰位一致,并未检 出I的信号,说明采用添加剂制备的钙钛矿太阳能电池能够抑制I离子的迁移,从而减少对金属电极的影响。The perovskite solar cells prepared using Example 1 and Comparative Example 1 were photoaged in a nitrogen environment at 85°C for 7 days, and the X-ray photoelectron spectrum of the gold electrode layer was tested. The measured results are shown in Figure 2. The X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Example 1 and the X-ray photoelectron spectrum of gold (Au) and iodine (I) measured in Comparative Example 1 correspond to Figures 2a, 2b and 2c, 2d, respectively. It can be seen from Figure 2 that, relative to Example 1, the binding energy of the gold electrode layer of the perovskite solar cell prepared using Comparative Example 1 shifts to a higher energy, and corresponds to the standard AuI peak position (88.1 eV), and an obvious I signal is also detected. However, the gold electrode layer of the perovskite solar cell prepared using Example 1 has no Au shift and is consistent with the standard peak position, and no I signal is detected. The signal of I is shown, indicating that the perovskite solar cell prepared with additives can inhibit the migration of I ions, thereby reducing the impact on the metal electrode.
(2)空穴传输层的X-射线光电子能谱测试(2) X-ray photoelectron spectroscopy test of hole transport layer
采用实施例1与对比例1制备的钙钛矿太阳能电池在85℃的氮气环境下光老化7天,测试空穴传输层的X-射线光电子能谱,测得结果参见图3。采用实施例1测得的铅(Pb)与碘(I)的X-射线光电子能谱图和对比例1测得的铅(Pb)与碘(I)的X-射线光电子能谱图分别对应图3a、图3b与图3c、图3d。从图3可以看出,相对于采用对比例1制备的钙钛矿太阳能电池的空穴传输层能够检出明显的Pb/I信号,采用实施例1制备的钙钛矿太阳能电池的空穴传输层未检出Pb/I信号,说明添加剂的使用对钙钛矿层中的离子在老化过程中,Pb/I的纵向迁移被添加剂抑制,从而实现抑制空穴传输层中离子迁移。The perovskite solar cells prepared in Example 1 and Comparative Example 1 were light aged for 7 days in a nitrogen environment at 85°C, and the X-ray photoelectron spectrum of the hole transport layer was tested. The measured results are shown in Figure 3. The X-ray photoelectron spectrum of lead (Pb) and iodine (I) measured in Example 1 and the X-ray photoelectron spectrum of lead (Pb) and iodine (I) measured in Comparative Example 1 correspond to Figures 3a, 3b and 3c, 3d, respectively. It can be seen from Figure 3 that, compared with the hole transport layer of the perovskite solar cell prepared in Comparative Example 1, an obvious Pb/I signal can be detected, while no Pb/I signal is detected in the hole transport layer of the perovskite solar cell prepared in Example 1, indicating that the use of the additives inhibits the longitudinal migration of Pb/I in the ions in the perovskite layer during the aging process, thereby inhibiting the migration of ions in the hole transport layer.
(3)光照稳定性测试(3) Light stability test
采用实施例1与对比例1制备的钙钛矿太阳能电池进行光照稳定性测试(室温,AM1.5G太阳光照射),测得的结果参见图4。从图4中可以看出,对比例1制备的钙钛矿太阳能电池的光电转换效率在200h内迅速衰减,而实施例1制备的钙钛矿太阳能电池的光电转换效率在600h内可保持在95%以上,且未出现衰减。相较之下,采用添加剂制备得到的钙钛矿太阳能电池光电转换效率更高,且在光照下能够保持更好的工况稳定性。The perovskite solar cells prepared in Example 1 and Comparative Example 1 were subjected to a light stability test (room temperature, AM1.5G sunlight irradiation), and the measured results are shown in Figure 4. As can be seen from Figure 4, the photoelectric conversion efficiency of the perovskite solar cell prepared in Comparative Example 1 decays rapidly within 200 hours, while the photoelectric conversion efficiency of the perovskite solar cell prepared in Example 1 can be maintained at more than 95% within 600 hours without decay. In comparison, the perovskite solar cell prepared using the additive has a higher photoelectric conversion efficiency and can maintain better operating stability under light.
(4)钙钛矿电池光电测试(4) Photovoltaic testing of perovskite cells
采用实施例1-4与对比例1制备的钙钛矿太阳能电池进行光电测试,测试结果参见表1。从表1可以看出,实施例1-4制备的钙钛矿太阳能电池在开路电压、短路电 流密度、填充因子、效率四类核心性能指标方面,均优于对比例1制备的钙钛矿太阳能电池,说明采用添加剂制备得到的钙钛矿太阳能电池光电性能更优。The perovskite solar cells prepared in Examples 1-4 and Comparative Example 1 were subjected to photoelectric tests, and the test results are shown in Table 1. As can be seen from Table 1, the perovskite solar cells prepared in Examples 1-4 have good open circuit voltage, short circuit voltage, and In terms of the four core performance indicators of flux density, filling factor, and efficiency, they are all better than the perovskite solar cell prepared in Comparative Example 1, indicating that the perovskite solar cell prepared using additives has better photoelectric performance.
采用实施例1与对比例1制备的钙钛矿太阳能电池多次重复测试光电转换效率,测试结果的统计分布图参见图5。从图5中可以看出,采用实施例1制备的钙钛矿太阳能电池具有更高的光电转换效率,器件性能更优,且具有更好的效率稳定性。The photoelectric conversion efficiency of the perovskite solar cells prepared in Example 1 and Comparative Example 1 was repeatedly tested, and the statistical distribution diagram of the test results is shown in Figure 5. As can be seen from Figure 5, the perovskite solar cell prepared in Example 1 has higher photoelectric conversion efficiency, better device performance, and better efficiency stability.
表1 采用实施例1-4与对比例1制备的钙钛矿太阳能电池光电测试结果
Table 1 Photoelectric test results of perovskite solar cells prepared by Examples 1-4 and Comparative Example 1
2、钙钛矿薄膜2. Perovskite thin film
(1)离子迁移测试(1) Ion migration test
采用实施例12与对比例2制备的钙钛矿薄膜在85℃的氮气环境下光老化7天后,进行铅(Pb)与碘(I)的X-射线光电子能谱测试,并对铅与碘的X-射线光电子能谱进行积分,所得到的碘/铅比例结果参见图6。从图6中可以看出,采用实施例12制备的钙钛矿薄膜,其在老化后的碘/铅比例更接近于3(钙钛矿为ABX3结构,碘/铅比例接近3,则说明离子迁移低),说明采用添加剂制备的钙钛矿薄膜的离子迁 移减缓,能够更加有效地抑制离子迁移。After the perovskite films prepared in Example 12 and Comparative Example 2 were light aged for 7 days in a nitrogen environment at 85°C, the X-ray photoelectron spectroscopy of lead (Pb) and iodine (I) was tested, and the X-ray photoelectron spectra of lead and iodine were integrated. The obtained iodine/lead ratio results are shown in Figure 6. As can be seen from Figure 6, the iodine/lead ratio of the perovskite film prepared in Example 12 after aging is closer to 3 (perovskite has an ABX 3 structure, and the iodine/lead ratio is close to 3, which indicates that the ion migration is low), indicating that the ion migration of the perovskite film prepared using the additive is The migration of ions can be slowed down and ion migration can be more effectively suppressed.
(2)光照稳定性测试(2) Light stability test
采用实施例12与对比例2制备的钙钛矿薄膜在85℃的氮气环境下光老化7天后,通过X射线衍射测试对比结晶峰强度与分解情况,测试结果参见图7。从图7中可以看出,采用对比例2制备的钙钛矿薄膜在经光照老化后,钙钛矿薄膜衍射峰强度降低,在13°出现更强的碘化铅的结晶峰,而采用实施例12制备的钙钛矿薄膜在经光照老化后钙钛矿薄膜衍射峰强度与未经光照老化的对比例2制备的钙钛矿薄膜相近,说明采用添加剂制备的钙钛矿薄膜具有更好的稳定性。After the perovskite films prepared in Example 12 and Comparative Example 2 were light aged for 7 days in a nitrogen environment at 85°C, the crystallization peak intensity and decomposition were compared by X-ray diffraction test, and the test results are shown in Figure 7. As can be seen from Figure 7, after the perovskite film prepared in Comparative Example 2 was light aged, the diffraction peak intensity of the perovskite film decreased, and a stronger crystallization peak of lead iodide appeared at 13°, while the diffraction peak intensity of the perovskite film prepared in Example 12 after light aging was similar to that of the perovskite film prepared in Comparative Example 2 without light aging, indicating that the perovskite film prepared using the additive has better stability.
3、沉积有金属的钙钛矿薄膜3. Deposition of metal-deposited perovskite films
(1)金属电极氧化电位测试(1) Metal electrode oxidation potential test
采用实施例13与对比例3制备的沉积有金属的钙钛矿薄膜,进行热退火处理,移除薄膜上的钙钛矿吸光层,得到待测金电极层后进行三电极体系循环伏安测试氧化还原电势(电解液为0.4mol/L Na2SO4水溶液,参比电极为浸泡在饱和氯化钾溶液中的Ag/AgCl电极,对电极为Pt电极,待金属电极层用电极夹固定后作为工作电极,采用Cyclic Voltammetry测试方法,扫描速度为5mV/s,多次扫描后取稳定谱图),测试结果参见图8。采用对比例3得到的待测金电极层以及实施例13得到的待测金电极层的氧化电位测试图分别如图8a和图8b所示。从图8中可以看出,相对于对比例3得到的待测金电极层,采用实施例13得到的待测金电极层(经添加剂修饰),其具有更高的氧化电位(1.34V),抗氧化能力增强。The metal-deposited perovskite film prepared in Example 13 and Comparative Example 3 was subjected to thermal annealing treatment to remove the perovskite light-absorbing layer on the film, and the gold electrode layer to be tested was obtained, and then the redox potential was tested by a three-electrode system cyclic voltammetry (the electrolyte was a 0.4 mol/L Na 2 SO 4 aqueous solution, the reference electrode was an Ag/AgCl electrode immersed in a saturated potassium chloride solution, the counter electrode was a Pt electrode, and the metal electrode layer was fixed with an electrode clamp as a working electrode, and the cyclic voltammetry test method was used, the scanning speed was 5 mV/s, and a stable spectrum was obtained after multiple scans), and the test results are shown in Figure 8. The oxidation potential test diagrams of the gold electrode layer to be tested obtained in Comparative Example 3 and the gold electrode layer to be tested obtained in Example 13 are shown in Figures 8a and 8b, respectively. As can be seen from Figure 8, compared with the gold electrode layer to be tested obtained in Comparative Example 3, the gold electrode layer to be tested (modified with additives) obtained in Example 13 has a higher oxidation potential (1.34 V) and enhanced antioxidant capacity.
(2)稳定性测试 (2) Stability test
采用实施例13与对比例3制备的沉积有金属的钙钛矿薄膜,在室内环境光下老化3天,通过扫描电子显微镜观察钙钛矿薄膜的表面形貌,直观对比检测金电极的腐蚀情况,测试得到的扫描电子显微镜图参见图9,避光处理的对比例3、经光照处理的对比例3以及经光照处理的实施例13的表面形貌分别如图9a、图9b和图9c所示。从图9中可以看出,对比例3制备的钙钛矿薄膜在光照老化前,其上方Au膜已出现了形貌上的破坏与腐蚀,在经光照老化后腐蚀情况严重恶化,而实施例13制备的钙钛矿薄膜在光照老化后,其上方的Au膜仍保持原始的致密与平整,稳定性更高。The metal-deposited perovskite films prepared in Example 13 and Comparative Example 3 were aged for 3 days under indoor ambient light, and the surface morphology of the perovskite films was observed by scanning electron microscopy, and the corrosion of the gold electrode was detected by direct comparison. The scanning electron microscope image obtained by the test is shown in Figure 9, and the surface morphologies of Comparative Example 3 treated with light, Comparative Example 3 treated with light, and Example 13 treated with light are shown in Figures 9a, 9b, and 9c, respectively. It can be seen from Figure 9 that the Au film on the upper surface of the perovskite film prepared in Comparative Example 3 has been morphologically damaged and corroded before light aging, and the corrosion situation has seriously deteriorated after light aging, while the Au film on the upper surface of the perovskite film prepared in Example 13 remains original dense and flat after light aging, and has higher stability.
以上所述,仅为本发明较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.
工业实用性Industrial Applicability
本发明公开了一种添加剂,包括第一组分,所述第一组分包括二茂铁及二茂铁类化合物中的至少一种、用于溶解所述二茂铁及二茂铁类化合物的极性溶剂。本发明提供的添加剂,能够用于金属电极的表面修饰、钙钛矿材料的表面钝化以及空穴传输层材料,可抑制离子迁移,并能够提升整体器件的光电转换效率与稳定性,尤其适合正置结构钙钛矿太阳能电池的高效空穴传输层材料的掺杂,具有工业实用性。 The present invention discloses an additive, comprising a first component, wherein the first component comprises at least one of ferrocene and ferrocene compounds, and a polar solvent for dissolving the ferrocene and ferrocene compounds. The additive provided by the present invention can be used for surface modification of metal electrodes, surface passivation of perovskite materials, and hole transport layer materials, can inhibit ion migration, and can improve the photoelectric conversion efficiency and stability of the overall device, and is particularly suitable for doping of high-efficiency hole transport layer materials of ortho-structure perovskite solar cells, and has industrial practicability.

Claims (15)

  1. 一种添加剂,其特征在于:包括第一组分,所述第一组分包括二茂铁及二茂铁类化合物中的至少一种、及用于溶解所述二茂铁及二茂铁类化合物的极性溶剂。An additive, characterized in that it comprises a first component, wherein the first component comprises at least one of ferrocene and ferrocene compounds, and a polar solvent for dissolving the ferrocene and ferrocene compounds.
  2. 根据权利要求1所述的一种添加剂,其特征在于:所述二茂铁及二茂铁类化合物的浓度为1-20mg/mL。The additive according to claim 1, characterized in that the concentration of ferrocene and ferrocene-based compounds is 1-20 mg/mL.
  3. 根据权利要求1或2所述的一种添加剂,其特征在于:所述二茂铁及二茂铁类化合物包括六氟磷酸二茂铁、四氟硼酸二茂铁、三氟磺酸二茂铁、碘代二茂铁、二茂铁中的至少一种。An additive according to claim 1 or 2, characterized in that the ferrocene and ferrocene compounds include at least one of ferrocene hexafluorophosphate, ferrocene tetrafluoroborate, ferrocene trifluorosulfonate, ferrocene iodide and ferrocene.
  4. 根据权利要求1至3任一项所述的一种添加剂,其特征在于:所述极性溶剂包括乙腈,N,N-二甲基甲酰胺,二甲基亚砜,N-甲基吡咯烷酮中的至少一种。An additive according to any one of claims 1 to 3, characterized in that the polar solvent comprises at least one of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
  5. 金属电极的表面修饰方法,其特征在于:采用权利要求1至4任一项所述的添加剂涂布在所述金属电极上或涂布在所述金属电极与相邻接触层之间以修饰所述金属电极的表面。A method for surface modification of a metal electrode, characterized in that the additive described in any one of claims 1 to 4 is coated on the metal electrode or between the metal electrode and an adjacent contact layer to modify the surface of the metal electrode.
  6. 钙钛矿表面钝化方法,其特征在于:采用权利要求1至4任一项所述的添加剂在有机卤化钙钛矿或无机卤化钙钛矿表面涂布以钝化所述钙钛矿表面。A method for passivating the surface of perovskite, characterized in that: the additive described in any one of claims 1 to 4 is coated on the surface of an organic halide perovskite or an inorganic halide perovskite to passivate the surface of the perovskite.
  7. 一种钙钛矿光电器件,其特征在于:钙钛矿吸光层经过权利要求1至4任一项所述的添加剂修饰,和/或金属电极经过权利要求1至4任一项所述的添加剂修饰。A perovskite photoelectric device, characterized in that: the perovskite light absorbing layer is modified by the additive according to any one of claims 1 to 4, and/or the metal electrode is modified by the additive according to any one of claims 1 to 4.
  8. 根据权利要求1至4任一项所述的一种添加剂,其特征在于:所述添加剂还包括第二组分,所述第二组分包括非质子非极性溶剂。An additive according to any one of claims 1 to 4, characterized in that the additive further comprises a second component, and the second component comprises an aprotic non-polar solvent.
  9. 根据权利要求8所述的一种添加剂,其特征在于:所述第一组分与所述第二组分的体积比为(1-10):100。 An additive according to claim 8, characterized in that the volume ratio of the first component to the second component is (1-10):100.
  10. 根据权利要求8所述的一种添加剂,其特征在于:所述非质子非极性溶剂包含乙醚、乙酸乙酯、氯苯、甲苯或三氯甲烷中的至少一种。An additive according to claim 8, characterized in that the aprotic non-polar solvent comprises at least one of ether, ethyl acetate, chlorobenzene, toluene or chloroform.
  11. 一种空穴传输层,其特征在于:所述空穴传输层采用权利要求8至10任一项所述的添加剂制备而成。A hole transport layer, characterized in that the hole transport layer is prepared using the additive according to any one of claims 8 to 10.
  12. 一种空穴传输层的制备方法,其特征在于,通过将空穴传输层材料加入到权利要求8至10任一项所述的添加剂中反应,得到混合溶液,涂布至基底上方制备而成。A method for preparing a hole transport layer, characterized in that the hole transport layer material is added to the additive according to any one of claims 8 to 10 to react to obtain a mixed solution, and the mixed solution is coated on a substrate to prepare the hole transport layer.
  13. 根据权利要求12所述的制备方法,其特征在于:所述二茂铁及二茂铁类化合物与所述空穴传输层材料的质量比为1:10-1:90。The preparation method according to claim 12, characterized in that the mass ratio of the ferrocene and ferrocene-based compounds to the hole transport layer material is 1:10-1:90.
  14. 根据权利要求12所述的制备方法,其特征在于:所述空穴传输层材料包括Spiro-OMeTAD、PTAA、P3HT、钛菁、NiOx中的至少一种。The preparation method according to claim 12 is characterized in that the hole transport layer material includes at least one of Spiro-OMeTAD, PTAA, P3HT, phthalocyanine, and NiO x .
  15. 一种钙钛矿光电器件,其特征在于,包括权利要求11所述的空穴传输层或采用权利要求12至14任一项所述制备方法制备的空穴传输层。 A perovskite photoelectric device, characterized in that it comprises the hole transport layer according to claim 11 or a hole transport layer prepared by the preparation method according to any one of claims 12 to 14.
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