CN117794266A - Hole transport layer, perovskite solar cell, and preparation method and application thereof - Google Patents
Hole transport layer, perovskite solar cell, and preparation method and application thereof Download PDFInfo
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- CN117794266A CN117794266A CN202311514114.3A CN202311514114A CN117794266A CN 117794266 A CN117794266 A CN 117794266A CN 202311514114 A CN202311514114 A CN 202311514114A CN 117794266 A CN117794266 A CN 117794266A
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 36
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- 238000000137 annealing Methods 0.000 claims description 24
- 238000002161 passivation Methods 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
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- 239000011521 glass Substances 0.000 claims description 19
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a hole transport layer, a perovskite solar cell, a preparation method and application thereof. The hole transport layer reduces stress in the perovskite thin film layer forming process by utilizing the self-sensitive photoinduced structure interconversion characteristic of the 6-bromocoumarin-3-ethyl formate, and simultaneously dynamically inhibits stress generated by light bath when the solar cell works, so that the stability of the solar cell is enhanced. And the preparation method of the hole transport layer is easy to operate, has good repeatability and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the field of perovskite solar cells, and particularly relates to a hole transport layer, a perovskite solar cell, and a preparation method and application thereof.
Background
Due to the excellent photoelectric properties of metal halide perovskite materials, perovskite solar cells have become an advantageous competitor for next generation photovoltaics, and laboratory photoelectric conversion efficiencies have broken through by 26%. However, the unavoidable stresses present in the perovskite thin films produced by thermal annealing result in a significant number of defects and perovskite lattice distortions at the thin film interface. The stress and the defects can lead to non-radiative charge recombination, increase device hysteresis, promote perovskite film degradation, and reduce battery performance and stability. When the perovskite solar cell is tested and operated, residual stress, particularly tensile stress, accelerates the damage of external water, oxygen, heat and ultraviolet rays to the performance of the perovskite solar cell, and limits the operation stability of the cell. In addition, the light bath will cause the perovskite layer to lattice expand and perovskite decompose, creating additional stress. Therefore, developing a technology for dynamically regulating and controlling the photo-induced stress of a perovskite thin film, improving the quality of the perovskite thin film, reducing the stress of the thin film, reducing the defect density and enhancing the performance and stability of a device is an urgent need to realize the industrialization of perovskite solar cells.
Disclosure of Invention
In order to improve the technical problems, the invention provides a hole transport layer, which comprises a substrate and a coating layer on the surface of the substrate, wherein the coating layer contains 6-bromocoumarin-3-ethyl formate.
According to an embodiment of the invention, the substrate of the hole transport layer is a nickel oxide nanoparticle film, and specifically, the hole transport layer comprises a nickel oxide nanoparticle film and a coating layer consisting of 6-bromocoumarin-3-ethyl formate, which is positioned on the surface of the film.
According to an embodiment of the invention, the thickness of the coating layer is 0.5-5nm.
According to an embodiment of the invention, the ethyl 6-bromocoumarin-3-carboxylate is applied as a solution of ethyl 6-bromocoumarin-3-carboxylate;
wherein the 6-bromocoumarin-3-ethyl formate solution is prepared by dissolving 6-bromocoumarin-3-ethyl formate in an organic solvent, wherein the organic solvent is at least one selected from DMF, DMSO, 2-methoxyethanol, N-methylpyrrolidone, gamma-butyrolactone, isopropanol, ethanol, chlorobenzene, toluene, ethyl acetate and the like. Preferably, the concentration of the 6-bromocoumarin-3-carboxylic acid ethyl ester solution is 0.05-5mg/mL, and still more preferably 0.2-4mg/mL.
The invention also provides a preparation method of the hole transport layer, which comprises the following steps: and coating a substrate of the hole transport layer with a 6-bromocoumarin-3-ethyl formate solution, and carrying out annealing treatment to obtain the hole transport layer.
According to an embodiment of the invention, the annealing treatment is carried out at a temperature of 40-120 ℃, preferably 60-100 ℃.
The invention also provides a perovskite solar cell, which sequentially comprises a conductive glass substrate, a hole transmission layer, a perovskite thin film layer, an electron transmission layer and a metal electrode.
According to an embodiment of the present invention, the coating layer on the hole transport layer is connected to the perovskite thin film layer.
According to an embodiment of the invention, the conductive glass substrate is FTO, ITO or a flexible substrate.
According to an embodiment of the invention, the electron transport layer is a PCBM electron transport layer or a C60 electron transport layer.
According to an embodiment of the invention, the perovskite thin film layer is ABX, wherein a comprises CH 3 NH 3+ 、HC(NH 2 ) 2+ 、Cs + And Rb + At least one of (a) and (b); b is Pb 2+ And Sn (Sn) 2+ At least one of (a) and (b); x is I-or a halogen or pseudo-halogen ion mixture containing at least I-.
According to the embodiment of the invention, a perovskite passivation layer is further arranged between the perovskite thin film layer and the electron transport layer; preferably, the perovskite passivation layer comprises at least one of PEAI, PEACl, PEABr and MeO-PEAI.
According to an embodiment of the present invention, the metal electrode is selected from one or two of Au, ag, al and Cu.
The invention also provides a preparation method of the solar cell, which comprises the following steps:
(S1) preparing a substrate in a hole transport layer on a hydrophilically treated conductive glass substrate, and performing an annealing treatment;
(S2) coating a 6-bromocoumarin-3-ethyl formate solution on a substrate in the annealed hole transport layer, and carrying out annealing treatment to obtain the hole transport layer;
(S3) coating perovskite precursor solution on the hole transport layer in the step (S2), and carrying out annealing treatment to obtain a perovskite film layer;
and (S4) preparing an electron transport layer above the perovskite thin film layer, and evaporating a metal electrode at the same time to obtain the perovskite solar cell.
According to an embodiment of the present invention, in step (S1), the substrate in the hole transport layer is a nickel oxide nanoparticle thin film.
According to an embodiment of the invention, in step (S1), the annealing treatment is carried out at a temperature of 80-150 ℃, preferably 100-130 ℃; the annealing treatment time is 10-60min, preferably 20-40min; the annealing treatment is performed in an air atmosphere.
According to an embodiment of the present invention, in step (S1), the method for preparing the substrate in the hole transport layer comprises: the hole transport layer substrate is prepared by diluting nickel oxide with water, and by at least one of spin coating, spray coating, sol-gel, and knife coating. Preferably, the nickel oxide is a nickel oxide nanoparticle. Preferably, the concentration of nickel oxide in water is 10-50mg/mL.
According to an embodiment of the present invention, in step (S1), the conductive glass substrate may be further subjected to pretreatment, ultrasonic cleaning, drying, and hydrophilic treatment, for example, hydrophilic treatment in ultraviolet ozone or oxygen Plasma for 20 minutes, for use.
In step (S1) of the present invention, the hydrophilic treatment of the conductive glass substrate is a conventional technique in the art.
According to an embodiment of the present invention, in the step (S2), the 6-bromocoumarin-3-carboxylic acid ethyl ester solution is 6-bromocoumarin-3-carboxylic acid ethyl ester dissolved in an organic solvent selected from at least one of DMF, DMSO, 2-methoxyethanol, N-methylpyrrolidone, γ -butyrolactone, isopropanol, ethanol, chlorobenzene, toluene, ethyl acetate, and the like. Preferably, the concentration of the 6-bromocoumarin-3-carboxylic acid ethyl ester solution is 0.05-5mg/mL, and still more preferably 0.2-4mg/mL.
According to an embodiment of the present invention, in the step (S2), the preparation method of the 6-bromocoumarin-3-carboxylic acid ethyl ester solution comprises: the ethyl 6-bromocoumarin-3-carboxylate was diluted with DMF solution.
According to an embodiment of the invention, in step (S2), the annealing treatment is carried out at a temperature of 40-120 ℃, preferably 60-100 ℃.
According to an embodiment of the present invention, in step (S3), the perovskite precursor solution is ABX dissolved in an organic solvent selected from at least one of DMF, DMSO, 2-methoxyethanol (2-ME), N-methylpyrrolidone (NMP) and γ -butyrolactone (GBL); wherein A comprises CH 3 NH 3+ 、HC(NH 2 ) 2 + 、Cs + And Rb + At least one of (a) and (b); b is Pb 2+ And Sn (Sn) 2 + At least one of (a) and (b); x is I - Or at least contain I - Or pseudo-halogen ion mixtures.
Preferably, the concentration of the perovskite precursor solution is 1.4 to 2.0M.
Preferably, the perovskite precursor solution is obtained by mixing a compound containing a, a compound containing B, and an organic solvent.
Preferably, the a-containing compound is selected, for example, from HC (CH 2 ) 2 I、CH 3 NH 3 At least one of Cl, csI, rbI, and the like.
Preferably, the B-containing compound is selected, for example, from PbI 2 、SnCl 2 At least one of the following.
Preferably, the perovskite precursor solution is, for example, FAPbI 3 Perovskite precursor, wherein FA is HC (CH 2 ) 2 I。
According to an embodiment of the present invention, in step (S3), the perovskite thin film layer is prepared by: and dissolving ABX in a mixed solvent formed by DMF and DMSO, vibrating and stirring the obtained solution for more than 4 hours, and filtering to obtain a clear perovskite precursor solution.
According to an embodiment of the present invention, in step (S3), the preparation method of the perovskite thin film layer includes, but is not limited to, one of spin coating, knife coating and slit coating.
According to an embodiment of the present invention, in step (S3), the method further comprises preparing a perovskite passivation layer on the surface of the perovskite thin film layer, wherein the preparation method of the perovskite passivation layer comprises: at least one of PEAI, PEACl, PEABr, meO-PEAI and the like is dissolved in a solvent to obtain an organic salt solution of the perovskite passivation layer, and the obtained solution is coated on the perovskite thin film layer to obtain the perovskite passivation layer. Preferably, the concentration of the perovskite passivation layer organic salt solution is 1-4 mg/mL. The solvent is at least one selected from isopropanol, chlorobenzene, toluene, anisole, diethyl ether, chlorobenzene, ethanol and the like.
According to an embodiment of the present invention, in the step (S4), when the electron transport layer is a PCBM electron transport layer, the method for preparing the PCBM electron transport layer includes: and diluting the PCBM with chlorobenzene, and preparing an electron transport layer from the diluted PCBM solution by a spin coating method.
According to an embodiment of the present invention, in the step (S4), when the electron transport layer is a C60 electron transport layer, the method for preparing the C60 electron transport layer is as follows: c60 was deposited by vacuum thermal evaporation to obtain a C60 electron transport layer.
According to an embodiment of the present invention, step (S4) is: and preparing an electron transport layer on the perovskite passivation layer, and simultaneously evaporating a metal electrode in a vacuum manner to obtain the perovskite solar cell.
According to an embodiment of the present invention, in the step (S4), the thickness of the metal electrode is 50 to 150nm.
As an exemplary embodiment of the present invention, the method for preparing the perovskite solar cell specifically includes the steps of:
(1) Pretreatment of a conductive glass substrate: placing the conductive glass substrate in deionized water for ultrasonic cleaning, respectively carrying out ultrasonic cleaning in ethanol, acetone and isopropanol, blow-drying by a nitrogen gun, and finally carrying out hydrophilic treatment in ultraviolet ozone;
(2) Spin-coating nickel oxide aqueous solution on the treated conductive glass substrate, and performing annealing treatment to obtain a hole transport layer substrate;
(3) Spin-coating a 6-bromocoumarin-3-ethyl formate organic solution on a hole transport layer substrate, and carrying out annealing treatment to obtain a hole transport layer;
(5) Spin-coating perovskite precursor solution on the hole transport layer, annealing, and cooling to obtain a perovskite film layer;
(6) Spin-coating an organic salt isopropanol solution of a perovskite passivation layer on the perovskite film layer to obtain the perovskite passivation layer;
(7) Preparing a PCBM electron transport layer or a C60 electron transport layer on the perovskite passivation layer;
(8) And preparing a metal electrode on the electron transport layer to obtain the perovskite solar cell.
The invention also provides application of the hole transport layer or the perovskite solar cell in the photoelectric field.
The beneficial effects of the invention are that
1. The hole transport layer reduces stress in the perovskite thin film layer forming process by utilizing the self-sensitive photoinduced structure interconversion characteristic of the 6-bromocoumarin-3-ethyl formate, and simultaneously dynamically inhibits stress generated by light bath when the solar cell works, so that the stability of the solar cell is enhanced. And the preparation method of the hole transport layer is easy to operate, has good repeatability and is suitable for industrial mass production.
2. The invention provides a preparation method of a perovskite solar cell, which uses 6-bromocoumarin-3-ethyl formate to modify the interface between a nickel oxide hole transport layer and a perovskite thin film layer, prepares the hole transport layer with high hole extraction capacity by regulating and controlling the surface of the nickel oxide hole transport layer, and simultaneously regulates and controls the subsequent perovskite thin film forming, so that a uniform, compact, stress-reduced and defect-density perovskite thin film layer is further obtained, carrier transport of the perovskite thin film is enhanced, and the obvious improvement of the efficiency of the perovskite solar cell is realized.
Drawings
FIG. 1 is an AFM comparison of the hole transport layer of example 1 with an untreated nickel oxide hole transport layer;
FIG. 2 is a graph showing the conductivity test of the hole transport layer in example 1 versus the untreated nickel oxide hole transport layer;
FIG. 3 is a graph of UV absorption contrast based on a perovskite film deposited on a hole transport layer and a perovskite film deposited on an untreated nickel oxide hole transport layer in example 1;
FIG. 4 is an AFM comparison of a perovskite film deposited on a hole transport layer and a perovskite film deposited on an untreated nickel oxide hole transport layer in example 1;
FIG. 5 is a graph of residual stress versus example 1 based on a perovskite film deposited on a hole transport layer and a perovskite film deposited on an untreated nickel oxide hole transport layer;
FIG. 6 is a graph comparing the J-V curves of the perovskite solar cell of example 10 with the perovskite layer interface of untreated nickel oxide layer;
FIG. 7 is a graph comparing the J-V curves of perovskite solar cell and untreated nickel oxide layer/perovskite layer interface of example 1;
fig. 8 is a graph comparing the photoelectric conversion efficiency of the perovskite solar cell of example 1 with respect to time under 365nm illumination, with respect to the perovskite solar cell of the untreated nickel oxide layer/perovskite layer interface.
Fig. 9 is a structural view of the perovskite solar cell of the present invention.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
A method for preparing a titanium ore solar cell, comprising the following steps:
(1) Preparation of perovskite precursor solution: weighing the molar ratio of HC (CH) 2 ) 2 I:PbI 2 ：CH 3 NH 3 Solute with cl=1:1:0.3, dissolved in mixed solvent of DMF and DMSO (v: v=4:1), in N 2 Stirring for more than 4h under atmosphere to completely dissolve to obtain 1.5M FAPbI 3 A perovskite precursor solution;
(2) Pretreatment of ITO/FTO conductive glass: the ITO/FTO conductive glass is placed in deionized water for ultrasonic cleaning for 20 minutes, then respectively in ethanol, acetone and isopropanol for ultrasonic cleaning for 20 minutes, then dried by a nitrogen gun, and finally placed in ultraviolet ozone for 20 minutes for standby.
(3) Preparing a nickel oxide hole transport layer substrate: the nickel oxide nanoparticles were diluted to 40mg/mL with deionized water and the nickel oxide hole transport layer substrate was prepared by spin coating. And (3) annealing the substrate formed by the conductive glass and the nickel oxide layer in an air atmosphere at 120 ℃ for 30 minutes, and rapidly transferring to a glove box after the temperature is reduced to room temperature.
(4) Preparation of nickel oxide layer/6-bromocoumarin-3-carboxylic acid ethyl ester layer (i.e. hole transport layer): spin-coating 0.4mg/mL of DMF solution of 6-bromocoumarin-3-ethyl formate on the surface of the nickel oxide hole transport layer substrate, and annealing at 70 ℃ for 30 minutes to obtain the hole transport layer.
(5) Preparation of perovskite thin film layer: spin-coating the prepared perovskite precursor solution on the hole transport layer, and then annealing to obtain the perovskite film. The conditions for spin coating the perovskite precursor solution were 4000 rpm spin coating 50s in a nitrogen atmosphere and annealing at 100 ℃ for 60 minutes.
(6) Spin-coating a pei (phenethylamine hydroiodinate) perovskite passivation layer: cooling the annealed perovskite film to room temperature, and spin-coating the prepared 1mg/mL PEAI isopropanol solution on the perovskite film layer, wherein spin-coating parameters are 4000 rpm and 30s; a perovskite passivation layer is formed. Interface defects are reduced, non-radiative recombination is inhibited, and Voc, jsc and fill factor FF of the device are improved through the passivation layer.
(7) Preparation of PCBM electron transport layer: 20mgPCBM was dissolved in 1mL of chlorobenzene, stirred with shaking for 6 hours, and completely dissolved for use. PCBM solution was spin coated on the perovskite passivation layer by a 2000 rpm, 30s process.
(8) Preparation of a metal electrode Ag: an Ag electrode with a thickness of 80-110 nm is evaporated by a thermal evaporation method.
Fig. 1 is a graph of AFM comparison of a hole transport layer (right side of fig. 1) prepared according to the present invention with an untreated nickel oxide hole transport layer (i.e., hole transport layer substrate) (left side of fig. 1). As can be seen from fig. 1, the RMS of the hole transport layer of the present invention is 4.336nm, and the RMS of the hole transport layer substrate is 4.563nm, and it can be seen that the roughness of the hole transport layer (Target) prepared by the present invention is reduced, which is beneficial to the subsequent formation of perovskite precursors, and reduces the lattice distortion of perovskite thin films.
Fig. 2 is a graph comparing conductivity tests of a hole transport layer prepared according to the present invention with that of an untreated nickel oxide hole transport layer. As can be seen from fig. 2, the hole transport layer (Target) prepared by the present invention has higher conductivity, which is beneficial to the transport of interfacial charges.
FIG. 3 is a graph of UV absorption contrast based on a perovskite film deposited on a hole transport layer and a perovskite film deposited on an untreated nickel oxide hole transport layer according to example 1 of the present invention. As can be seen from the ultraviolet visible absorption curve of fig. 3, the absorption of the perovskite thin film (Target) prepared by the invention is obviously enhanced; meanwhile, the modification of the 6-bromocoumarin-3-ethyl formate has no obvious influence on the energy band of the perovskite absorption layer.
FIG. 4 is an AFM comparison of a perovskite film deposited on a hole transport layer according to the present invention with a perovskite film deposited on an untreated nickel oxide hole transport layer. The perovskite film (Target) prepared based on the hole transport layer has smoother surface, is compact, has smaller roughness, and is beneficial to the photoelectric conversion performance of the device.
FIG. 5 is a graph comparing residual stress of a perovskite film deposited on a hole transport layer prepared according to the present invention with a perovskite film deposited on an untreated nickel oxide hole transport layer. As can be seen from the graph, the perovskite thin film (Target) prepared based on the hole transport layer of the present invention has smaller residual tensile stress in the perovskite thin film layer before and after 365nm ultraviolet irradiation compared with the perovskite thin film (left side of fig. 5) prepared from the untreated nickel oxide hole transport layer, which is helpful for improving the performance and ultraviolet irradiation stability of the battery device.
FIG. 7 is a graph comparing J-V curves of perovskite solar cell and untreated nickel oxide layer/perovskite layer interface prepared in example 1. The perovskite solar cell prepared based on the hole transport layer of the invention obtained a photoelectric conversion efficiency of 25.35%, with voc=1.161 v, jsc=26.27 mA/cm 2 Ff=83.13%. The perovskite solar cell prepared by the untreated nickel oxide hole transport layer only has 24.36% photoelectric conversion efficiency, with voc=1.145 v and jsc=25.80 mA/cm 2 ，FF＝82.46％。
Fig. 8 is a graph comparing the photoelectric conversion efficiency of the perovskite solar cell prepared in example 1 with that of the perovskite solar cell of the untreated nickel oxide layer/perovskite layer interface under 365nm illumination over time. As can be seen from fig. 7, the perovskite solar cell prepared based on the hole transport layer of the present invention exhibited good stability under 365nm illumination, while the reference-like device performance decayed rapidly. The nickel oxide hole transport layer modified by the 6-bromocoumarin-3-ethyl formate can obviously improve the illumination stability of the battery device.
Fig. 9 is a structural diagram of a perovskite solar cell of the invention. In fig. 9, the solar cell has a structure sequentially comprising common glass or non-conductive glass, a conductive glass substrate ITO, a hole transport layer substrate nickel oxide, a 6-bromocoumarin-3-ethyl formate coating layer, a perovskite thin film layer, an electron transport layer PCBM or C60, and a metal electrode.
Example 2
Example 2 differs from example 1 in that: the concentration of the DMF solution of the ethyl 6-bromocoumarin-3-carboxylate in the step (4) is 0.2mg/mL.
Example 3
Example 3 differs from example 1 in that: the concentration of the DMF solution of the ethyl 6-bromocoumarin-3-carboxylate in the step (4) is 0.5mg/mL.
Example 4
Example 4 differs from example 1 in that: the concentration of the DMF solution of the ethyl 6-bromocoumarin-3-carboxylate in the step (4) is 1mg/mL.
Example 5
Example 5 differs from example 1 in that: the concentration of the DMF solution of the ethyl 6-bromocoumarin-3-carboxylate in the step (4) is 2mg/mL.
Example 6
Example 6 differs from example 1 in that: the concentration of the DMF solution of the ethyl 6-bromocoumarin-3-carboxylate in the step (4) is 4mg/mL.
Example 7
A method for preparing a perovskite solar cell, comprising the following preparation steps:
(1) Preparation of perovskite precursor solution: weighing the molar ratio of HC (CH) 2 ) 2 I:CsI:PbI 2 ：CH 3 NH 3 Solute with cl=0.95:0.05:1:0.3, dissolved in mixed solvent of DMF and DMSO (v: v=4:1), in N 2 Stirring for more than 4h under atmosphere to completely dissolve to obtain 1.8M FAPbI 3 A perovskite precursor solution;
(2) Pretreatment of ITO/FTO conductive glass: the same as in step (2) of example 1;
(3) Preparation of a nickel oxide hole transport layer: the same as in step (3) of example 1;
(4) Preparation of nickel oxide layer/6-bromocoumarin-3-carboxylic acid ethyl ester layer: the same as in step (4) of example 1;
(5) Preparation of perovskite thin film layer: the same as in step (5) of example 1;
(6) Spin-coating a pei (phenethylamine hydroiodinate) perovskite passivation layer: the same as in step (6) of example 1;
(7) Preparation of C60 electron transport layer: evaporating C60 with the thickness of 20nm by a thermal evaporation method to serve as an electron transport layer;
(8) Preparation of a metal electrode Ag: an Ag electrode with a thickness of 80-110 nm is evaporated by a thermal evaporation method.
Example 8
A method for preparing a perovskite solar cell, comprising the following preparation steps:
(1) The same as in step (1) of example 7;
(2) Pretreatment of ITO/FTO conductive glass: the same as in step (2) of example 1;
(3) Preparation of a nickel oxide hole transport layer: the same as in step (3) of example 1;
(4) Preparation of nickel oxide layer/6-bromocoumarin-3-carboxylic acid ethyl ester layer: the same as in step (4) of example 2;
(5) Preparation of perovskite thin film layer: the same as in step (5) of example 1;
(6) Spin-coating a pei (phenethylamine hydroiodinate) perovskite passivation layer: the same as in step (6) of example 1;
(7) Preparation of C60 electron transport layer: the same as in step (7) of example 7;
(8) Preparation of a metal electrode Ag: an Ag electrode with a thickness of 80-110 nm is evaporated by a thermal evaporation method.
Example 9
A method for preparing a perovskite solar cell, comprising the following preparation steps:
(1) The same as in step (1) of example 7;
(2) Pretreatment of ITO/FTO conductive glass: the same as in step (2) of example 1;
(3) Preparation of a nickel oxide hole transport layer: the same as in step (3) of example 1;
(4) Preparation of nickel oxide layer/6-bromocoumarin-3-carboxylic acid ethyl ester layer: the same as in step (4) of example 3;
(5) Preparation of perovskite thin film layer: the same as in step (5) of example 1;
(6) Spin-coating a pei (phenethylamine hydroiodinate) perovskite passivation layer: the same as in step (6) of example 1;
(7) Preparation of C60 electron transport layer: the same as in step (7) of example 7;
(8) Preparation of a metal electrode Ag: an Ag electrode with a thickness of 80-110 nm is evaporated by a thermal evaporation method.
Example 10
Example 10 differs from example 1 in that: example 10 does not contain step (6);
in the step (7), 20mgPCBM is dissolved in 1mL of chlorobenzene, and the mixture is stirred for 6h by shaking, so that the PCBM is completely dissolved and is ready for use. PCBM solution was spin coated on the perovskite thin film layer by a 2000 rpm, 30s process.
FIG. 6 is a graph comparing J-V curves of perovskite solar cell and untreated nickel oxide layer/perovskite layer interface prepared in example 10, wherein the perovskite layer surface has no passivation layer. Perovskite solar cells prepared with untreated nickel oxide hole transport layers achieved only 21.07% photoelectric conversion efficiency with voc=1.053v, jsc=24.81 mA/cm 2 Ff= 80.44%. Voc=1.064v, jsc=25.11 mA/cm for perovskite solar cells prepared based on hole transport layers of the present invention 2 Ff= 82.44%, with a battery efficiency of 22.12% significantly higher than the control group.
As can be seen from comparing examples 1 and 10, and fig. 6 and 7, interface defects are reduced, non-radiative recombination is suppressed, and Voc, jsc and fill factor FF of the device are improved by the passivation layer.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (10)
1. A hole transport layer, wherein the hole transport layer comprises a substrate and a coating layer on the surface of the substrate, and the coating layer contains 6-bromocoumarin-3-ethyl formate.
2. The hole transport layer of claim 1, wherein the substrate of the hole transport layer is a nickel oxide nanoparticle film;
specifically, the hole transport layer comprises a nickel oxide nanoparticle film and a coating layer which is positioned on the surface of the film and consists of 6-bromocoumarin-3-ethyl formate.
3. The hole transport layer according to claim 1 or 2, wherein the thickness of the coating layer is 0.5-5nm.
4. A perovskite solar cell, characterized in that the solar cell has a structure comprising a conductive glass substrate, the hole transport layer of any one of claims 1 to 3, a perovskite thin film layer, an electron transport layer and a metal electrode in this order.
5. The perovskite solar cell of claim 4, wherein the coating layer on the hole transport layer interfaces with the perovskite thin film layer;
preferably, a perovskite passivation layer is further arranged between the perovskite thin film layer and the electron transport layer; preferably, the perovskite passivation layer comprises at least one of PEAI, PEACl, PEABr and MeO-PEAI.
6. A method of producing a perovskite solar cell as claimed in claim 4 or 5, wherein the method comprises:
(S1) preparing a substrate in a hole transport layer on a hydrophilically treated conductive glass substrate, and performing an annealing treatment;
(S2) coating a 6-bromocoumarin-3-ethyl formate solution on a substrate in the annealed hole transport layer, and carrying out annealing treatment to obtain the hole transport layer;
(S3) coating perovskite precursor solution on the hole transport layer in the step (S2), and carrying out annealing treatment to obtain a perovskite film layer;
and (S4) preparing an electron transport layer above the perovskite thin film layer, and evaporating a metal electrode at the same time to obtain the perovskite solar cell.
7. The method of claim 6, wherein in step (S1), the substrate in the hole transport layer is a nickel oxide nanoparticle film;
preferably, in the step (S1), the temperature of the annealing treatment is 80-150 ℃; the annealing treatment time is 10-60min; the annealing treatment is performed in an air atmosphere.
8. The method according to claim 6, wherein in the step (S2), the 6-bromocoumarin-3-carboxylic acid ethyl ester solution is a solution of 6-bromocoumarin-3-carboxylic acid ethyl ester dissolved in an organic solvent, specifically, at least one selected from DMF, DMSO, 2-methoxyethanol, N-methylpyrrolidone, γ -butyrolactone, isopropanol, ethanol, chlorobenzene, toluene, and ethyl acetate;
preferably, the concentration of the 6-bromocoumarin-3-carboxylic acid ethyl ester solution is 0.05-5mg/mL;
preferably, in step (S2), the annealing treatment is performed at a temperature of 40 to 120 ℃.
Preferably, in the step (S4), the thickness of the metal electrode is 50 to 150nm.
9. A perovskite solar cell prepared by the method of any one of claims 6-8.
10. Use of a hole transport layer according to any of claims 1 to 3 or a perovskite solar cell according to claim 4, 5 or 9 in the photovoltaic field.
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