WO2023098021A1 - Method for preparing perovskite layer by dry method and perovskite solar device - Google Patents

Method for preparing perovskite layer by dry method and perovskite solar device Download PDF

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WO2023098021A1
WO2023098021A1 PCT/CN2022/098610 CN2022098610W WO2023098021A1 WO 2023098021 A1 WO2023098021 A1 WO 2023098021A1 CN 2022098610 W CN2022098610 W CN 2022098610W WO 2023098021 A1 WO2023098021 A1 WO 2023098021A1
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perovskite
layer
film
methylamine
iodide
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PCT/CN2022/098610
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French (fr)
Chinese (zh)
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肖平
许世森
赵志国
王力军
秦校军
刘家梁
李梦洁
熊继光
黄斌
赵东明
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中国华能集团清洁能源技术研究院有限公司
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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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • 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

Definitions

  • the invention belongs to the technical field of preparation of perovskite materials, and in particular relates to a dry method for preparing a perovskite layer and a perovskite solar device.
  • Perovskite materials are widely used in optoelectronic devices due to their long carrier diffusion length, high carrier mobility, and high photoluminescence quantum yield. It has a good application prospect in flexible devices.
  • the object of the present invention is to provide a dry method for preparing a perovskite layer and a perovskite solar device.
  • the method does not use solvents, is environmentally friendly, and the prepared solar device has higher efficiency.
  • the invention provides a method for preparing a perovskite layer by a dry method, comprising the following steps:
  • the iodide is selected from PbI 2 and/or SnI 2 ;
  • the amine halide is selected from methylamine iodide, methylamine bromide, and formamidine iodine and one or more of formamidine bromide;
  • the film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite film.
  • the electrostatic spraying pressure is 0.1-10 Pa, and the spraying distance is 1-100 cm. In a specific embodiment, the electrostatic spraying pressure is 1 Pa, and the spraying distance is 10 cm.
  • the thickness of the formed film is preferably 300 to 400 nm, more preferably 350 nm.
  • the mass ratio of the iodide to the amine halide is (1:3) ⁇ (3:1).
  • the particle size of the perovskite precursor material is 50-1000nm, preferably 100-500nm, more preferably 150-250nm; in a specific embodiment, the particle size of the perovskite precursor material is 200nm.
  • the concentration of the methylamine gas is 0.1-3 mol/L, preferably 0.15-1 mol/L; in a specific embodiment, the density of methylamine is 0.2 mol/L.
  • the vacuum degree of the vacuum heat treatment is 1 ⁇ 10 -5 ⁇ 1 ⁇ 10 -1 Pa; the temperature of the vacuum heat treatment is 80-150°C.
  • the vacuum degree of the vacuum heat treatment is 1 ⁇ 10 -4 Pa.
  • the structural composition of the perovskite film is MAX FA 1-X PbSn 1-y I 3 Br 3-z ;
  • the value of X is 0-1, the value of y is 0-1, and the value of z is 0-0.8.
  • the raw material is selected from PbI 2 and MAI with a mass ratio of 3:3.15;
  • the invention provides a perovskite solar device, which comprises a conductive electrode base layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer and a metal counter electrode layer arranged in sequence;
  • the perovskite light-absorbing layer is prepared by the method described in the above technical solution.
  • 102 represents the conductive electrode base layer
  • 104 represents the hole transport layer
  • 106 represents the perovskite light-absorbing layer
  • 108 represents the electron transport layer
  • 110 represents the metal counter electrode layer.
  • the base layer of the conductive electrode is an FTO transparent electrode
  • the slurry used in the hole transport layer is a commercial PEDOT:PSS (AI 4083) aqueous solution; the present invention uses isopropanol to dilute according to the volume ratio of 1:3, and the scraper coating speed is 10-20mm/s, preferably 15mm/s; the coating temperature is 45-70°C, preferably 55°C; the distance between the scraper and the substrate is 50 ⁇ m; after coating, it is annealed at 80-100°C in nitrogen for 10-20 minutes; the annealing temperature is preferably 90°C, and the time Preferably 15 minutes.
  • the thickness of the hole transport layer is preferably 95-105 nm, more preferably 100 nm.
  • the particle size of the material used in the perovskite light-absorbing layer is preferably 200 nm.
  • An electron transport layer 108 prepared by vapor deposition on the perovskite light-absorbing layer; the material used for the electron transport layer is C60, and the electron transport layer is prepared by vapor deposition, and the vapor deposition rate is 0.1-0.5A/s, More preferably, it is 0.3 A/s; the thickness of the electron transport layer is 40-50 nm.
  • the metal counter electrode layer 110 is vapor-deposited on the electron transport layer, and the material is high-purity copper (>99.99%); the speed of vapor deposition is 0.1 ⁇ 0.5A/s, more preferably 0.3A/s; the thickness of the copper film is preferably 95 to 105 nm, more preferably 100 nm.
  • the invention provides a dry method for preparing a perovskite layer, comprising the following steps: uniformly blending and dispersing iodide and ammonium halide to obtain a perovskite precursor material; the iodide is selected from PbI2 and/or SnI 2 ; the amine halide is selected from one or more of methylamine iodine, methylamine bromide, formamidine iodine and formamidine bromide; the perovskite precursor material is sprayed into a film by electrostatic spraying to obtain a thin film ; The film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite film.
  • the method does not use solvents, and uses a dry method to prepare the perovskite layer, that is, electrostatic spraying + MA assistance, which reduces the amount of precursor materials used, effectively improves the quality of film formation, reduces non-radiative recombination defects, and improves the efficiency of perovskite solar devices. higher.
  • Fig. 1 is a schematic structural view of a perovskite solar device provided by the present invention.
  • Conductive electrode substrate 102 Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
  • the hole transport layer 104 prepared by doctor blade coating method, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol Dilute according to the volume ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50 ⁇ m; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the hole transport The layer thickness is about 100nm;
  • the perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
  • the abrasive particle size is 200nm; the perovskite precursor material is sprayed into a film by electrostatic spraying method, the electrostatic spraying pressure is 1Pa, the spraying distance is 10cm, and the film thickness is 350nm; the obtained film is placed in methylamine gas, wherein The amine concentration is 0.2mol/L; the film is vacuum-heated to form a perovskite film, wherein the vacuum degree is 1 ⁇ 10 -4 Pa, and the heating temperature is 120°C;
  • the metal counter electrode layer 110 deposited on the electron transport layer is made of high-purity copper (>99.99%).
  • the evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
  • Example 3 The perovskite solar device prepared by the perovskite light-absorbing layer 106 is referred to as Example 3.
  • Conductive electrode substrate 102 Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
  • the hole transport layer 104 prepared by doctor blade coating, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol According to the dilution ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50 ⁇ m; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the thickness of the hole transport layer is obtained. About 100nm;
  • the perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
  • the abrasive particle size is 200nm; the perovskite precursor material is sprayed into a film by electrostatic spraying method, the electrostatic spraying pressure is 1Pa, the spraying distance is 10cm, and the film thickness is 350nm;
  • the metal counter electrode layer 110 vapor-deposited on the electron transport layer is made of high-purity copper (>99.99%).
  • the evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
  • Conductive electrode substrate 102 Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
  • the hole transport layer 104 prepared by doctor blade coating, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol Dilute according to the volume ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50 ⁇ m; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the hole transport The layer thickness is about 100nm;
  • the perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
  • the abrasive particle size is 200nm; and it is compacted into a target material, and the radio frequency power supply is 10W by the method of magnetron sputtering, and the Ar pressure is stabilized at 2Pa, and the film is formed by sputtering;
  • the metal counter electrode layer 110 vapor-deposited on the electron transport layer is made of high-purity copper (>99.99%).
  • the evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
  • the present invention adopts the following method to test cell efficiency to the above-mentioned perovskite solar device that embodiment 1 ⁇ 3 and comparative example 1 ⁇ 3 make:
  • the active area of the module is 30m 2 .
  • Example 1 Comparative example 1 Example 2
  • Example 3 Comparative example 2 Comparative example 3 battery efficiency 13% 0.2% 12.8% 11.25% 9% 5%
  • the present invention provides a dry method for preparing a perovskite layer, comprising the following steps: uniformly blending and dispersing iodide and ammonium halide to obtain a perovskite precursor material; the iodide is selected from PbI 2 or SnI 2 ; the halide amine is selected from one or more of methylamine iodine, methylamine bromide, formamidine iodine and formamidine bromide; the perovskite precursor material is sprayed into film to obtain a thin film; the thin film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite thin film.
  • the method does not use solvents, and uses a dry method to prepare the perovskite layer, that is, electrostatic spraying + MA assistance, which reduces the amount of precursor materials used, effectively improves the quality of film formation, reduces non-radiative recombination defects, and improves the efficiency of perovskite solar devices. higher.

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Abstract

The present invention provides a method for preparing a perovskite layer by a dry method and a perovskite solar device. The method comprises the following steps: blending and uniformly dispersing iodide and halogenated amine to obtain a perovskite precursor material, wherein the iodide is selected from PbI2 or SnI2, and the halogenated amine is selected from one or more of methylamine iodine, methylamine bromine, formamidine iodine and formamidine bromine; and applying the perovskite precursor material by adopting an electrostatic spraying method to form a film, so as to obtain a thin film; and placing the thin film in methylamine gas, and then carrying out vacuum heating treatment to obtain a perovskite thin film. Instead of a solvent, the present invention adopts a dry method to prepare a perovskite layer, i.e., electrostatic spraying and MA assistance, the use amount of a precursor material is reduced, the film forming quality is effectively improved, non-radiation composite defects are reduced, and an obtained perovskite solar device is high in efficiency.

Description

一种干法制备钙钛矿层的方法和钙钛矿型太阳能器件A dry method for preparing perovskite layer and perovskite solar device
本申请要求于2021年12月02日提交中国专利局、申请号为202111454859.6、发明名称为“一种干法制备钙钛矿层的方法和钙钛矿型太阳能器件”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 02, 2021, with the application number 202111454859.6, and the title of the invention is "a method for preparing a perovskite layer by a dry method and a perovskite solar device", The entire contents of which are incorporated by reference in this application.
技术领域technical field
本发明属于钙钛矿材料的制备技术领域，尤其涉及一种干法制备钙钛矿层的方法和钙钛矿型太阳能器件。The invention belongs to the technical field of preparation of perovskite materials, and in particular relates to a dry method for preparing a perovskite layer and a perovskite solar device.
背景技术Background technique
钙钛矿材料由于其载流子扩散长度长、载流子迁移率高、光致发光量子产率高等优点被广泛应用在光电器件中，此外，可溶液加工和可印刷的特性使得其在商业化柔性器件中具有很好的应用前景。Perovskite materials are widely used in optoelectronic devices due to their long carrier diffusion length, high carrier mobility, and high photoluminescence quantum yield. It has a good application prospect in flexible devices.
然而，常规溶液法制备钙钛矿材料层的过程中，使用大量溶液，造成环境污染，具有毒性。However, in the process of preparing the perovskite material layer by the conventional solution method, a large amount of solution is used, which causes environmental pollution and is toxic.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种干法制备钙钛矿层的方法和钙钛矿型太阳能器件，该方法不采用溶剂，对环境友好，且制备的太阳能器件具有较高的效率。In view of this, the object of the present invention is to provide a dry method for preparing a perovskite layer and a perovskite solar device. The method does not use solvents, is environmentally friendly, and the prepared solar device has higher efficiency.
本发明提供了一种干法制备钙钛矿层的方法，包括以下步骤：The invention provides a method for preparing a perovskite layer by a dry method, comprising the following steps:
将碘化物和卤化胺共混分散均匀，得到钙钛矿前体材料；所述碘化物选自PbI 2和/或SnI 2；所述卤化胺选自甲胺碘、甲胺溴、甲脒碘和甲脒溴中的一种或多种； Blending and dispersing the iodide and amine halide evenly to obtain a perovskite precursor material; the iodide is selected from PbI 2 and/or SnI 2 ; the amine halide is selected from methylamine iodide, methylamine bromide, and formamidine iodine and one or more of formamidine bromide;
采用静电喷涂法将所述钙钛矿前体材料喷涂成膜，得到薄膜；Spraying the perovskite precursor material to form a film by using an electrostatic spraying method to obtain a film;
将所述薄膜置于甲胺气体中后再进行真空加热处理，得到钙钛矿薄膜。The film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite film.
在本发明中，所述静电喷涂的压力为0.1～10Pa，喷涂的距离为1～100cm。具体实施例中，所述静电喷涂的压力为1Pa，喷涂距离为10cm。成膜的厚度优选为300～400nm，更优选为350nm。In the present invention, the electrostatic spraying pressure is 0.1-10 Pa, and the spraying distance is 1-100 cm. In a specific embodiment, the electrostatic spraying pressure is 1 Pa, and the spraying distance is 10 cm. The thickness of the formed film is preferably 300 to 400 nm, more preferably 350 nm.
在本发明中，所述碘化物和卤化胺的质量比为(1:3)～(3:1)。In the present invention, the mass ratio of the iodide to the amine halide is (1:3)˜(3:1).
在本发明中，所述钙钛矿前体材料的粒度为50～1000nm，优选为 100～500nm，更优选为150～250nm；具体实施例中，钙钛矿前体材料的粒度为200nm。In the present invention, the particle size of the perovskite precursor material is 50-1000nm, preferably 100-500nm, more preferably 150-250nm; in a specific embodiment, the particle size of the perovskite precursor material is 200nm.
在本发明中，所述甲胺气体的浓度为0.1～3mol/L，优选为0.15～1mol/L；具体实施例中，甲胺的密度为0.2mol/L。In the present invention, the concentration of the methylamine gas is 0.1-3 mol/L, preferably 0.15-1 mol/L; in a specific embodiment, the density of methylamine is 0.2 mol/L.
在本发明中，所述真空加热处理的真空度为1×10 -5～1×10 -1Pa；真空加热处理的温度为80～150℃。真空加热处理的真空度为1×10 -4Pa。 In the present invention, the vacuum degree of the vacuum heat treatment is 1×10 -5 ~ 1×10 -1 Pa; the temperature of the vacuum heat treatment is 80-150°C. The vacuum degree of the vacuum heat treatment is 1×10 -4 Pa.
所述钙钛矿薄膜的结构组成为MA XFA 1-XPbSn 1-yI 3Br 3-z； The structural composition of the perovskite film is MAX FA 1-X PbSn 1-y I 3 Br 3-z ;
所述X的取值为0～1，所述y的取值为0～1，所述z的取值为0～0.8。The value of X is 0-1, the value of y is 0-1, and the value of z is 0-0.8.
在本发明中，原料选自质量比为3：3.15的PbI 2和MAI； In the present invention, the raw material is selected from PbI 2 and MAI with a mass ratio of 3:3.15;
或选自质量比为3:3.15：0.3的PbI 2、MAI和MABr； Or selected from PbI 2 , MAI and MABr with a mass ratio of 3:3.15:0.3;
或选自质量比为3:0.3:3:0.1的PbI 2、MABr、FAI和FABr。 Or selected from PbI 2 , MABr, FAI and FABr with a mass ratio of 3:0.3:3:0.1.
本发明提供了一种钙钛矿型太阳能器件，包括依次设置的导电电极基底层、空穴传输层、钙钛矿吸光层、电子传输层和金属对电极层；The invention provides a perovskite solar device, which comprises a conductive electrode base layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer and a metal counter electrode layer arranged in sequence;
所述钙钛矿吸光层由上述技术方案所述方法制得。The perovskite light-absorbing layer is prepared by the method described in the above technical solution.
参见图1，其中，102代表导电电极基底层，104代表空穴传输层，106代表钙钛矿吸光层，108代表电子传输层，110代表金属对电极层。Referring to FIG. 1 , 102 represents the conductive electrode base layer, 104 represents the hole transport layer, 106 represents the perovskite light-absorbing layer, 108 represents the electron transport layer, and 110 represents the metal counter electrode layer.
在本发明中，所述导电电极基底层为FTO透明电极；In the present invention, the base layer of the conductive electrode is an FTO transparent electrode;
所述空穴传输层采用的浆料为商品化PEDOT：PSS(AI 4083)水溶液；本发明采用异丙醇按照体积比1：3配比稀释，刮刀涂布速度为10-20mm/s，优选为15mm/s；涂布温度为45-70℃，优选为55℃；刮刀与基底间距为50μm；涂布后经氮气中80-100℃退火10-20分钟；退火温度优选为90℃，时间优选为15分钟。所述空穴传输层的厚度优选为95～105nm，更优选为100nm。The slurry used in the hole transport layer is a commercial PEDOT:PSS (AI 4083) aqueous solution; the present invention uses isopropanol to dilute according to the volume ratio of 1:3, and the scraper coating speed is 10-20mm/s, preferably 15mm/s; the coating temperature is 45-70°C, preferably 55°C; the distance between the scraper and the substrate is 50μm; after coating, it is annealed at 80-100°C in nitrogen for 10-20 minutes; the annealing temperature is preferably 90°C, and the time Preferably 15 minutes. The thickness of the hole transport layer is preferably 95-105 nm, more preferably 100 nm.
所述钙钛矿吸光层采用的物料的粒度优选为200nm。The particle size of the material used in the perovskite light-absorbing layer is preferably 200 nm.
在钙钛矿吸光层上通过蒸镀法制备的电子传输层108；所述电子传输层采用的材料为C60，采用蒸镀的方式制备电子传输层，蒸镀速度为0.1～0.5A/s，更优选为0.3A/s；电子传输层的厚度为40～50nm。An electron transport layer 108 prepared by vapor deposition on the perovskite light-absorbing layer; the material used for the electron transport layer is C60, and the electron transport layer is prepared by vapor deposition, and the vapor deposition rate is 0.1-0.5A/s, More preferably, it is 0.3 A/s; the thickness of the electron transport layer is 40-50 nm.
在电子传输层上蒸镀金属对电极层110，材料为高纯铜(＞99.99％)；蒸镀的速度为0.1～0.5A/s，更优选为0.3A/s；铜膜的厚度优选为95～105nm，更优选为100nm。The metal counter electrode layer 110 is vapor-deposited on the electron transport layer, and the material is high-purity copper (>99.99%); the speed of vapor deposition is 0.1～0.5A/s, more preferably 0.3A/s; the thickness of the copper film is preferably 95 to 105 nm, more preferably 100 nm.
本发明提供了一种干法制备钙钛矿层的方法，包括以下步骤：将碘化物和卤化胺共混分散均匀，得到钙钛矿前体材料；所述碘化物选自PbI 2和/或SnI 2；所述卤化胺选自甲胺碘、甲胺溴、甲脒碘和甲脒溴中的一种或多种；采用静电喷涂法将所述钙钛矿前体材料喷涂成膜，得到薄膜；将所述薄膜置于甲胺气体中后再进行真空加热处理，得到钙钛矿薄膜。该方法不采用溶剂，采用干法制备钙钛矿层，即静电喷涂+MA辅助，减少前驱体材料的使用量，有效提高了成膜质量，减少非辐射复合缺陷，所得钙钛矿太阳能器件的效率较高。 The invention provides a dry method for preparing a perovskite layer, comprising the following steps: uniformly blending and dispersing iodide and ammonium halide to obtain a perovskite precursor material; the iodide is selected from PbI2 and/or SnI 2 ; the amine halide is selected from one or more of methylamine iodine, methylamine bromide, formamidine iodine and formamidine bromide; the perovskite precursor material is sprayed into a film by electrostatic spraying to obtain a thin film ; The film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite film. The method does not use solvents, and uses a dry method to prepare the perovskite layer, that is, electrostatic spraying + MA assistance, which reduces the amount of precursor materials used, effectively improves the quality of film formation, reduces non-radiative recombination defects, and improves the efficiency of perovskite solar devices. higher.
附图说明Description of drawings
图1为本发明提供的钙钛矿太阳能器件的结构示意图。Fig. 1 is a schematic structural view of a perovskite solar device provided by the present invention.
具体实施方式Detailed ways
为了进一步说明本发明，下面结合实施例对本发明提供的一种干法制备钙钛矿层的方法和钙钛矿型太阳能器件进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a method for preparing a perovskite layer by a dry method and a perovskite solar device provided by the present invention will be described in detail below in conjunction with examples, but they should not be construed as limiting the protection scope of the present invention.
实施例1～3Examples 1-3
1)导电电极基底102：以沉积在透明的FTO透明电极为器件的基底为例，基底面积不限(本例为5×5cm 2)，此类产品有规模化量产的商品化产品可以直接使用。使用前，应将电极表面依次分别使用去离子水、丙酮、异丙醇超声处理15分钟，然后使用紫外光清洗机清洁10分钟，氮气流吹干备用； 1) Conductive electrode substrate 102: Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
2)在导电电极基底上，利用刮刀涂布的方法制备得到的空穴传输层104，以PEDOT：PSS为例，使用的浆料为商品化PEDOT：PSS(AI 4083)水溶液，使用异丙醇按照体积比1：3配比稀释，刮刀涂布速度为15mm/s；涂布温度为55℃；刮刀与基底间距为50μm；涂布后经氮气中90℃退火15分钟，得到的空穴传输层厚度约为100nm；2) On the conductive electrode substrate, the hole transport layer 104 prepared by doctor blade coating method, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol Dilute according to the volume ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50μm; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the hole transport The layer thickness is about 100nm;
3)在空穴传输层上制备的钙钛矿吸光层106，结构为MA XFA 1-XPbSn 1-yI 3Br 3-z： 3) The perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
a)PbI 2：SnI 2：MAI：MABr：FAI：FABr＝3：0：3.15：0：0：0； a) PbI2 : SnI2 :MAI:MABr:FAI:FABr=3:0:3.15:0:0:0;
b)PbI 2：SnI 2：MAI：MABr：FAI：FABr＝3：0：3.15：0.3：0：0； b) PbI2 : SnI2 :MAI:MABr:FAI:FABr=3:0:3.15:0.3:0:0;
c)PbI 2：SnI 2：MAI：MABr：FAI：FABr＝3：0：0：0.3：3：0.1； c) PbI2 : SnI2 :MAI:MABr:FAI:FABr=3:0:0:0.3:3:0.1;
研磨粒径为200nm；采用静电喷涂法将钙钛矿前体材料喷涂成膜，静电喷涂压力为1Pa，喷涂距离为10cm，成膜厚度为350nm；将所得薄膜置入甲胺气体中，其中甲胺浓度为0.2mol/L；将薄膜进行真空加热处理形成钙钛矿薄膜，其中真空度1×10 -4Pa，加热温度120℃； The abrasive particle size is 200nm; the perovskite precursor material is sprayed into a film by electrostatic spraying method, the electrostatic spraying pressure is 1Pa, the spraying distance is 10cm, and the film thickness is 350nm; the obtained film is placed in methylamine gas, wherein The amine concentration is 0.2mol/L; the film is vacuum-heated to form a perovskite film, wherein the vacuum degree is 1×10 -4 Pa, and the heating temperature is 120°C;
4)在钙钛矿吸光层上通过蒸镀法制备的电子传输层108，材料为C60，蒸镀速度为0.3A/s；厚度约为45nm；4) An electron transport layer 108 prepared by vapor deposition on the perovskite light-absorbing layer, the material is C60, the vapor deposition rate is 0.3A/s; the thickness is about 45nm;
5)在电子传输层上蒸镀的金属对电极层110，材料为高纯铜(>99.99％)。蒸镀速度为0.3A/s，铜膜的厚度约100nm，得到钙钛矿太阳能器件。5) The metal counter electrode layer 110 deposited on the electron transport layer is made of high-purity copper (>99.99%). The evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
a)组成分的钙钛矿吸光层106制备的钙钛矿太阳能器件记作实施例1；a) The perovskite solar device prepared by the perovskite light-absorbing layer 106 of composition is recorded as embodiment 1;
b)组成分的钙钛矿吸光层106制备的钙钛矿太阳能器件记作实施例2；b) The perovskite solar device prepared by the perovskite light-absorbing layer 106 of composition is recorded as embodiment 2;
c)组成分的钙钛矿吸光层106制备的钙钛矿太阳能器件记作实施例3。c) The perovskite solar device prepared by the perovskite light-absorbing layer 106 is referred to as Example 3.
对比例1Comparative example 1
与实施例1相比，不同之处在于，PbI 2：SnI 2：MAI：MABr：FAI：FABr＝2：1：3.15：0：0：0。 Compared with Example 1, the difference is that PbI 2 :SnI 2 :MAI:MABr:FAI:FABr=2:1:3.15:0:0:0.
对比例2Comparative example 2
1)导电电极基底102：以沉积在透明的FTO透明电极为器件的基底为例，基底面积不限(本例为5×5cm 2)，此类产品有规模化量产的商品化产品可以直接使用。使用前，应将电极表面依次分别使用去离子水、丙酮、异丙醇超声处理15分钟，然后使用紫外光清洗机清洁10分钟，氮气流吹干备用； 1) Conductive electrode substrate 102: Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
2)在导电电极基底上，利用刮刀涂布的方法制备得到的空穴传输层104，以PEDOT：PSS为例，使用的浆料为商品化PEDOT：PSS(AI 4083)水溶液，使用异丙醇按照1：3配比稀释，刮刀涂布速度为15mm/s；涂布温度为55℃；刮刀与基底间距为50μm；涂布后经氮气中90℃退火15分钟，得到的空穴传输层厚度约为100nm；2) On the conductive electrode substrate, the hole transport layer 104 prepared by doctor blade coating, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol According to the dilution ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50μm; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the thickness of the hole transport layer is obtained. About 100nm;
3)在空穴传输层上制备的钙钛矿吸光层106，结构为MA XFA 1-XPbSn 1-yI 3Br 3-z： 3) The perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
a)PbI 2：SnI 2：MAI：MABr：FAI：FABr＝3：0：3.15：0：0：0； a) PbI2 : SnI2 :MAI:MABr:FAI:FABr=3:0:3.15:0:0:0;
研磨粒径为200nm；采用静电喷涂法将钙钛矿前体材料喷涂成膜，静电喷涂压力为1Pa，喷涂距离为10cm，成膜厚度为350nm；The abrasive particle size is 200nm; the perovskite precursor material is sprayed into a film by electrostatic spraying method, the electrostatic spraying pressure is 1Pa, the spraying distance is 10cm, and the film thickness is 350nm;
4)在钙钛矿吸光层上通过热蒸发法制备的电子传输层108，材料为C60，蒸镀速度为0.3A/s；厚度约为45nm；4) The electron transport layer 108 prepared by thermal evaporation on the perovskite light-absorbing layer, the material is C60, the evaporation rate is 0.3A/s; the thickness is about 45nm;
5)在电子传输层上蒸镀的金属对电极层110，材料为高纯铜(＞99.99％)。蒸镀速度为0.3A/s，铜膜的厚度约100nm，得到钙钛矿太阳能器件。5) The metal counter electrode layer 110 vapor-deposited on the electron transport layer is made of high-purity copper (>99.99%). The evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
对比例3Comparative example 3
1)导电电极基底102：以沉积在透明的FTO透明电极为器件的基底为例，基底面积不限(本例为5×5cm 2)，此类产品有规模化量产的商品化产品可以直接使用。使用前，应将电极表面依次分别使用去离子水、丙酮、异丙醇超声处理15分钟，然后使用紫外光清洗机清洁10分钟，氮气流吹干备用； 1) Conductive electrode substrate 102: Take the substrate deposited on the transparent FTO transparent electrode as the device as an example . use. Before use, the surface of the electrode should be ultrasonically treated with deionized water, acetone, and isopropanol for 15 minutes, then cleaned with a UV cleaner for 10 minutes, and dried with nitrogen flow for later use;
2)在导电电极基底上，利用刮刀涂布的方法制备得到的空穴传输层104，以PEDOT：PSS为例，使用的浆料为商品化PEDOT：PSS(AI 4083)水溶液，使用异丙醇按照体积比1：3配比稀释，刮刀涂布速度为15mm/s；涂布温度为55℃；刮刀与基底间距为50μm；涂布后经氮气中90℃退火15分钟，得到的空穴传输层厚度约为100nm；2) On the conductive electrode substrate, the hole transport layer 104 prepared by doctor blade coating, taking PEDOT:PSS as an example, the slurry used is a commercial PEDOT:PSS (AI 4083) aqueous solution, using isopropanol Dilute according to the volume ratio of 1:3, the coating speed of the blade is 15mm/s; the coating temperature is 55°C; the distance between the blade and the substrate is 50μm; after coating, it is annealed at 90°C in nitrogen for 15 minutes, and the hole transport The layer thickness is about 100nm;
3)在空穴传输层上制备的钙钛矿吸光层106，结构为MA XFA 1-XPbSn 1-yI 3Br 3-z： 3) The perovskite light-absorbing layer 106 prepared on the hole transport layer has a structure of MAX FA 1-X PbSn 1-y I 3 Br 3-z :
a)PbI 2：SnI 2：MAI：MABr：FAI：FABr＝3：0：3.15：0：0：0； a) PbI2 : SnI2 :MAI:MABr:FAI:FABr=3:0:3.15:0:0:0;
研磨粒径为200nm；并压实为靶材，通过磁控溅射的方法，射频电源功率为10W，Ar气压稳定在2Pa，溅射成膜；The abrasive particle size is 200nm; and it is compacted into a target material, and the radio frequency power supply is 10W by the method of magnetron sputtering, and the Ar pressure is stabilized at 2Pa, and the film is formed by sputtering;
4)在钙钛矿吸光层上通过热蒸发法制备的电子传输层108，材料为C60，蒸镀速度为0.3A/s；厚度为45nm；4) An electron transport layer 108 prepared by thermal evaporation on the perovskite light-absorbing layer, the material is C60, the evaporation rate is 0.3A/s; the thickness is 45nm;
5)在电子传输层上蒸镀的金属对电极层110，材料为高纯铜(＞99.99％)。蒸镀速度为0.3A/s，铜膜的厚度约100nm，得到钙钛矿太阳能器件。5) The metal counter electrode layer 110 vapor-deposited on the electron transport layer is made of high-purity copper (>99.99%). The evaporation rate is 0.3A/s, the thickness of the copper film is about 100nm, and a perovskite solar device is obtained.
本发明对实施例1～3和对比例1～3制得的上述钙钛矿太阳能器件采用以下方法测试电池效率:The present invention adopts the following method to test cell efficiency to the above-mentioned perovskite solar device that embodiment 1～3 and comparative example 1～3 make:
将完整的电池置于模拟标准太阳光(AM 1.5G，100mW/cm 2)下，其光强用NREL认证的标准参考电池标定，用Keithley 2400数字源表记录得到电池的电流密度-电压(J-V)曲线； Put the complete battery under simulated standard sunlight (AM 1.5G, 100mW/cm 2 ), the light intensity is calibrated with a standard reference battery certified by NREL, and the current density-voltage (JV )curve;
组件的有效面积为30m 2。 The active area of the module is 30m 2 .
测试结果见表1：The test results are shown in Table 1:
表1 实施例和对比例制备的太阳能器件的电池效率The cell efficiency of the solar device prepared by table 1 embodiment and comparative example
 the 实施例1Example 1 对比例1Comparative example 1 实施例2Example 2 实施例3Example 3 对比例2Comparative example 2 对比例3Comparative example 3
电池效率battery efficiency 13％13% 0.2％0.2% 12.8％12.8% 11.25％11.25% 9％9% 5％5%
由以上实施例可知，本发明提供了一种干法制备钙钛矿层的方法，包括以下步骤：将碘化物和卤化胺共混分散均匀，得到钙钛矿前体材料；所述碘化物选自PbI 2或SnI 2；所述卤化胺选自甲胺碘、甲胺溴、甲脒碘和甲脒溴中的一种或多种；采用静电喷涂法将所述钙钛矿前体材料喷涂成膜，得到薄膜；将所述薄膜置于甲胺气体中后再进行真空加热处理，得到钙钛矿薄膜。该方法不采用溶剂，采用干法制备钙钛矿层，即静电喷涂+MA辅助，减少前驱体材料的使用量，有效提高了成膜质量，减少非辐射复合缺陷，所得钙钛矿太阳能器件的效率较高。 As can be seen from the above examples, the present invention provides a dry method for preparing a perovskite layer, comprising the following steps: uniformly blending and dispersing iodide and ammonium halide to obtain a perovskite precursor material; the iodide is selected from PbI 2 or SnI 2 ; the halide amine is selected from one or more of methylamine iodine, methylamine bromide, formamidine iodine and formamidine bromide; the perovskite precursor material is sprayed into film to obtain a thin film; the thin film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite thin film. The method does not use solvents, and uses a dry method to prepare the perovskite layer, that is, electrostatic spraying + MA assistance, which reduces the amount of precursor materials used, effectively improves the quality of film formation, reduces non-radiative recombination defects, and improves the efficiency of perovskite solar devices. higher.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (9)

  1. 一种干法制备钙钛矿层的方法，包括以下步骤：A dry method for preparing a perovskite layer, comprising the following steps:
    将碘化物和卤化胺共混分散均匀，得到钙钛矿前体材料；所述碘化物选自PbI 2或SnI 2；所述卤化胺选自甲胺碘、甲胺溴、甲脒碘和甲脒溴中的一种或多种； Blending and dispersing iodide and amine halide evenly to obtain a perovskite precursor material; the iodide is selected from PbI 2 or SnI 2 ; the amine halide is selected from methylamine iodide, methylamine bromide, formamidine iodine and formamide One or more of amidine bromides;
    采用静电喷涂法将所述钙钛矿前体材料喷涂成膜，得到薄膜；Spraying the perovskite precursor material to form a film by using an electrostatic spraying method to obtain a film;
    将所述薄膜置于甲胺气体中后再进行真空加热处理，得到钙钛矿层。The film is placed in methylamine gas and then subjected to vacuum heat treatment to obtain a perovskite layer.
  2. 根据权利要求1所述的方法，其特征在于，所述静电喷涂的压力为0.1～10Pa，喷涂的距离为1～100cm。The method according to claim 1, characterized in that the electrostatic spraying pressure is 0.1-10 Pa, and the spraying distance is 1-100 cm.
  3. 根据权利要求1所述的方法，其特征在于，所述碘化物和卤化胺的质量比为(1:3)～(3:1)。The method according to claim 1, characterized in that the mass ratio of the iodide to the amine halide is (1:3)˜(3:1).
  4. 根据权利要求1所述的方法，其特征在于，所述钙钛矿前体材料的粒度为50～1000nm。The method according to claim 1, characterized in that the particle size of the perovskite precursor material is 50-1000 nm.
  5. 根据权利要求1所述的方法，其特征在于，所述甲胺气体的浓度为0.1～3mol/L。The method according to claim 1, characterized in that the concentration of the methylamine gas is 0.1-3 mol/L.
  6. 根据权利要求1所述的方法，其特征在于，所述真空加热处理的真空度为1×10 -5～1×10 -1Pa； The method according to claim 1, characterized in that the vacuum degree of the vacuum heat treatment is 1×10 -5 ~ 1×10 -1 Pa;
    真空加热处理的温度为80～150℃。The temperature of the vacuum heat treatment is 80-150°C.
  7. 根据权利要求1所述的方法，其特征在于，所述钙钛矿层的组成为MA XFA 1-XPbSn 1-yI 3Br 3-z； The method according to claim 1, wherein the composition of the perovskite layer is MAX FA 1-X PbSn 1-y I 3 Br 3-z ;
    所述X的取值为0～1，所述y的取值为0～1，所述z的取值为0～0.8。The value of X is 0-1, the value of y is 0-1, and the value of z is 0-0.8.
  8. 根据权利要求1所述的方法，其特征在于，原料选自质量比为3：3.15的PbI 2和MAI； The method according to claim 1, wherein the raw material is selected from PbI and MAI with a mass ratio of 3:3.15;
    或选自质量比为3:3.15:0.3的PbI 2、MAI和MABr； Or selected from PbI 2 , MAI and MABr with a mass ratio of 3:3.15:0.3;
    或选自质量比为3:0.3:3:0.1的PbI 2、MABr、FAI和FABr。 Or selected from PbI 2 , MABr, FAI and FABr with a mass ratio of 3:0.3:3:0.1.
  9. 一种钙钛矿型太阳能器件，其特征在于，包括依次设置的导电电极基底层、空穴传输层、钙钛矿吸光层、电子传输层和金属对电极层；A perovskite solar device, characterized in that it includes a conductive electrode base layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer and a metal counter electrode layer arranged in sequence;
    所述钙钛矿吸光层为权利要求1～8任一项所述方法制得的钙钛矿层。The perovskite light-absorbing layer is the perovskite layer prepared by the method described in any one of claims 1-8.
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