Preparation method of perovskite solar cell and perovskite solar cell

Abstract

The application belongs to the technical field of solar cells, and relates to a preparation method of a perovskite solar cell and the perovskite solar cell, wherein the preparation method of the perovskite solar cell comprises the following steps: 1) selecting a conductive glass layer substrate; 2) preparing a perovskite light-absorbing layer containing an organic molecular additive on the conductive glass layer substrate; 3) sequentially spin-coating an electron transport layer and an electron buffer layer on the perovskite light-absorbing layer; and 4) heat evaporating a metal electrode on the electron buffer layer to obtain the perovskite solar cell. The application provides a preparation method of a perovskite solar cell and the perovskite solar cell, which can improve the overall photoelectric conversion efficiency of the perovskite solar cell device.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solar cells, and relates to a preparation method of a perovskite solar cell and the perovskite solar cell, in particular to a preparation method of a perovskite solar cell based on organic molecule modification and the perovskite solar cell. BACKGROUND

[0002] Organic-inorganic hybrid perovskite materials have attracted the attention of many researchers due to their excellent photoelectric performance, low cost and rich sources. The photoelectric conversion efficiency of perovskite solar cells has rapidly climbed from the initial 3.8% to 26.7%, and is considered as the most potential new generation of solar cells.

[0003] However, defects in the perovskite crystal can cause non-radiative recombination of carriers, thereby reducing the photoelectric conversion efficiency of the device. By introducing additive molecules to regulate the perovskite surface interface structure, the quality of the thin film can be significantly improved and the interface contact with the transport layer material can be optimized, thereby improving the photoelectric conversion efficiency of the solar cell. Therefore, developing efficient additives is of great significance to improve the performance of perovskite solar cells.

[0004] The large number of molecules in the chemical space provides a new possibility for improving the performance of perovskite solar cells. At present, although many molecules have been widely used in the medical field, the application of these molecules in the research of perovskite materials is still relatively limited. In view of the unique chemical properties and potential functions of these molecules, it shows great application potential to introduce them as additives into perovskite solar cells, which is expected to improve the photoelectric conversion efficiency. Therefore, applying medical molecules to perovskite solar cells not only helps to broaden the application range of materials, but also promotes the further improvement of the efficiency of solar cells. SUMMARY

[0005] In order to solve the above technical problems in the background art, the application provides a preparation method of a perovskite solar cell capable of improving the overall photoelectric conversion efficiency of the perovskite solar cell device and the perovskite solar cell.

[0006] In order to achieve the above purpose, the application adopts the following technical scheme:

[0007] The application of an organic molecule additive in improving the overall photoelectric conversion efficiency of a perovskite solar cell is characterized in that the organic molecule additive is risendronic acid or Boc-L-threonine N-hydroxysuccinimidyl ester.

[0008] A preparation method of a perovskite solar cell is characterized in that the preparation method of the perovskite solar cell comprises the following steps:

[0009] 1) Selecting a conductive glass layer substrate;

[0010] 2) Preparing a perovskite light-absorbing layer containing an organic molecule additive on the conductive glass layer substrate;

[0011] 3) Sequentially spin-coating an electron transport layer and an electron buffer layer on the perovskite light-absorbing layer;

[0012] 4) Thermal evaporation of a metal electrode on the electron buffer layer to obtain a perovskite solar cell.

[0013] Preferably, the specific implementation of step 2) used in the present application is:

[0014] 2.a.1) Preparing an organic molecule additive solution;

[0015] 2.a.2) Spin-coating a perovskite precursor solution on the conductive glass layer substrate covered with a hole transport layer, and heat treating to form a perovskite thin film on the substrate;

[0016] 2.a.3) Spin-coating the organic molecule additive solution prepared in step 2.a.1) on the perovskite thin film obtained in step 2.a.2);

[0017] 2.a.4) Sequentially heat treating and ultraviolet irradiating the product obtained in step 2.a.3) to obtain a perovskite light-absorbing layer containing an organic molecule additive.

[0018] Preferably, the specific implementation of step 2.a.1) used in the present application is: selecting an organic molecule additive and an organic solvent, dissolving the organic molecule additive in the organic solvent to obtain an organic molecule additive solution with a concentration of 0.01-10 mg / mL; the organic molecule additive is risendronic acid or Boc-L-threonine N-hydroxysuccinimidyl ester; the organic solvent is one of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol, and chloroform, or a combination of any two of the above; when the organic solvent is a combination of any two of the above, the volume ratio of the mixed solvent is 5:1-1:1.

[0019] Preferably, the preparation method of the perovskite precursor solution in step 2.a2) used in the present application is: dissolving the perovskite precursor in the perovskite precursor solvent in anhydrous and anaerobic environment, heating and stirring at 25-100°C for 1-12h to obtain a perovskite precursor solution with a concentration of 1.0-1.7M;

[0020] Preferably, the perovskite precursor is an AX or BX2 type compound, A is MA + (CH3NH3 + ), FA + [HC(=NH)NH2+ ]、Cs + and K + in combination; the B is Pb 2+ and / or Sn 2+ ; the X is one or more combinations of halogen ions; the perovskite precursor solvent is one or a mixture of any two of diethanol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and when any two are mixed, the volume ratio of the perovskite precursor solvent is 5:1 to 1:1.

[0021] Preferably, the spin-coating speed of the perovskite precursor solution in step 2.a.2) is 2500-5000 rpm / min, the spin-coating time is 30-60 s, and the thickness of the perovskite film obtained by spin-coating is 250-750 nm; the heat treatment temperature in step 2.a.2) is 80-120 °C, and the heat treatment time is 1-30 min; preferably, the spin-coating speed of the organic molecular additive solution in step 2.a.3) is 1500-5000 rpm / min, and the spin-coating time is 15-60 s; preferably, the heat treatment temperature in step 2.a.4) is 80-120 °C, and the heat treatment time is 1-30 min; preferably, the wavelength of the ultraviolet lamp in step 2.a.4) is 254 nm, and the irradiation time is 1-30 min.

[0022] Preferably, the specific implementation of step 2) of the present application is:

[0023] 2.b.1) preparing an organic molecular additive solution;

[0024] 2.b.2) adding the organic molecular additive solution prepared in step 2.b.1) to the perovskite precursor solution to obtain a perovskite precursor mixed solution with a concentration of 0.01-10 mg / mL;

[0025] 2.b.3) spin-coating the perovskite precursor mixed solution prepared in step 2.b.2) on a conductive glass layer substrate covered with a hole transport layer;

[0026] 2.b.4) sequentially subjecting the product obtained in step 2.b.3) to heat treatment and ultraviolet lamp irradiation treatment to obtain a perovskite light-absorbing layer containing an organic molecular additive.

[0027] Preferably, the specific implementation of step 2.b.1) used in the present application is: selecting an organic molecular additive and an organic solvent, dissolving the organic molecular additive in the organic solvent to obtain an organic molecular additive solution with a concentration of 0.01-10 mg / mL; the organic molecular additive is risedronate or Boc-L-threonine N-hydroxysuccinimidyl ester; the organic solvent is one of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform, or a combination of any two of the organic solvents; when the organic solvent is a combination of any two of the organic solvents, the volume ratio of the mixed solvents is 5:1-1:1.

[0028] Preferably, the preparation method of the perovskite precursor solution in step 2.b.2) used in the present application is: dissolving the perovskite precursor in the perovskite precursor solvent in anhydrous and anaerobic environment, heating and stirring at 25-100°C for 1-12 h to obtain a perovskite precursor solution with a concentration of 1.0-1.7 M;

[0029] Preferably, the perovskite precursor is a compound of AX or BX2 type, wherein A is a combination of one or more of MA + (CH3NH3 + ), FA + [HC(=NH)NH2 + ], Cs + and K + ; B is Pb 2+ and / or Sn 2+ ; X is a combination of one or more of halogen ions; the perovskite precursor solvent is one of diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, or a mixture of any two of the solvents; when the perovskite precursor solvent is a mixture of any two of the solvents, the volume ratio of the perovskite precursor solvent is 5:1-1:1;

[0030] Preferably, in step 2.b.3), when the perovskite precursor mixed solution is spin-coated on the conductive glass layer substrate covered with the hole transport layer, the spin-coating speed is 2500-5000 rpm / min, the spin-coating time is 30-60 s; the spin-coating thickness is 250-750 nm;

[0031] Preferably, in step 2.b.4), the heat treatment temperature is 100-150°C, and the heat treatment time is 15-60 min;

[0032] Preferably, in step 2.b.4), the wavelength of the ultraviolet lamp is 254 nm during the ultraviolet irradiation treatment, and the irradiation time is 1-30 min.

[0033] A perovskite solar cell prepared based on a preparation method of the perovskite solar cell as described above.

[0034] The present application has the following beneficial effects:

[0035] The present application provides a preparation method of a perovskite solar cell, comprising: 1) selecting a conductive glass layer substrate; 2) preparing a perovskite light-absorbing layer containing an organic molecule additive on the conductive glass layer substrate; 3) sequentially spin-coating an electron transport layer and an electron buffer layer on the perovskite light-absorbing layer; 4) thermally evaporating a metal electrode on the electron buffer layer to obtain the perovskite solar cell. The risedronic acid molecule used in the present application is applied to the surface of the perovskite thin film through interface modification, which helps to promote the charge exchange between the interfaces, thereby improving the efficiency of the device. The Boc-L-threonine N-hydroxysuccinimide ester molecule of the present application is incorporated in the perovskite precursor solution in the bulk phase, which regulates the perovskite crystallization during the annealing process, thereby improving the film quality, promoting the carrier transport, and improving the photoelectric conversion efficiency. The perovskite solar cell regulated by the organic molecule of the present application has high photoelectric conversion efficiency and good repeatability. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a structure diagram of the perovskite solar cell of the present application with molecular interface modification and bulk phase incorporation.

[0037] Figure 2 is a structure diagram of the risedronic acid molecule of the present application.

[0038] Figure 3 is a current-voltage curve diagram of the perovskite solar cell with risedronic acid molecule interface modification prepared in Experimental Example 1 of the present application.

[0039] Figure 4 is a current-voltage curve diagram of the perovskite solar cell with risedronic acid molecule interface modification prepared in Experimental Example 2 of the present application.

[0040] Figure 5 is a current-voltage curve diagram of the perovskite solar cell with risedronic acid molecule interface modification prepared in Experimental Example 3 of the present application.

[0041] Figure 6 is a structure diagram of the Boc-L-threonine N-hydroxysuccinimide ester molecule of the present application.

[0042] Figure 7 is a current-voltage curve diagram of the perovskite solar cell with bulk phase incorporation of the Boc-L-threonine N-hydroxysuccinimide ester molecule prepared in Experimental Example 4 of the present application.

[0043] Figure 8is the current-voltage curve diagram of the perovskite solar cell to which Boc-L-threonine N-hydroxysuccinimide ester is molecularly incorporated, which is prepared in Experimental Example 5 of the present application.

[0044] Figure 9 is the current-voltage curve diagram of the perovskite solar cell to which Boc-L-threonine N-hydroxysuccinimide ester is molecularly incorporated, which is prepared in Experimental Example 6 of the present application.

[0045] Figure 10 is the current-voltage curve diagram of the perovskite solar cell prepared in Comparative Example 1 of the present application.

[0046] Explanation of reference signs:

[0047] 1 - conductive glass layer; 2 - hole transport layer; 3 - perovskite light-absorbing layer containing organic molecular additive; 4 - organic molecule; 5 - electron transport layer; 6 - electron buffer layer; 7 - metal electrode layer. DETAILED DESCRIPTION

[0048] The principles and features of the present application are described below in conjunction with the accompanying drawings, and the examples are only used to illustrate the content of the present application and do not constitute a limitation on the scope of the present application.

[0049] In the actual research and development process, it is found that the organic molecular additive Risedronic acid (RIS) or Boc-L-threonine N-hydroxysuccinimide ester (BTN) can be used to improve the overall photoelectric conversion efficiency of the perovskite solar cell, therefore, based on this content, the present application provides a preparation method of a perovskite solar cell and a perovskite solar cell prepared based on the preparation method. Figure 1 From the structure, the perovskite solar cell provided by the present application comprises, from bottom to top, a conductive glass layer 1, a hole transport layer 2, a perovskite light-absorbing layer 3 containing an organic molecular additive, an electron transport layer 5, an electron buffer layer 6, and a metal electrode layer 7.

[0050] The technical solutions provided by the present application are described in detail below in conjunction with the accompanying drawings:

[0051] The preparation method of the perovskite solar cell provided by the present application can be two ways:

[0052] Way one:

[0053] A preparation method of a perovskite solar cell, comprising the following steps:

[0054] 1. Preparation of an organic molecular additive solution:

[0055] The organic molecular additive is dissolved in an organic solvent to obtain an organic molecular additive solution with a concentration of 0.01-10 mg / mL; wherein the organic molecule is a risedronate molecule, and the organic solvent is one or a mixture of any two of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform.

[0056] 2) Preparation of an organic molecular modified perovskite solar cell:

[0057] First, spin-coat a perovskite precursor solution on a conductive glass layer substrate covered with a hole transport layer at a spin-coating speed of 2500-5000 rpm / min for 30-60 s; perform heat treatment at a heat treatment temperature of 100-150 °C for 15-60 min; after the heat treatment is completed, a perovskite thin film with a thickness of 250-750 nm is obtained, i.e., a perovskite thin film is formed on the substrate. The perovskite precursor solution is prepared by dissolving a perovskite precursor in a perovskite precursor solvent to obtain a perovskite precursor solution with a concentration of 1.0-1.7 M; the perovskite precursor is one or more of AX and BX2 type compounds, wherein A is one or more of MA + (CH3NH3 + ), FA + [HC(=NH)NH2 + ], Cs + , K + ; B is one or more of Pb 2+ , Sn 2+ ; X is one or more of halogen ions; and the perovskite precursor solvent is a mixture of one or any two of diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone.

[0058] Second, spin-coat the organic molecular additive solution on the perovskite thin film at a spin-coating speed of 2500-5000 rpm / min for 15-60 s; sequentially perform heat treatment and ultraviolet irradiation treatment to form a perovskite light-absorbing-molecule composite layer of the cell on the substrate; wherein the heat treatment temperature is 80-120 °C, and the heat treatment time is 1-30 min; the wavelength of the ultraviolet lamp in the subsequent ultraviolet irradiation treatment is 254 nm, and the irradiation time is 1-30 min.

[0059] Finally, spin-coat an electron transport layer and an electron buffer layer on the perovskite light-absorbing-molecule composite layer in sequence, and evaporate a metal electrode on the electron buffer layer to obtain a molecular modified perovskite solar cell, and the molecular modification is molecular interface modification. See Figure 1, the battery obtained by the way is from bottom to top conductive glass layer 1, hole transport layer 2, perovskite light absorption layer, electron transport layer 5, electron buffer layer 6, metal electrode layer 7. Risedronate molecules 4 are above the perovskite light absorption layer, wherein the perovskite light absorption layer is a perovskite light absorption-molecule composite layer. As shown in Figure 2 , it is the structure of risedronate molecule.

[0060] Referring to Figure 3 , Figure 4 and Figure 5 , different embodiments based on mode one are as follows:

[0061] Embodiment 1:

[0062] In this embodiment, the preparation of perovskite solar cell modified by risedronate is adopted, the solvent of the molecular additive solution is isopropanol, and the modification concentration is 0.1 mg / mL. In the specific preparation process, the following steps are included:

[0063] S1: Preparation of molecular additive solution: in anhydrous and oxygen-free environment, a proper amount of risedronate molecules is dissolved in isopropanol to obtain a molecular additive solution with a concentration of 0.1 mg / mL;

[0064] S2: Preparation of perovskite precursor solution: in anhydrous and oxygen-free environment, CsI, MABr, FAI, PbI2 and PbBr2 are dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 according to a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, stirred at 50°C for 2h, and then filtered through an organic filter to obtain a perovskite precursor solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3 with a concentration of 1.4M;

[0065] S3: Preparation of hole transport layer substrate: the FTO conductive glass is placed in the UV cleaning machine for 30min, 50μL of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl] phosphonic acid (MeO-2PACz) dimethoxyethanol solution is slowly dropped on the FTO conductive glass, and the hole transport layer substrate is obtained after spin coating and heat treatment.

[0066] S4: Preparation of perovskite light-molecule composite layer: 40 μL of perovskite precursor solution is first dropped on the hole transport layer substrate at a rotation speed of 3500 rpm / min for 50 s, and then annealed at 110°C to form a perovskite film. After cooling, 50 μL of the above-mentioned S1 molecule additive solution is coated on the perovskite film, and then irradiated with a 254 nm ultraviolet lamp for 1 min to obtain a perovskite light-molecule composite layer after heat treatment;

[0067] S5: Preparation of electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) chlorobenzene solution is spin-coated on the perovskite layer, and then heat-treated to obtain an electron transport layer;

[0068] S6: Preparation of electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) isopropanol solution is slowly dropped on the electron transport layer, and then heat-treated to obtain an electron buffer layer;

[0069] S7: Preparation of metal electrode layer: 80 nm of silver is evaporated on the electron buffer layer by a thermal evaporation method.

[0070] Referring to Figure 3 , the photoelectric conversion efficiency of the perovskite solar cell in Example 1 is measured to be 23.81%, and the effective area is 0.05 cm 2 .

[0071] Example 2:

[0072] In this example, the preparation of a perovskite solar cell is modified by using risedronic acid, and the solvent of the molecule additive solution is isopropanol, and the modification concentration is 0.3 mg / mL:

[0073] S1: Preparation of molecule additive solution: In anhydrous and oxygen-free environment, a proper amount of risedronic acid molecules is dissolved in isopropanol to obtain a molecule additive solution with a concentration of 0.3 mg / mL;

[0074] S2: Preparation of perovskite precursor solution: In an anhydrous and oxygen-free environment, CsI, MABr, FAI, PbI2 and PbBr2 are dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 in a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, and stirred at 50°C for 2 h. After filtration with an organic filter, a 1.4 M perovskite precursor solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0075] S3: Preparation of hole transport layer substrate: FTO conductive glass was placed in the UV cleaning machine for 30 min, 50 μL of [2-(3,6-dimethoxy-9H-carbazole-9-yl) ethyl] phosphonic acid (MeO-2PACz) dimethoxy ethanol solution was slowly dropped on the FTO conductive glass, and the hole transport layer substrate was obtained after spin coating and heat treatment;

[0076] S4: Preparation of perovskite light-molecule composite layer: 40 μL of perovskite precursor solution was first taken and dropped on the hole transport layer substrate at a speed of 3500 rpm / min for 50 s, and then annealed at 110°C to form a perovskite film. After cooling, 50 μL of the above-mentioned S1 molecule additive solution was coated on the perovskite film, and then heat treated and irradiated with a 254 nm ultraviolet lamp for 1 min to obtain a perovskite light-molecule composite layer;

[0077] S5: Preparation of electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM) chlorobenzene solution was spin-coated on the perovskite layer, and then heat treated to prepare an electron transport layer;

[0078] S6: Preparation of electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) isopropanol solution was slowly dropped on the electron transport layer, and then heat treated to prepare an electron buffer layer;

[0079] S7: Preparation of metal electrode layer: 80 nm of silver was evaporated on the electron buffer layer by using a thermal evaporation method.

[0080] Reference Figure 4 The photoelectric conversion efficiency of the perovskite solar cell in Example 2 was measured to be 24.38%, and the effective area was 0.05 cm 2 .

[0081] Example 3:

[0082] In this example, the preparation of perovskite solar cells was modified by using risedronic acid, the solvent of the molecule additive solution was isopropanol, and the modification concentration was 0.5 mg / mL:

[0083] S1: Preparation of molecule additive solution: In anhydrous and oxygen-free environment, a proper amount of risedronic acid molecules was dissolved in isopropanol to obtain a molecule additive solution with a concentration of 0.5 mg / mL;

[0084] S2: Preparation of perovskite precursor solution: In anhydrous and anaerobic environment, CsI, MABr, FAI, PbI2 and PbBr2 were dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 in a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, stirred at 50°C for 2h, filtered through an organic filter head to obtain a 1.4M perovskite precursor solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0085] S3: Preparation of hole transport layer substrate: FTO conductive glass was placed in a UV cleaning machine for 30min, 50μL of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) solution in dimethoxyethanol was slowly dropped on the FTO conductive glass, and the hole transport layer substrate was obtained after spin coating and heat treatment;

[0086] S4: Preparation of perovskite light-absorbing-molecule composite layer: 40μL of perovskite precursor solution was first dropped on the hole transport layer substrate at a speed of 3500rpm / min for 50s, and then annealed at 110°C to form a perovskite film. After cooling, 50μL of the above-mentioned molecular additive solution in S1 was coated on the perovskite film, and the perovskite light-absorbing-molecule composite layer was obtained after heat treatment and irradiation with a 254nm ultraviolet lamp for 1min;

[0087] S5: Preparation of electron transport layer: 40μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) solution in chlorobenzene was spin-coated on the perovskite layer, and the electron transport layer was prepared after heat treatment;

[0088] S6: Preparation of electron buffer layer: 200μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) solution in isopropanol was slowly dropped on the electron transport layer, and the electron buffer layer was prepared after heat treatment;

[0089] S7: Preparation of metal electrode layer: 80nm of silver was evaporated on the electron buffer layer by thermal evaporation method.

[0090] Referring to Figure 5 , the photoelectric conversion efficiency of the perovskite solar cell in Example 3 was measured to be 23.83%, and the effective area was 0.05cm 2 .

[0091] Method two:

[0092] A method for preparing a perovskite solar cell, comprising the following steps:

[0093] 1. A step of preparing an organic molecule additive solution:

[0094] Dissolving the organic molecule additive in an organic solvent to obtain an organic molecule additive solution with a concentration of 0.01-10 mg / mL; wherein the organic molecule is Boc-L-threonine N-hydroxysuccinimide ester molecule, and the organic solvent is one or more of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform.

[0095] 2. A step of preparing an organic molecule modified perovskite solar cell:

[0096] First, the obtained molecule additive solution is added to a perovskite precursor solution to obtain a perovskite precursor mixed solution with a concentration of 0.01-10 mg / mL;

[0097] wherein, the same as mode one, the perovskite precursor solution is prepared by dissolving perovskite precursors in a perovskite precursor solvent to obtain a perovskite precursor solution with a concentration of 1.0-1.7 M; the perovskite precursor is a compound of AX and BX2 type, wherein A is one or more of MA + (CH3NH3 + ), FA + [HC(=NH)NH2 + ], Cs + , K + ; B is one or more of Pb 2+ , Sn 2+ ; X is one or more of halogen ions; and the perovskite precursor solvent is formed by mixing one or any two of diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone.

[0098] Second, spin-coating the perovskite precursor mixed solution on a conductive glass layer substrate covered with a hole transport layer, and then sequentially performing heat treatment and ultraviolet lamp irradiation treatment to form a molecule-perovskite light-absorbing layer on the substrate; wherein the spin-coating speed is 2500-5000 rpm / min, the spin-coating time is 30-60 s; the heat treatment temperature is 100-150℃, and the annealing time is 15-60 min; after the heat treatment, the obtained molecule-perovskite light-absorbing layer has a thickness of 250-750 nm, and the ultraviolet irradiation treatment is performed by using an ultraviolet lamp with a wavelength of 254 nm for 1-30 min.

[0099] Finally, the electron transport layer and the electron buffer layer are spin-coated on the molecule-perovskite light-absorbing layer in sequence, and a metal electrode is evaporated on the electron buffer layer to obtain a molecule-modified perovskite solar cell, wherein the molecule modification is a molecule bulk phase doping modification.

[0100] The battery structure obtained by the second method is the same as that obtained by the first method, and is not described here. The Boc-L-threonine N-hydroxysuccinimide ester molecules 4 are inside the perovskite light-absorbing layer, i.e., the molecule-perovskite light-absorbing layer. As shown in Figure 6 , it is the structural formula of the Boc-L-threonine N-hydroxysuccinimide ester molecule.

[0101] Referring to Figure 7 , Figure 8 and Figure 9 , different embodiments based on the second method are as follows:

[0102] Example 4:

[0103] The preparation of the Boc-L-threonine N-hydroxysuccinimide ester molecule bulk phase doping perovskite solar cell, the solvent of the molecule additive solution is N,N-dimethylformamide, and the modification concentration is 0.05 mg / mL.

[0104] S1: Preparation of a molecule additive solution: In anhydrous and oxygen-free environment, a proper amount of Boc-L-threonine N-hydroxysuccinimide ester molecules are dissolved in N,N-dimethylformamide to obtain a molecule additive solution with a concentration of 0.05 mg / mL;

[0105] S2: Preparation of a perovskite precursor mixed solution: In an anhydrous and oxygen-free environment, CsI, MABr, FAI, PbI2 and PbBr2 are dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 according to a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, and 10 μL of the molecule additive solution in S1 is added, stirred at 50°C for 2 h, and filtered through an organic filter to obtain a 1.4M perovskite precursor mixed solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0106] S3: Preparation of hole transport layer substrate: FTO conductive glass was placed in the UV cleaning machine for 30 min, 50 μL of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl] phosphonic acid (MeO-2PACz) dimethoxyethanol solution was slowly dropped on the FTO conductive glass, and the hole transport layer substrate was obtained after spin coating and heat treatment;

[0107] S4: Preparation of molecular-perovskite light-absorbing layer: 40 μL of perovskite precursor mixed solution was first dropped on the hole transport layer substrate at a speed of 3500 rpm / min for 50 s, and then annealed at 110°C to form a perovskite film, and a molecular-perovskite light-absorbing layer was obtained by irradiation with a 254 nm ultraviolet lamp for 3 min;

[0108] S5: Preparation of electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) chlorobenzene solution was spin-coated on the perovskite layer, and an electron transport layer was prepared after heat treatment;

[0109] S6: Preparation of electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) isopropanol solution was slowly dropped on the electron transport layer, and an electron buffer layer was prepared after heat treatment;

[0110] S7: Preparation of metal electrode layer: 80 nm of silver was evaporated on the electron buffer layer by using a thermal evaporation method.

[0111] Referring to Figure 7 , the photoelectric conversion efficiency of the perovskite solar cell in Example 4 was measured to be 24.58%, and the effective area was 0.05 cm 2 .

[0112] Example 5:

[0113] Preparation of Boc-L-threonine N-hydroxysuccinimide ester molecular phase doping perovskite solar cell, the solvent of the molecular additive solution is N,N-dimethylformamide, and the modification concentration is 0.10 mg / mL.

[0114] S1: Preparation of molecular additive solution: In anhydrous and oxygen-free environment, a proper amount of Boc-L-threonine N-hydroxysuccinimide ester molecule was dissolved in N,N-dimethylformamide to obtain a molecular additive solution with a concentration of 0.10 mg / mL;

[0115] S2: Preparation of perovskite precursor mixed solution: In anhydrous and anaerobic environment, CsI, MABr, FAI, PbI2 and PbBr2 were dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 in a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, and then 10 μL of the molecular additive solution in S1 was added. The solution was stirred at 50°C for 2 h, and then filtered through an organic filter head to obtain a perovskite precursor mixed solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0116] S3: Preparation of hole transport layer substrate: The FTO conductive glass was placed in a UV cleaning machine for 30 min, and 50 μL of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) in dimethoxyethanol was slowly dropped onto the FTO conductive glass. After spin coating and heat treatment, a hole transport layer substrate was obtained.

[0117] S4: Preparation of molecular-perovskite light absorbing layer: 40 μL of perovskite precursor mixed solution was first taken and dropped on the hole transport layer substrate at a rotation speed of 3500 rpm / min for 50 s, and then annealed at 110°C to form a perovskite film. The film was irradiated with a 254 nm ultraviolet lamp for 3 min to obtain a molecular-perovskite light absorbing layer.

[0118] S5: Preparation of electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in chlorobenzene was spin-coated on the perovskite layer, and then heat-treated to obtain an electron transport layer.

[0119] S6: Preparation of electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol was slowly dropped on the electron transport layer, and then heat-treated to obtain an electron buffer layer.

[0120] S7: Preparation of metal electrode layer: 80 nm of silver was evaporated on the electron buffer layer by a thermal evaporation method.

[0121] Referring to Figure 8 , the photoelectric conversion efficiency of the perovskite solar cell in Example 5 was measured to be 25.20%, and the effective area was 0.05 cm 2 .

[0122] Example 6:

[0123] Preparation of Boc-L-threonine N-hydroxysuccinimidyl ester molecular phase incorporation perovskite solar cell, the solvent of the molecular additive solution is N,N-dimethylformamide, and the modification concentration is 0.15 mg / mL.

[0124] S1: preparing a molecular additive solution: in anhydrous and anaerobic environment, a proper amount of Boc-L-threonine N-hydroxysuccinimidyl ester molecules are dissolved in N,N-dimethylformamide to obtain a molecular additive solution with a concentration of 0.15 mg / mL;

[0125] S2: preparing a perovskite precursor mixed solution: in anhydrous and anaerobic environment, CsI, MABr, FAI, PbI2 and PbBr2 are dissolved in a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 according to a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, and then 10 μL of the molecular additive solution in S1 is added, and the mixture is stirred at 50°C for 2 h, and then filtered through an organic filter head to obtain a perovskite precursor mixed solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0126] S3: preparing a hole transport layer substrate: the FTO conductive glass is placed in a UV cleaning machine for 30 min, 50 μL of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) in dimethoxyethanol is slowly dropped on the FTO conductive glass, and after spin coating and heat treatment, a hole transport layer substrate is obtained;

[0127] S4: preparing a molecular-perovskite light absorption layer: 40 μL of the perovskite precursor mixed solution is first taken and dropped on the hole transport layer substrate at a rotation speed of 3500 rpm / min for 50 s, and then annealed at 110°C to form a perovskite film, and then irradiated with a 254 nm ultraviolet lamp for 3 min to obtain a molecular-perovskite light absorption layer;

[0128] S5: preparing an electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) in chlorobenzene is taken and spin-coated on the perovskite layer, and then heat-treated to obtain an electron transport layer;

[0129] S6: preparing an electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol is slowly dropped on the electron transport layer, and then heat-treated to obtain an electron buffer layer;

[0130] S7: Preparation of metal electrode layer: 80 nm of silver was evaporated on the electron buffer layer by using thermal evaporation method.

[0131] Referring to Figure 9 , the photoelectric conversion efficiency of the perovskite solar cell in Example 6 was measured to be 24.48%, and the effective area was 0.05 cm 2 .

[0132] Comparative Example 1: Preparation of perovskite solar cell without adding organic molecular additive.

[0133] S1: Preparation of perovskite precursor solution: In anhydrous and anaerobic environment, CsI, MABr, FAI, PbI2 and PbBr2 were dissolved in a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide with a volume ratio of 4:1 in a molar ratio of 0.05:0.0475:0.9025:0.94875:0.05125, stirred at 50°C for 2h, and then filtered through an organic filter to obtain a 1.4M perovskite precursor solution Cs 0.05 (MA 0.05 FA 0.95 ) 0.95 Pb(I 0.95 Br 0.05 )3;

[0134] S2: Preparation of hole transport layer substrate: the FTO conductive glass was placed in the UV cleaning machine for 30 min, 50 μL of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) solution in dimethoxyethanol was slowly dropped on the FTO conductive glass, and the hole transport layer substrate was obtained after spin coating and heat treatment;

[0135] S3: Preparation of perovskite light absorbing layer: 40 μL of perovskite precursor mixed solution was dropped on the hole transport layer substrate at a speed of 3500 rpm / min for 50 s, and the perovskite light absorbing layer was formed by annealing at 110°C;

[0136] S4: Preparation of electron transport layer: 40 μL of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) solution in chlorobenzene was spin-coated on the perovskite layer, and the electron transport layer was prepared after heat treatment;

[0137] S5: Preparation of electron buffer layer: 200 μL of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) solution in isopropanol was slowly dropped on the electron transport layer, and the electron buffer layer was prepared after heat treatment;

[0138] S6: Preparation of metal electrode layer: 80 nm of silver was evaporated on the electron buffer layer by using thermal evaporation method.

[0139] As shown in Figure 10 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.11%, and the effective area is 0.05cm 2 .

[0140] In combination with the data in Figures 3-5 , Figures 7-9 and Figure 10 , the experimental results show that the current of the device is improved, which indicates that the risedronic acid or Boc-L-threonine N-hydroxysuccinimide ester molecule can effectively improve the extraction and transmission of charges, thereby improving the photoelectric conversion efficiency of the perovskite solar cell, and showing high commercial application potential.

[0141] The above is only a preferred experimental case of the present application, and does not limit the scope of the present application. Any modification, equivalent replacement or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a perovskite solar cell, characterized by: The preparation method of the perovskite solar cell comprises the following steps: 1) selecting a conductive glass layer substrate; 2) preparing a perovskite light-absorbing layer containing an organic molecular additive on the conductive glass layer substrate, the organic molecular additive being risedronic acid or Boc-L-threonine N-hydroxysuccinimide ester; 3) sequentially spin-coating an electron transport layer and an electron buffer layer on the perovskite light-absorbing layer; 4) hot evaporating a metal electrode on the electron buffer layer to obtain the perovskite solar cell.

2. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The specific implementation mode of the step 2) is: 2.a.1) preparing an organic molecular additive solution; 2.a.2) spin-coating a perovskite precursor solution on the conductive glass layer substrate covered with a hole transport layer, and performing heat treatment to form a perovskite thin film on the substrate; 2.a.3) spin-coating the organic molecular additive solution prepared in the step 2.a.1) on the perovskite thin film obtained in the step 2.a.2); 2.a.4) sequentially performing heat treatment and ultraviolet irradiation treatment on the product obtained in the step 2.a.3) to obtain the perovskite light-absorbing layer containing the organic molecular additive.

3. The method for preparing a perovskite solar cell according to claim 2, characterized in that: The specific implementation mode of the step 2.a.1) is: selecting an organic molecular additive and an organic solvent, dissolving the organic molecular additive in the organic solvent to obtain an organic molecular additive solution with a concentration of 0.01-10 mg / mL; the organic molecular additive is risedronic acid or Boc-L-threonine N-hydroxysuccinimide ester; the organic solvent is one or a combination of any two of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform; when the organic solvent is a combination of any two of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform, the volume ratio of the mixed solvent is 5:1-1:

1.

4. The method for preparing a perovskite solar cell according to claim 3, characterized in that: The preparation mode of the perovskite precursor solution in the step 2.a.2) is: dissolving the perovskite precursor in a perovskite precursor solvent in anhydrous and anaerobic environment, heating and stirring at 25-100℃ for 1-12h to obtain a perovskite precursor solution with a concentration of 1.0-1.7M; The perovskite precursor is a combination of one or more of AX or BX2type compounds, the A is a combination of one or more of MA + , FA + , Cs + , and K + ; the B is Pb 2+ and / or Sn 2+ ; the X is a combination of one or more of halogen ions; the perovskite precursor solvent is one or a mixture of any two of diethanol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, and N-methyl pyrrolidone, when the perovskite precursor solvent is a mixture of any two, the volume ratio of the perovskite precursor solvent is 5:1 to 1:

1.

5. The method for preparing a perovskite solar cell according to claim 4, characterized in that: The spin-coating speed of the perovskite precursor solution in the step 2.a.2) is 2500-5000 rpm, the spin-coating time is 30-60s, and the thickness of the perovskite thin film obtained by spin-coating is 250-750nm; the heat treatment temperature in the step 2.a.2) is 80-120℃, and the heat treatment time is 1-30min; the spin-coating speed of the organic molecular additive solution on the perovskite thin film in the step 2.a.3) is 1500-5000 rpm, and the spin-coating time is 15-60s; the heat treatment temperature in the step 2.a.4) is 80-120℃, and the heat treatment time is 1-30min; the ultraviolet lamp wavelength for ultraviolet irradiation treatment in the step 2.a.4) is 254nm, and the irradiation time is 1-30min.

6. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The specific implementation mode of the step 2) is: 2.b.1) preparing an organic molecular additive solution; 2.b.2) adding the organic molecule additive solution prepared in step 2.b.1) into the perovskite precursor solution to obtain a perovskite precursor mixed solution with a concentration of 0.01-10 mg / mL; 2.b.3) spin-coating the perovskite precursor mixed solution prepared in step 2.b.2) on a conductive glass layer substrate covered with a hole transport layer; 2.b.4) sequentially subjecting the product obtained in step 2.b.3) to heat treatment and ultraviolet lamp irradiation treatment to obtain a perovskite light-absorbing layer containing an organic molecule additive.

7. The method for preparing a perovskite solar cell according to claim 6, characterized in that: The specific implementation of step 2.b.1) is as follows: selecting an organic molecule additive and an organic solvent, dissolving the organic molecule additive in the organic solvent to obtain an organic molecule additive solution with a concentration of 0.01-10 mg / mL; the organic molecule additive is risedronic acid or Boc-L-threonine N-hydroxysuccinimidyl ester; the organic solvent is one or a combination of any two of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform; when the organic solvent is a combination of any two of isopropyl alcohol, methanol, ethanol, dimethoxy ethanol and chloroform, the volume ratio of the mixed solvent is 5:1-1:

1.

8. The method for preparing a perovskite solar cell according to claim 7, characterized in that: The preparation method of the perovskite precursor solution in step 2.b.2) is as follows: in anhydrous and anaerobic environment, dissolving the perovskite precursor in a perovskite precursor solvent, heating and stirring at 25-100°C for 1-12 h to obtain a perovskite precursor solution with a concentration of 1.0-1.7 M; the perovskite precursor is a combination of one or more of AX or BX2type compounds, the A is a combination of one or more of MA + , FA + , Cs + , and K + ; the B is Pb 2+ and / or Sn 2+ ; the X is a combination of one or more of halide ions; the perovskite precursor solvent is one or a mixture of any two of diethanol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, and N-methyl pyrrolidone, when the perovskite precursor solvent is a mixture of any two, the volume ratio of the perovskite precursor solvent is 5:1 to 1:

1. In step 2.b.3), when spin-coating the perovskite precursor mixed solution on the conductive glass layer substrate covered with a hole transport layer, the spin-coating speed is 2500-5000 rpm, the spin-coating time is 30-60 s; the spin-coating thickness is 250-750 nm; In step 2.b.4), the heat treatment temperature is 100-150°C, and the heat treatment time is 15-60 min; In step 2.b.4), the wavelength of the ultraviolet lamp for ultraviolet irradiation treatment is 254 nm, and the irradiation time is 1-30 min.

9. A perovskite solar cell prepared by the method according to any one of claims 1-8.

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