CN110224067B - Hole transport material of perovskite solar cell, and preparation method and application thereof - Google Patents
Hole transport material of perovskite solar cell, and preparation method and application thereof Download PDFInfo
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- CN110224067B CN110224067B CN201910565227.3A CN201910565227A CN110224067B CN 110224067 B CN110224067 B CN 110224067B CN 201910565227 A CN201910565227 A CN 201910565227A CN 110224067 B CN110224067 B CN 110224067B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- 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
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- Y02E10/549—Organic PV cells
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Abstract
The invention provides a hole transport material of a perovskite solar cell, and a preparation method and application thereof. The hole transport material composition comprises an inorganic hole transport material and rare metal elements, wherein the molar ratio of the metal elements in the inorganic hole transport material to the rare metal elements is N1 (N is more than or equal to 20 and less than or equal to 100000). The hole transport layer of the perovskite solar cell is prepared from the hole transport material composition of the perovskite solar cell. The perovskite solar cell has good stability and high conversion efficiency.
Description
Technical Field
The invention relates to a material of a hole transport layer of a perovskite solar cell, and belongs to the technical field of solar cell materials.
Background
Solar cells can directly convert light energy into electrical energy. The main products of photovoltaic power generation in the market at present are silicon crystals or cadmium telluride, gallium arsenide and other compound crystals. However, the preparation of these photovoltaic materials is complex and energy-consuming, which limits the development of the photovoltaic industry to a certain extent. As a representative of the third generation of solar cells, the conversion efficiency of perovskite solar cells is over 23% from the first 3.8% to the present in a few years, which makes the photovoltaic industry look at the great potential for developing perovskite solar cells.
In order to further increase the efficiency of the perovskite solar cell, the light absorbing layer and the carrier transporting layer of the perovskite solar cell need to be optimized. The inorganic hole transport material has lower efficiency than the Spiro-OMeTAD hole transport material, but the prepared perovskite solar cell has stability and price superior to the Spiro-OMeTAD organic hole transport material. Therefore, the perovskite solar cell with high efficiency and high stability is prepared by using the inorganic material hole transport layer, and the method has important significance for industrialization.
However, the open circuit voltage and the filling factor of the perovskite battery prepared by the traditional inorganic hole transport layer material are not high enough, which is mainly caused by insufficient matching of the self energy band structure and the perovskite energy band structure and low carrier transport efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a perovskite solar cell with higher open-circuit voltage and conversion efficiency.
In order to achieve the technical purpose, the invention firstly provides a hole transport material composition of a perovskite solar cell, which comprises an inorganic hole transport material and rare metal elements, wherein the molar ratio of the metal elements in the inorganic hole transport material to the rare metal elements is N1 (N is more than or equal to 20 and less than or equal to 100000).
According to the hole transport material composition of the perovskite solar cell, rare metal element ions with a specific proportion are introduced into the inorganic hole transport material, so that the rare metal element ions replace metal ions in the inorganic hole transport material or are filled into crystal lattices of the inorganic hole transport material, and the concentration of holes in the inorganic hole transport material is improved. The rare metal element ions in the inorganic hole material can not only lower the valence band top of the inorganic hole transport material and enable the energy band of the hole transport material to be better matched with the energy band of perovskite, but also improve the coverage of the perovskite film on the hole transport layer. The photoelectric conversion efficiency of the perovskite solar cell prepared based on the hole transport material composition disclosed by the invention is improved by more than 10%.
In one embodiment of the present invention, the rare metal element used is one or a combination of two or more of beryllium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, gallium, indium, thallium, germanium, rhenium, tin, and arsenic.
In one embodiment of the present invention, the rare metal element used is one or a combination of two or more compounds containing beryllium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, gallium, indium, thallium, germanium, rhenium, tin, arsenic metal ions.
In one embodiment of the present invention, rare metal ions are used in a valence state of one or a combination of two or more of monovalent, divalent, trivalent, and tetravalent.
In a specific embodiment of the present invention, the rare metal compound used may be one or a combination of two or more of a rare metal halide, sulfide, nitride, oxide, phosphide (an anion centered on phosphorus element, including but not limited to a phosphorylate), thiocyanide, acetate.
In one embodiment of the present invention, the inorganic hole transport material used is nickel oxide, cuI, cu 2 O, cuSCN, or a combination of two or more thereof.
The invention also provides a method for preparing a hole transport layer precursor liquid of the perovskite solar cell by using the hole transport material composition of the perovskite solar cell, which comprises the following steps:
mixing the solution of the inorganic hole transport material with the solution containing rare metal ions, and stirring for more than 12 hours at 55-85 ℃ to obtain the hole transport layer precursor liquid of the perovskite solar cell.
Wherein, the concentration ratio of the solution of the inorganic hole transport material to the solution containing rare metal ions is as long as the molar ratio of the metal ions to the rare metal ions is N1 (N is more than or equal to 20 and less than or equal to 100000).
In a specific embodiment of the present invention, the solvent used for the solution of the inorganic hole transport material is one or a combination of two or more of acetonitrile, ethanol, N-dimethylformamide and dimethyl sulfoxide.
Specifically, the preparation method of the hole transport material precursor liquid of the perovskite solar cell comprises the following steps:
preparing a solution of an inorganic hole transport material, wherein the inorganic hole transport material can be nickel oxide, cuI or Cu 2 O, cuSCN, or a combination of two or more thereof; the solvent used for preparing the solution of the inorganic hole transport material may beOne or more of acetonitrile, ethanol, N-dimethylformamide and dimethyl sulfoxide;
preparing a solution containing rare metal ions;
adding a solution containing rare metal ions into the solution of the inorganic hole transport material, and stirring for more than 12 hours at 55-85 ℃ to obtain the hole transport material composition of the perovskite solar cell, wherein the molar ratio of the metal element of the inorganic hole transport material to the rare metal element is N1 (N is more than or equal to 20 and less than or equal to 100000).
The hole transport material composition of the perovskite solar cell is prepared by doping rare metals into inorganic hole transport materials. The rare metal ions function to replace inorganic hole elements in the inorganic hole transport material or to fill in lattice gaps of the inorganic hole transport material. The rare metal ions can improve the hole concentration in the inorganic hole transport material and improve the contact between the surface of the inorganic hole transport material and the perovskite material, so that the energy level matching degree of the hole transport material and the perovskite and the adhesiveness of the perovskite material on the surface of the inorganic hole transport material are improved, and the coverage rate of the prepared perovskite film on the hole transport layer is improved.
The invention also provides a perovskite solar cell, and the hole transport layer of the perovskite solar cell is prepared from the precursor liquid of the hole transport layer of the perovskite solar cell.
In a specific embodiment of the present invention, the hole transport layer precursor solution for forming a perovskite solar cell of the present invention may be prepared by one or a combination of two or more of spin coating, slit coating, doctor blading, spray coating and printing.
In one embodiment of the present invention, the hole transport layer has a thickness of 10nm to 1000nm.
In one embodiment of the invention, the perovskite solar cell comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a counter electrode and the like from bottom to top, wherein the hole transport layer is prepared from the hole transport material composition of the perovskite solar cell.
Specifically, the conductive substrate of the perovskite solar cell comprises conductive materials such as FTO or ITO.
Specifically, the molecular formula of the light absorption layer material of the perovskite solar cell is ABX 3 Wherein A comprises CH 3 NH 3+ 、NH 2 CHNH 2+ 、CS + 、Rb + Plasma cation, B includes Pb 2+ 、Sn 2+ 、Ge 2+ 、Sr 2+ 、Cu 2+ 、Bi 3+ 、Sb 3+ Plasma, X includes I - 、Cl - Or Br (Br) - And halogen anions.
Specifically, the electron transport layer of the perovskite solar cell is formed of TiO 2 、ZnO、SnO 2 The inorganic electron transport material or the organic electron transport material such as PCBM may be a mixture of at least two of the above electron transport materials.
Specifically, the material of the perovskite solar cell counter electrode is one or a combination of more than two of Al, ag, au, mo, cr, C.
According to the hole transport material composition of the perovskite solar cell, rare metals are introduced into the inorganic hole transport material, so that the energy band structure of the hole transport layer is effectively improved, and the effect of energy band matching with the perovskite material is achieved. Meanwhile, the concentration of carriers in the hole transport layer is also greatly improved. Based on the hole transport layer formed, the photoelectric conversion efficiency of the perovskite solar cell is improved by more than 10%.
Drawings
Fig. 1 is a structural diagram of a perovskite solar cell in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Comparative example 1
The comparative example provides a perovskite solar cell prepared by the steps of:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Hole transport layer preparation: preparing nickel oxide solution. The concentration of the solution was 10mg/mL. Heating the glass in the step (1), filtering the prepared hole transport layer material solution, and spraying the filtered solution by a spray gun.
(3) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing the perovskite thin film light absorption layer on the hole transport layer prepared in the step (2) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(4) And (3) preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(5) Preparing a counter electrode: the vacuum chamber was evacuated to 2.0X10 -4 Pa is pre-evaporated for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 1
The present embodiment provides a perovskite solar cell having a structure as shown in fig. 1, which is prepared by the steps of:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Indium chloride with the mole ratio of 0.5% is mixed with nickel oxide as solute, then 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotating table at 65 ℃ for 12 hours, if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution, and the concentration of the prepared nickel oxide is 10mg/mL.
(3) Hole transport layer preparation: and (3) heating the glass in the step (1), filtering the prepared precursor liquid of the hole transport layer material, and spraying the filtered precursor liquid by using a spray gun.
(4) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing a perovskite thin film light absorption layer on the hole transport layer prepared in the step (3) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(5) And (3) preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: vacuum chamber was pumped to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 2
The embodiment provides a perovskite solar cell, which is prepared by the following steps:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Beryllium bromide with the mole ratio of 0.5% is mixed with nickel oxide as solute, then 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotating table at 65 ℃ for 5 hours, if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution, and the concentration of the prepared nickel oxide is 10mg/mL.
(3) Hole transport layer preparation: and (3) heating the glass in the step (1), filtering the prepared hole transport layer material precursor liquid, and spraying the filtered precursor liquid by using a spray gun.
(4) The perovskite light absorbing layer is prepared. The light absorbing layer is made of MAPbI 3 . And (3) preparing a perovskite thin film light absorption layer on the hole transport layer prepared in the step (3) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(5) And (3) preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Comparative example 2
The comparative example provides a perovskite solar cell prepared by the steps of:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Hole transport layer preparation: preparing a CuI solution. The concentration of the solution was 30mg/mL. Heating the glass in the step (1), filtering the prepared hole transport layer material solution, and spraying the filtered solution by a spray gun.
(3) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing the perovskite thin film light absorption layer on the hole transport layer prepared in the step (2) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(4) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(5) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 3
The embodiment provides a perovskite solar cell, which is prepared by the following steps:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Indium chloride with the molar ratio of 0.3% is mixed with CuI as a solute, 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotary table for 5 hours, and if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution in a proper amount.
(3) Hole transport layer preparation: and (3) heating the glass in the step (1), filtering the prepared hole transport layer material precursor liquid, and spraying the filtered precursor liquid by using a spray gun.
(4) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing a perovskite thin film light absorption layer on the hole transport layer prepared in the step (3) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(5) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 4
The embodiment provides a perovskite solar cell, which is prepared by the following steps:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Beryllium bromide with the mole ratio of 0.3% is mixed with CuI as a solute, 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotary table for 5 hours, and if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution in a proper amount.
(3) And (3) heating the glass in the step (1), filtering the prepared hole transport layer material precursor liquid, and spraying the filtered precursor liquid by using a spray gun.
(4) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . Prepared in step (3) by spin coatingAnd preparing a perovskite thin film light absorption layer on the hole transmission layer. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(5) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Comparative example 3
The comparative example provides a perovskite solar cell prepared by the steps of:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Hole transport layer preparation: a CuSCN solution was formulated. The concentration of the solution was 20mg/mL. Heating the glass in the step (1), filtering the prepared hole transport layer material solution, and spraying the filtered solution by a spray gun.
(3) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing the perovskite thin film light absorption layer on the hole transport layer prepared in the step (2) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(4) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(5) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 5
The embodiment provides a perovskite solar cell, which is prepared by the following steps:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Beryllium bromide with the mole ratio of 0.2% is mixed with CuSCN as a solute, 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotary table for 5 hours, and if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution in a proper amount.
(3) Hole transport layer preparation: and (3) heating the glass in the step (1), filtering the prepared hole transport layer material precursor liquid, and spraying the filtered precursor liquid by using a spray gun.
(4) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing a perovskite thin film light absorption layer on the hole transport layer prepared in the step (3) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10ml of DMF.
(5) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
Example 6
The embodiment provides a perovskite solar cell, which is prepared by the following steps:
(1) And (3) cleaning glass: and (3) etching the FTO glass by adding zinc powder and dilute hydrochloric acid, and cutting the etched glass into small glass with the thickness of 2.5 multiplied by 2.5 cm. Sequentially using detergent, deionized water, ethanol and acetone to carry out ultrasonic treatment on the small glass for 20 minutes. After being dried by nitrogen, the mixture was treated in an ultraviolet ozone machine for 30 minutes.
(2) Preparing a hole transport layer preparation precursor solution: an inorganic hole transport material solution containing rare metal element ions is prepared. Tungsten sulfide with the mole ratio of 0.2% is mixed with CuSCN as a solute, 35mL of acetonitrile and 5mL of ethanol are added into the mixture, the mixture is rotated on a rotary table for 5 hours, and if a small amount of solute is added into the solution, 1-2mL of DMSO can be added into the solution in a proper amount.
(3) Hole transport layer preparation: and (3) heating the glass in the step (1), filtering the prepared hole transport layer material precursor liquid, and spraying the filtered precursor liquid by using a spray gun.
(4) Preparing a perovskite light absorption layer: the light absorbing layer is made of MAPbI 3 . And (3) preparing a perovskite thin film light absorption layer on the hole transport layer prepared in the step (3) through a spin coating method. MAI/PbI 2 Concentration of PbI in 1:1 solution 2 600mg/mL and 198mg/mL MAI. 1 washed 20mL brown reagent bottle was taken, and 6g of PbI was measured 2 And 1.9g of MAI were added sequentially to the flask, followed by 10mL of DMF.
(5) Preparing an electron transport layer: PCBM and BCP are sequentially spin-coated on the prepared perovskite film. PCBM was applied in an amount of 2.5X2.5 cells per block at 500. Mu.l, and after spin-coating, heated on a hot plate at 75℃for 10 minutes. The amount of BCP was 800. Mu.l, and after spin coating, it was heated on a hot plate for 10 minutes.
(6) Preparing a counter electrode: the vacuum chamber was evacuated to 2.1X10 -4 Pa, pre-vapor deposition is carried out for 5 minutes. The evaporation rate of Ag is 100nm0.5A/S before, and the 100-1000nm can be about 6A/S.
The efficiency of the solar cells prepared in the above comparative example and example was compared. The results are shown in Table 1.
TABLE 1
From the data in table 1, it can be seen that by doping nickel oxide, cuI and CuSCN with a certain proportion of rare metal elements, the short-circuit current, the filling factor and the conversion efficiency of the perovskite solar cell are all obviously high, which is attributed to the fact that after doping of the rare metal elements, the hole concentration in the nickel oxide, cuI and CuSCN is greatly improved, the carrier mobility is basically unchanged, the morphology of the surface of the nickel oxide layer is improved, and the crystallization and film forming characteristics of the perovskite on the surface of the perovskite solar cell are better.
The above examples show that the invention provides a feasible idea for preparing perovskite solar cells with high efficiency and good stability.
Claims (6)
1. The hole transport material composition of the perovskite solar cell comprises an inorganic hole transport material and rare metal elements, wherein the molar ratio of the metal elements in the inorganic hole transport material to the rare metal elements is N:1, N is more than or equal to 20 and less than or equal to 100000, and the rare metal elements are beryllium.
2. The hole transporting material composition of claim 1, wherein the inorganic hole transporting material is nickel oxide, cuI, cu 2 O, cuSCN, or a combination of two or more thereof.
3. A method for preparing a hole transport layer precursor liquid for a perovskite solar cell using a hole transport material composition for a perovskite solar cell according to claim 1 or 2, wherein the method comprises the steps of:
mixing the solution of the inorganic hole transport material with the solution containing rare metal ions, and stirring for more than 12 hours at 55-85 ℃ to obtain the hole transport layer precursor liquid of the perovskite solar cell.
4. The method according to claim 3, wherein the solvent used for the solution of the inorganic hole transport material is one or a combination of two or more of acetonitrile, ethanol, N-dimethylformamide and dimethyl sulfoxide.
5. A perovskite solar cell, wherein the hole transport layer of the perovskite solar cell is prepared from the hole transport layer precursor solution of the perovskite solar cell of claim 3.
6. The perovskite solar cell of claim 5, wherein the hole transport layer has a thickness of 10nm-1000nm.
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