CN114394968B - Conjugated organic ionic salt, preparation method and application in perovskite solar cell - Google Patents
Conjugated organic ionic salt, preparation method and application in perovskite solar cell Download PDFInfo
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Abstract
The invention discloses a conjugated organic ion salt. The invention also discloses a preparation method and application of the perovskite solar cell. The conjugated organic ion salt provided by the invention comprises two parts, namely a ligand main body and an ionic group, so that the conjugate organic ion salt has amphipathy; when the material is used as a material for preparing an anode modification layer in a perovskite solar cell, the wettability of a perovskite precursor solution can be changed, the crystallization of perovskite is promoted, and the film quality is improved; the defects of the perovskite layer are passivated, and the non-radiative recombination of the perovskite layer is reduced; the components of the perovskite layer are finely adjusted, and the efficiency and the stability of the perovskite solar cell device are improved.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a conjugated organic ionic salt, a preparation method and application in perovskite solar cells.
Background
Metal halide perovskite solar cells have attracted considerable attention as a new green energy power generation technology due to their excellent photovoltaic properties and simple solution processing. By regulating the iodine/bromine ratio of the perovskite components, the precise regulation of the optical band gap of the mixed metal halide perovskite can be realized, the great commercial potential of the halide perovskite technology is proved, and the applications of series photovoltaic, indoor photovoltaic and the like can be realized.
Due to the multilayer solution processing technology of perovskite solar cells, achieving mild layer-to-layer compatibility and good wettability is one of the key problems in obtaining high quality perovskite thin films. The perovskite grows on the substrate in an in-situ growth mode, so that the perovskite layer solution and the lower transmission layer need to have proper compatibility and wettability, and the perovskite solar cell with high efficiency and stability is more favorably realized.
Surface defects at the junction of the transport layer and the perovskite layer, as well as grain boundary defects of the perovskite film, are important factors affecting the efficiency and stability of the perovskite device. The generation of defects can cause non-radiative recombination and reduce the efficiency; in addition, the defect site is easily invaded by external factors such as water, oxygen, heat, and the like, and the decomposition of perovskite is easily caused. For example, lead ions that are not coordinated in the perovskite layer seriously affect the efficiency and stability of the device; therefore, the organic molecules capable of coordinating with metal cations are selected to passivate defect sites on the surface and the grain boundary through coordination bonds, and a research method is provided for solving the technical problems. Another method for realizing a highly efficient and stable perovskite solar cell is component engineering, namely, the perovskite component is finely adjusted, the tolerance of the perovskite is improved, and the highly efficient and stable perovskite solar cell is realized. Many researches adopt methods of introducing functional organic/inorganic materials to change interface wettability, passivate perovskite and regulate perovskite components to realize efficient and stable perovskite solar cells. However, most of the materials used at present only have one function, and multiple materials are needed to be matched for realizing efficient and stable devices, so that the method is complex and inconvenient.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the interface wettability can be changed, the perovskite can be passivated and the perovskite component can be regulated and controlled only by matching various materials in the conventional perovskite solar cell, so that the conjugated organic ionic salt, the preparation method and the application in the perovskite solar cell are provided.
Therefore, the invention adopts the following technical scheme:
a conjugated organic ion salt having the formula:
wherein X is one of nitrogen or phosphorus, Y is one of oxygen or sulfur, and Z is one of hydrogen, lithium, sodium, potassium, rubidium, cesium or ammonium ions.
Further, X is nitrogen and Y is oxygen.
Preferably, Z is one of lithium, potassium or cesium, and the conjugated organic ion salt has a structural formula:
the invention also provides a preparation method of the conjugated organic ion salt, which comprises the following steps:
s1: is structured as
The compound (b) is mixed with alkaline inorganic salt and organic solvent to react, the product after the reaction is dripped into dichloromethane, and the precipitate is taken after filtration to obtain a crude product;
s2: and dissolving the crude product, and then passing through an alkaline alumina chromatographic column to obtain the conjugated organic ionic salt.
Further, in step S1, the molar ratio of the compound to the basic inorganic salt is 1: 1-6;
the mixing environment is a nitrogen atmosphere at room temperature, and the mixing time is 30-90 min;
the reaction environment is nitrogen atmosphere, the temperature is 50-65 ℃, and the reaction time is 5-8 h.
In step S2, the eluent from the basic alumina column is methanol.
Preferably, in step S1, the alkaline inorganic salt includes one of carbonate, silicate, sulfite, acetate, bicarbonate, phosphate, hypochlorite and sulfide salt;
the organic solvent comprises one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, formamide, methanol, ethanol, tetrahydrofuran and acetonitrile.
The invention also provides application of the conjugated organic ion salt in preparation of perovskite solar cells.
The invention also provides a perovskite solar cell which comprises an anode layer, an anode transmission layer, an anode modification layer, a perovskite layer, a cathode transmission layer and a metal electrode which are sequentially arranged, wherein the anode modification layer is a conjugated organic ionic salt.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
cleaning and washing an ITO glass substrate; preparing an ITO glass substrate by spin coating a PTAA toluene solution, and annealing to obtain an anode transmission layer; spin-coating a methanol solution of the conjugated organic ionic salt on the anode transmission layer to obtain an anode modification layer; depositing a perovskite thin film on a substrate by a one-step deposition method; depositing a cathode transmission layer on the perovskite film by adopting a vacuum evaporation method; and finally, preparing the Ag electrode by adopting a thermal evaporation method to obtain the perovskite solar cell.
The technical scheme of the invention has the following advantages:
(1) the conjugated organic ion salt provided by the invention comprises two parts, namely a ligand main body and an ionic group, and the conjugated organic ion salt has amphipathy, wherein phenanthroline of the ligand main body has a plane rigid structure and a stronger conjugated system, and N atoms on aromatic rings of the phenanthroline have good electron transfer performance; in addition, phenanthroline belongs to a bidentate ligand, and two N at the 1 and 10 positions of phenanthroline can be chelated with a metal to form a stable metal complex; meanwhile, the structure of the complex is easy to modify, so that the phenanthroline derivative is prepared, and the complex formed by chelating the phenanthroline derivative with different metals has stable properties and different properties. Namely, the phenanthroline has the characteristics of strong conductivity, excellent coordination capacity with metal, simple synthesis and stable product. In the limited ionic group, lithium, potassium and cesium are adopted, and the three metals belong to alkali metal cations, so that the components of the perovskite can be adjusted, the defects in the perovskite can be reduced, and the electron-phonon coupling degree in the perovskite system can be reduced, thereby inhibiting the separation of halogen and enhancing the light stability of the perovskite solar cell. Therefore, the addition of the three alkali metal cations can finely adjust the perovskite components, reduce the defects of the perovskite layer and improve the stability of the device.
(2) The conjugated organic ionic salt provided by the application is used as a material for preparing the anode modification layer in the perovskite solar cell, so that the wettability of a perovskite precursor solution on a hole transport layer (such as PTAA) can be changed, the crystallization of perovskite is promoted, and the quality of a film is improved; two nitrogen atoms on the phenanthroline can be coordinated with uncoordinated lead, so that the defect of the perovskite layer is passivated, and the non-radiative recombination of the perovskite layer is reduced; in addition, cations in the material can finely adjust the components of the perovskite layer, and the efficiency and stability of the perovskite solar cell device are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a hydrogen spectrum of a conjugated organic ion salt obtained in example 1 of the present invention;
FIG. 2 is a carbon spectrum of a conjugated organic ion salt obtained in example 1 of the present invention;
FIG. 3 is a hydrogen spectrum of a conjugated organic ion salt obtained in example 2 of the present invention;
FIG. 4 is a carbon spectrum of a conjugated organic ion salt obtained in example 2 of the present invention;
FIG. 5 is a hydrogen spectrum of a conjugated organic ion salt obtained in example 3 of the present invention;
FIG. 6 is a carbon spectrum of a conjugated organic ion salt obtained in example 3 of the present invention;
FIG. 7 is a schematic device structure of a perovskite solar cell in an embodiment of the invention;
FIG. 8 is a photograph of dropping a perovskite dope onto the anode transport layer coated with the anode modification layer in examples 1 to 3 of the present invention and onto the anode transport layer in comparative example 1;
FIG. 9 is a photograph of perovskite thin films obtained in the process of manufacturing a perovskite solar cell in examples 1 to 3 of the present invention and comparative example 1;
FIG. 10 is a current density versus voltage (J-V) plot of the perovskite solar cell obtained in example 1 under illumination with an intensity of 100 milliwatts per square centimeter;
FIG. 11 is a current density versus voltage (J-V) curve for the perovskite solar cell obtained in example 2 under illumination at an intensity of 100 milliwatts per square centimeter;
FIG. 12 is a current density versus voltage (J-V) plot of the perovskite solar cell obtained in example 3 under illumination with an intensity of 100 milliwatts per square centimeter;
FIG. 13 is a current density versus voltage (J-V) plot of the perovskite solar cell obtained in comparative example 1 under illumination with an intensity of 100 milliwatts per square centimeter;
FIG. 14 is a current density versus voltage (J-V) plot of the perovskite solar cell obtained in comparative example 2 under illumination with an intensity of 100 milliwatts per square centimeter.
Reference numerals:
1-a substrate; 2-an anode layer; 3-an anode transport layer; 4-an anode modification layer; 5-a perovskite layer; 6-a cathode transport layer; 7-metal electrode, 8-wire; 9-load or test device; 10-incident light.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
This example provides a conjugated organic ion salt having the structure
The preparation method comprises the following steps:
(1) in a two-necked flask, 4, 7-dihydroxy-1, 10-phenanthroline (321 mg, 1.5 mmol), lithium carbonate (145mg, 2mmol) and 15ml dry DMF were added. Stirring was carried out under nitrogen atmosphere at room temperature for 30 minutes, followed by reaction at 60 ℃ for 6 hours. After cooling to room temperature, the solution was filtered and then precipitated in dichloromethane to give the crude product.
(2) The crude product was purified using basic alumina chromatography column to give the final product with a hydrogen carbon spectrum as shown in fig. 1 and fig. 2, Phen-OLi: 1H NMR (400 MHz, DMSO) δ 7.94 (d, J = 6.5 Hz, 1H), 7.75 (s, 1H), 6.13 (d, J = 6.5 Hz, 1H). 13C NMR (151 MHz, DMSO) δ 174.93(s), 143.62(s), 139.31(s), 125.50(s), 116.92(s), 110.50(s).
The embodiment also provides a perovskite solar cell, which uses the conjugated organic ionic salt, and the structure of the perovskite solar cell is as shown in fig. 7, wherein an anode layer 2, an anode transport layer 3, an anode modification layer 4, a perovskite layer 5 and a cathode transport layer 6 are sequentially deposited on a substrate 1; metal electrodes 7 are arranged on the cathode transmission layer 6 and the anode layer 2 without other layers and are connected with a load or test device 9 through leads 8; incident light 10 enters the perovskite solar cell from the anode layer 2 to operate.
The perovskite solar cell is prepared by the following specific preparation method:
1. cleaning an ITO glass substrate: the substrate cleaning sequence was by ultrasonic cleaning in detergent, water, deionized water, acetone and isopropanol for 15 minutes. The ITO substrate was then dried in an oven at 150 ℃ for 5 minutes and then treated with ultraviolet ozone (UVO) for 15 minutes.
2. Preparing an anode transmission layer on the transparent ITO conductive layer: a toluene solution of PTAA was spin-coated on an ITO substrate at 4000rpm, and then it was annealed at 150 ℃ for 10 minutes on a hot stage to prepare an anode transport layer. Then, the conjugated organic ion salt was dissolved in methanol (0.5 mg/ml), and spin-coated on the anode transport layer at 5000rpm to obtain an anode modification layer.
3. Depositing a perovskite thin film on a substrate by a one-step deposition method: first, 50. mu.L of a perovskite precursor solution (77.62 mg CsI, 162.15 mg FAI, 112.13mg PbBr)2、2.83mg MACl、11.68mg PbCl2、425.15 mg PbI2Dissolution in DMSO: DMF (1: 3) mixed solution) was coated on the substrate at a speed of 5000 rpm. Next, 300ul of the anti-solvent chlorobenzene was dropped on the perovskite thin film at the 25 th s of the spin-coating process. Then followed by annealing at 100 ℃ for 30 minutes to obtain a perovskite thin film.
4. Depositing a cathode transmission layer on the perovskite layer by adopting a vacuum evaporation method: and (3) performing vacuum evaporation on the prepared perovskite thin film to form 30nm of C60 and 8nm of BCP, and preparing a cathode transmission layer.
5. And preparing an Ag electrode with the thickness of 100nm by adopting a thermal evaporation method to obtain the perovskite solar cell, and connecting the perovskite solar cell with a load or a testing device through a lead.
Example 2
This example provides a conjugated organic ion salt having the structure
The preparation method comprises the following steps:
(1) in a two-necked flask, 4, 7-dihydroxy-1, 10-phenanthroline (321 mg, 1.5 mmol), potassium carbonate (554mg, 2mmol) and 15ml dry DMF were added. Stirring was carried out under nitrogen atmosphere at room temperature for 30 minutes, followed by reaction at 60 ℃ for 6 hours. After cooling to room temperature, the solution was filtered and then precipitated in dichloromethane to give the crude product.
(2) The crude product was purified using basic alumina chromatography column to give the final product with a hydrogen carbon spectrum as shown in fig. 3 and 4, Phen-OK: 1H NMR (400 MHz, DMSO) δ 7.88 (d, J = 6.5 Hz, 1H), 7.68 (s, 1H), 6.05 (d, J = 6.5 Hz, 1H). 13C NMR (151 MHz, DMSO) δ 175.39(s), 143.41(s), 139.39(s), 125.75(s), 116.64(s), 110.43(s).
The embodiment also provides a perovskite solar cell, which uses the conjugated organic ionic salt, and the structure of the perovskite solar cell is as shown in fig. 7, wherein an anode layer 2, an anode transmission layer 3, an anode modification layer 4, a perovskite layer 5 and a cathode transmission layer 6 are sequentially deposited on a substrate 1; metal electrodes 7 are arranged on the cathode transmission layer 6 and the anode layer 2 without other layers and are connected with a load or test device 9 through leads 8; incident light 10 enters the perovskite solar cell from the anode layer 2 to operate.
The perovskite solar cell is prepared by the following specific preparation method:
1. cleaning an ITO glass substrate: the substrate cleaning sequence was by ultrasonic cleaning in detergent, water, deionized water, acetone and isopropanol for 15 minutes. The ITO substrate was then dried in an oven at 150 ℃ for 5 minutes and then treated with ultraviolet ozone (UVO) for 15 minutes.
2. Preparing an anode transmission layer on the transparent ITO conductive layer: a toluene solution of PTAA was spin-coated on an ITO substrate at 4000rpm, and then it was annealed at 150 ℃ for 10 minutes on a hot stage to prepare an anode transport layer. Then, the conjugated organic ion salt is dissolved in methanol (0.5 mg/ml), and the solution is spin-coated on the anode transmission layer at the rotation speed of 5000rpm, so as to obtain an anode modification layer.
3. Depositing a perovskite thin film on a substrate by a one-step deposition method: first, 50. mu.L of a perovskite precursor solution (77.62 mg CsI, 162.15 mg FAI, 112.13mg PbBr)2、2.83mg MACl、11.68mg PbCl2、425.15 mg PbI2Dissolution in DMSO: DMF (1: 3) mixed solution) was coated on the substrate at a speed of 5000 rpm. Next, 300ul of the anti-solvent chlorobenzene was dropped on the perovskite thin film at the 25 th s of the spin-coating process. Then followed by annealing at 100 ℃ for 30 minutes to obtain a perovskite thin film.
4. Depositing a cathode transmission layer on the perovskite layer by adopting a vacuum evaporation method: and (3) performing vacuum evaporation on the prepared perovskite thin film to form 30nm of C60 and 8nm of BCP, and preparing a cathode transmission layer.
5. And preparing an Ag electrode with the thickness of 100nm by adopting a thermal evaporation method to obtain the perovskite solar cell, and connecting the perovskite solar cell with a load or a testing device through a lead.
Example 3
This example provides a conjugated organic ion salt having the structure
The preparation method comprises the following steps:
(1) in a two-necked flask, 4, 7-dihydroxy-1, 10-phenanthroline (321 mg, 1.5 mmol), cesium carbonate (652mg, 2mmol) and 15ml dry DMF were added. Stirred under nitrogen atmosphere at room temperature for 30 minutes and then reacted at 60 ℃ for 6 hours. After cooling to room temperature, the solution was filtered and then precipitated in dichloromethane to give the crude product.
(2) The crude product was purified using basic alumina chromatography column to give the final product with a hydrogen carbon spectrum as shown in FIGS. 5 and 6, Phen-OCs:1H NMR (400 MHz, DMSO). delta.7.88 (d, J = 6.5 Hz, 1H), 7.68 (s, 1H), 6.05 (d, J = 6.5 Hz, 1H). 13C NMR (151 MHz, DMSO). delta.176.06(s), 143.79(s), 139.91(s), 126.36(s), 116.95(s), 110.88(s).
The embodiment also provides a perovskite solar cell, which uses the conjugated organic ionic salt, and the structure of the perovskite solar cell is as shown in fig. 7, wherein an anode layer 2, an anode transmission layer 3, an anode modification layer 4, a perovskite layer 5 and a cathode transmission layer 6 are sequentially deposited on a substrate 1; metal electrodes 7 are arranged on the cathode transmission layer 6 and the anode layer 2 without other layers and are connected with a load or test device 9 through leads 8; incident light 10 enters the perovskite solar cell from the anode layer 2 to operate.
The perovskite solar cell is prepared by the following specific preparation method:
1. cleaning an ITO glass substrate: the substrate cleaning sequence was by ultrasonic cleaning in detergent, water, deionized water, acetone and isopropanol for 15 minutes. The ITO substrate was then dried in an oven at 150 ℃ for 5 minutes and then treated with ultraviolet ozone (UVO) for 15 minutes.
2. Preparing an anode transmission layer on the transparent conductive layer of the ITO: a toluene solution of PTAA was spin-coated on an ITO substrate at 4000rpm, and then it was annealed at 150 ℃ for 10 minutes on a hot stage to prepare an anode transport layer. Then, the conjugated organic ion salt was dissolved in methanol (0.5 mg/ml), and spin-coated on the anode transport layer at 5000rpm to obtain an anode modification layer.
3. Depositing a perovskite thin film on a substrate by a one-step deposition method: first, 50. mu.L of a perovskite precursor solution (77.62 mg CsI, 162.15 mg FAI, 112.13mg PbBr)2、2.83mg MACl、11.68mg PbCl2、425.15 mg PbI2Dissolution in DMSO: DMF (1: 3) mixed solution) was coated on the substrate at a speed of 5000 rpm. Next, 300ul of the anti-solvent chlorobenzene was dropped on the perovskite thin film at the 25 th s of the spin-coating process. Then followed by annealing at 100 ℃ for 30 minutes to obtain a perovskite thin film.
4. Depositing a cathode transmission layer on the perovskite layer by adopting a vacuum evaporation method: and (3) performing vacuum evaporation on the prepared perovskite thin film to form 30nm of C60 and 8nm of BCP, and preparing a cathode transmission layer.
5. And preparing an Ag electrode with the thickness of 100nm by adopting a thermal evaporation method to obtain the perovskite solar cell, and connecting the perovskite solar cell with a load or a testing device through a lead.
Comparative example 1
The present comparative example 1 provides a perovskite solar cell, which is different from the examples in that a conjugated organic ion salt is not used as an anode modification layer, and the specific preparation method is as follows:
1. and cleaning the ITO glass substrate. The substrate cleaning sequence was 15 minutes in detergent, water, deionized water, acetone and isopropyl alcohol by ultrasonic cleaning. The ITO substrate was then dried in an oven at 150 ℃ for 5 minutes and then treated with ultraviolet ozone (UVO) for 15 minutes.
2. And preparing an anode transmission layer on the ITO transparent conductive layer. A toluene solution of PTAA was spin-coated on an ITO substrate at 4000rpm, and then it was annealed at 150 ℃ for 10 minutes on a hot stage to prepare an anode transport layer.
3. And then depositing the perovskite thin film on the substrate by a one-step deposition method. First, 50. mu.L of a perovskite precursor solution (77.62 mg CsI, 162.15 mg FAI, 112.13mg PbBr)2、2.83mg MACl、11.68mg PbCl2、425.15 mg PbI2Dissolution in DMSO: DMF (1: 3) mixed solution) was coated on the substrate at a speed of 5000 rpm. Next, 300ul of the anti-solvent chlorobenzene was dropped on the perovskite thin film at the 25 th s of the spin-coating process. Then followed by annealing at 100 ℃ for 30 minutes to obtain a perovskite thin film.
4. And depositing a cathode transmission layer on the perovskite layer by adopting a vacuum evaporation method. Vacuum evaporating 30nm C on the prepared perovskite film60And 8nm of BCP to prepare a cathode transport layer.
5. And preparing an Ag electrode with the thickness of 100nm by adopting a thermal evaporation method to obtain the perovskite solar cell.
Comparative example 2
The present comparative example provides a perovskite solar cell, which is different from the examples in that PFN-Br is used as an anode modification layer, and the specific preparation method is as follows:
1. and cleaning the ITO glass substrate. The substrate cleaning sequence was by ultrasonic cleaning in detergent, water, deionized water, acetone and isopropanol for 15 minutes. The ITO substrate was then dried in an oven at 150 ℃ for 5 minutes and then treated with ultraviolet ozone (UVO) for 15 minutes.
2. And preparing an anode transmission layer on the ITO transparent conductive layer. A toluene solution of PTAA was spin-coated on an ITO substrate at 4000rpm, and then it was annealed at 150 ℃ for 10 minutes on a hot stage to prepare an anode transport layer. PFN-Br was then dissolved in methanol (0.5 mg/ml) and spin coated onto the anode transport layer at 5000rpm to obtain an anode modification layer.
3. And then depositing the perovskite thin film on the substrate by a one-step deposition method. First, 50. mu.L of a perovskite precursor solution (77.62 mg CsI, 162.15 mg FAI, 112.13mg PbBr)2、2.83mg MACl、11.68mg PbCl2、425.15 mg PbI2Dissolution in DMSO: DMF (1: 3) mixed solution) was coated on the substrate at a speed of 5000 rpm. Next, 300ul of the anti-solvent chlorobenzene was dropped on the perovskite thin film at the 25 th s of the spin-coating process. Then followed by annealing at 100 ℃ for 30 minutes to obtain a perovskite thin film.
4. And depositing a cathode transmission layer on the perovskite layer by adopting a vacuum evaporation method. Vacuum evaporating 30nm C on the prepared perovskite film60And 8nm of BCP to prepare a cathode transport layer.
5. And preparing an Ag electrode with the thickness of 100nm by adopting a thermal evaporation method to obtain the perovskite solar cell.
Test example 1
The perovskite dope was dropped onto the anode transport layer coated with the anode modification layer in examples 1 to 3 of the present invention and onto the anode transport layer in comparative example 1, and the results are shown in fig. 8, in which (a) in fig. 8 corresponds to comparative example 1, (B) in fig. 8 corresponds to example 1, (C) in fig. 8 corresponds to example 2, and (D) in fig. 8 corresponds to example 3, and it can be seen that the wettability was improved by introducing the conjugated organic ion salt in each example;
observing that the perovskite thin film is obtained in the process of manufacturing the perovskite solar cell in examples 1 to 3 of the present invention and comparative example 1, as shown in fig. 9, wherein (a) in fig. 9 corresponds to comparative example 1, (B) in fig. 9 corresponds to example 1, (C) in fig. 9 corresponds to example 2, and (D) in fig. 9 corresponds to example 3, the surface of comparative example 1 is not completely covered, is not uniform, and some pinholes appear, and the coverage of each example is uniform.
The two figures prove that the introduction of the conjugated organic ion salt effectively improves the wettability of the perovskite precursor solution on a hole transport layer (such as PTAA), and the film quality is improved.
Test example 2
The perovskite solar cells obtained in the examples and comparative examples were subjected to performance tests to obtain current density versus voltage (J-V) curves, as shown in fig. 10-14, under illumination at an intensity of 100 milliwatts per square centimeter, with the results shown in table 1:
table 1 performance of the perovskite solar cell obtained in the examples and comparative examples
As can be seen from the above table, the open circuit voltages of the three examples using the conjugated organic ion salt were: (as compared with comparative example 1) ((r))V OC) The defects in perovskite are passivated by phenanthroline part, so that non-radiative recombination in a perovskite layer is inhibited, and voltage loss is reduced; in addition, the alkali metal ions regulate and control the components of the perovskite, so that the defects are reduced. Similarly, the Filling Factor (FF) of the embodiment is greatly improved, because the introduction of the conjugated organic ion salt changes the wettability of the perovskite solution, improves the quality of the perovskite thin film and improves the quality of the device. In addition, short-circuit current of the embodiment (A), (B), (C)J SC) There is a slight improvement because the added salt of the conjugated organic ion has good conductivity, facilitating charge transport in the device. Finally, three implementations compared to comparative example 1The efficiency of the embodiment is greatly improved, and the fact that the introduced conjugated organic ionic salt achieves fine adjustment of components of a perovskite layer, passivation of defects and improvement of film quality is proved, and the method has a great positive effect on improvement of device efficiency. In comparative example 2, interface material PFN-Br capable of changing PTAA wettability was used as an anode modification layer, and as can be seen from table 1, the performance in all aspects was improved compared to comparative example 1, because PFN-Br improves wettability and quality of the perovskite thin film. However, there is a large gap compared to the embodiments of the present application, which demonstrates that the use of the salt of a conjugated organic ion can further promote the performance of the device by its functions such as passivation, etc., in addition to improving wettability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (8)
1. A conjugated organic ion salt, characterized in that its structural formula is as follows:
wherein X is nitrogen and Y is oxygen;
z is one of lithium, potassium or cesium, and the structural formula of the conjugated organic ion salt is as follows:
2. a method of preparing a conjugated organic ion salt according to claim 1, comprising the steps of:
s1: is structured as
The compound (b) is mixed with alkaline inorganic salt and organic solvent and then reacts, the product after the reaction is dripped into dichloromethane, and after filtration, the precipitate is taken out to obtain a crude product;
s2: and dissolving the crude product, and then passing through an alkaline alumina chromatographic column to obtain the conjugated organic ionic salt.
3. The method according to claim 2, wherein in step S1, the molar ratio of the compound to the basic inorganic salt is 1:1 to 6;
the mixing environment is a nitrogen atmosphere at room temperature, and the mixing time is 30-90 min;
the reaction environment is nitrogen atmosphere, the temperature is 50-65 ℃, and the reaction time is 5-8 h.
4. The method according to claim 2 or 3, wherein the eluent from the basic alumina column is methanol in step S2.
5. The method according to claim 4, wherein in step S1, the alkali inorganic salt includes one of carbonate, silicate, sulfite, acetate, bicarbonate, phosphate, hypochlorite, and sulfide;
the organic solvent comprises one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, formamide, methanol, ethanol, tetrahydrofuran and acetonitrile.
6. Use of the conjugated organic ion salt according to claim 1 or the conjugated organic ion salt prepared by the preparation method according to any one of claims 2 to 5, for preparing a perovskite solar cell.
7. A perovskite solar cell, comprising an anode layer, an anode transmission layer, an anode modification layer, a perovskite layer, a cathode transmission layer and a metal electrode which are sequentially arranged, wherein the anode modification layer is the conjugated organic ionic salt of claim 1 or the conjugated organic ionic salt prepared by the preparation method of any one of claims 2 to 5.
8. The method of fabricating the perovskite solar cell as claimed in claim 7, comprising the steps of:
cleaning and washing an ITO glass substrate; preparing an ITO glass substrate by spin coating a PTAA toluene solution, and annealing to obtain an anode transmission layer; spin-coating a methanol solution of the conjugated organic ionic salt on the anode transmission layer to obtain an anode modification layer; depositing a perovskite thin film on a substrate by a one-step deposition method; depositing a cathode transmission layer on the perovskite film by adopting a vacuum evaporation method; and finally, preparing the Ag electrode by adopting a thermal evaporation method to obtain the perovskite solar cell.
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