An organic-inorganic hybrid perovskite solar cell and a preparation method thereof

Abstract

The application belongs to the technical field of solar cells, and specifically provides an organic-inorganic hybrid perovskite solar cell and a preparation method thereof, which comprises a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a charge blocking layer, a back electrode layer, and molecular modifiers and molecular passivators prepared by using alliin decomposition product molecules (diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiocyclohexane-4-ene and 3-vinyl-1,2-dithiocyclohexane-5-ene), vinyl diphenyl phosphine, diphenyl styryl phosphine oxide and diphenyl p-styryl phosphine. The prepared perovskite solar cell improves the transport and exchange efficiency of charges at the interface of the perovskite light absorption layer, and effectively improves the overall photoelectric conversion efficiency and stability of the device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solar cells, and particularly relates to an organic-inorganic hybrid perovskite solar cell and a preparation method thereof. BACKGROUND

[0002] The organic-inorganic hybrid perovskite material has been widely concerned in the photovoltaic field due to its excellent photoelectric performance, low cost and wide source, and the photoelectric conversion efficiency of the organic-inorganic hybrid perovskite solar cell has increased from 3.8% in 2009 to 26.1% in 2023 after ten years of technical development, which is close to the level of the current market crystalline silicon solar cell, and is considered as the third generation solar cell with the most commercialization potential.

[0003] However, there are still many problems in the perovskite solar cell prepared by the low-temperature spin coating method, for example, too many defects in the interior will cause non-radiative recombination of carriers, reducing the photoelectric conversion efficiency of the device; in addition, external factors such as water and oxygen will cause decomposition of the perovskite material, greatly reducing the performance of the device, which are major challenges for the commercialization application of the perovskite solar cell.

[0004] At present, in view of these problems, the perovskite thin film can be regulated and controlled by using a multifunctional molecule strategy, the quality of the perovskite thin film is improved, and the contact between the perovskite thin film and the transport layer material is optimized, so as to improve the photoelectric conversion efficiency and stability of the perovskite solar cell. However, it is currently urgent to solve the problem of how to use a multifunctional molecule strategy to comprehensively improve the photoelectric conversion efficiency and stability of the perovskite solar cell. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application respectively uses four product molecules of alliin decomposition products (diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiacyclohex-4-ene and 3-vinyl-1,2-dithiacyclohex-5-ene), vinyl diphenyl phosphine, diphenyl styryl phosphine and diphenyl p-styryl phosphine to improve the perovskite crystallization process, to form a corresponding polymer molecular crosslinking network by heat treatment polymerization, and to improve the transport efficiency of the carriers at the interface of the perovskite light absorption layer; at the same time, the decomposition products of alliin, vinyl diphenyl phosphine and diphenyl p-styryl phosphine molecules have the functions of improving the conductivity and passivation, so as to improve the overall photoelectric conversion efficiency of the device while improving the stability of the device.

[0006] In order to solve the problems existing in the prior art, the present application provides an organic-inorganic hybrid perovskite solar cell, which comprises: a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a charge blocking layer, a back electrode layer, and a molecular modifier and a molecular passivation agent for modifying the perovskite solar cell.

[0007] wherein the upper interface or the lower interface of the perovskite light-absorbing layer is coated with a molecular modifier, or the perovskite light-absorbing layer is added with a molecular passivation agent;

[0008] The molecular modifier and the molecular passivation agent each contain one or more of an alliin decomposition product, a vinyl diphenyl phosphine, a diphenyl styryl phosphine and a diphenyl p-styryl phosphine.

[0009] Further, the molecular modifier further contains a first organic solvent, and the first organic solvent is one or more of methanol, isopropyl alcohol, 2-methoxy propanol and chlorobenzene.

[0010] Further, the molecular passivation agent further contains a second organic solvent, and the second organic solvent is at least one of acetonitrile, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.

[0011] Further, the alliin decomposition product is one or more of four product molecules of diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiocyclohex-4-ene and 3-vinyl-1,2-dithiocyclohex-5-ene.

[0012] The application further provides a preparation method of the above organic-inorganic hybrid perovskite solar cell, and the preparation method comprises the following steps:

[0013] S1, preparing a perovskite precursor solution; dissolving a perovskite precursor in a third organic solvent in a waterless and oxygenless nitrogen glove box to configure a perovskite precursor solution with a concentration of 1.3-1.8 M, and heating and stirring at a temperature of 20-80 ℃ for 2-12 h; the third organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and when the third organic solvent is a plurality of solvents, the volume ratio of the plurality of solvents is 6:1-2:1;

[0014] S2, pre-treating a conductive substrate; the pre-treatment is ultraviolet ozone surface pre-treatment or plasma surface pre-treatment on the conductive substrate;

[0015] S3, spin-coating a hole transport layer solution on the pre-treated conductive substrate, and performing annealing treatment to obtain a hole transport layer; the spin-coating time of the hole transport layer solution is 40 s, and the annealing temperature is 110 ℃;

[0016] S4, preparing a perovskite light-absorbing layer with a molecular modification on the hole transport layer to obtain a perovskite light-absorbing layer-upper interface modification layer or a perovskite light-absorbing layer-lower interface modification layer or a perovskite light-absorbing layer added with a molecular passivation agent;

[0017] S5, spin-coating an electron transport layer and an electron blocking layer on the perovskite light-absorbing layer with the molecular modification in sequence, and then evaporating a metal electrode layer on the electron blocking layer to obtain an organic-inorganic hybrid perovskite solar cell.

[0018] Further, when the step S4 is to prepare the perovskite light-absorbing layer-lower interface modification layer, the molecular modifier is first spin-coated on the hole transport layer obtained in the step S3, and then the perovskite precursor solution in the step S1 is spin-coated on the conductive substrate with the hole transport layer and the lower interface modification to obtain the perovskite light-absorbing layer-lower interface modification layer.

[0019] In the method, the spin-coating speed of the molecular modifier on the hole transport layer is 2000-4000 rpm / min, and the spin-coating time is 10-40 s; the annealing temperature is 100-150℃, and the annealing time is 10-20 min.

[0020] Further, when the step S4 is to prepare the perovskite light-absorbing layer-upper interface modification layer, the perovskite precursor solution in the step S1 is first spin-coated on the hole transport layer obtained in the step S3, and then the molecular modifier is spin-coated or blade-coated on the perovskite light-absorbing layer to obtain the perovskite light-absorbing layer-upper interface modification layer after annealing.

[0021] In the method, the spin-coating speed of the perovskite precursor solution on the hole transport layer is 3000-6000 rpm / min, the spin-coating time is 10-60 s, and the amount of the perovskite precursor solution added dropwise is 30-70 μL; the annealing temperature is 100-160℃, and the annealing time is 10-30 min.

[0022] Further, when the step S4 is to add the molecular passivation agent to the perovskite light-absorbing layer, the molecular passivation agent and the perovskite precursor solution in the step S1 are mixed and then spin-coated on the conductive substrate with the hole transport layer to obtain the perovskite light-absorbing layer with the added molecular passivation agent after annealing.

[0023] In the method, when the molecular passivation agent and the perovskite precursor solution are mixed, the amount of the molecular passivation agent added is 2.5 μL-15 μL.

[0024] Further, the concentration of the spin-coated molecular modifier is 0.1-5 mg / mL.

[0025] Further, the concentration of the added molecular passivation agent is 0.01-0.5 mg / mL.

[0026] Compared with the prior art, the method has the following beneficial technical effects:

[0027] 1. The present invention utilizes allicin decomposition product molecules, distyrylphosphine oxide, vinyldiphenylphosphine and diphenyl-p-phenylenediphosphine molecules as interface modifiers to modify the perovskite surface. After annealing heat treatment, the molecules undergo cross-linking polymerization to form a dense molecular network above the perovskite, which hinders the invasion of external water and oxygen, prevents the perovskite from decomposing, and improves the stability of the perovskite light-absorbing layer. At the same time, the formation of the molecular network is conducive to improving the charge transport efficiency of the light-absorbing layer and the electron transport layer, reducing the hysteresis of the device and improving the efficiency of the device. Moreover, the S atoms and P atoms in the allicin decomposition product molecules, distyrylphosphine oxide, vinyldiphenylphosphine and diphenyl-p-phenylenediphosphine molecules can interact with defects on the surface of the perovskite film, thereby inhibiting non-radiative recombination of carriers, passivating related defects, and further improving the photoelectric conversion efficiency.

[0028] 2. The present invention utilizes allicin decomposition product molecules, distyrylphosphine oxide, vinyldiphenylphosphine and diphenyl-p-styrylphosphine molecules to modify the lower interface of the perovskite device, which can significantly passivate the defects between the hole transport layer and the perovskite light absorption layer, improve the efficiency of the perovskite device, reduce hysteresis, and at the same time, increase the wettability and uniformity of the perovskite light absorption layer in the hole transport layer, further improving performance.

[0029] 3. The present invention utilizes allicin decomposition products, vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl-p-styryl phosphine molecules mixed into the perovskite precursor solution, which can improve the crystallization process of the perovskite device during annealing heat treatment, thereby improving the quality of the perovskite film. At the same time, the S atoms and P atoms in the allicin decomposition products, distyryl phosphine oxide, vinyl diphenylphosphine and diphenyl-p-styryl phosphine molecules can coordinate with Pb+ in the perovskite precursor solution, reducing defects in the perovskite bulk phase and further improving performance.

[0030] 4. The molecular protection effect of the present invention is not restricted by position. It can be used as a modifier to modify the upper and lower surfaces of the perovskite light-absorbing layer, and can also be added into the perovskite light-absorbing layer as a molecular passivator, achieving multi-position optimization effects. It is also compatible with other perovskite surface passivation technologies and is repeatable. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings of the embodiments will be briefly described below. It should be noted that the drawings described below only relate to some embodiments of the present disclosure and are not intended to limit the present disclosure.

[0032] Figure 1 This is a diagram of the structure of a perovskite solar cell showing the positions of the lower interface modification, upper interface modification, and bulk addition of molecules provided by the present invention;

[0033] Figure 2 are structural formulas of the molecules provided by the present application before and after heat treatment, wherein (a) is a structural formula of diallyl disulfide molecules before and after heat treatment, (b) is a structural formula of diallyl sulfide before and after heat treatment, (c) is a structural formula of 3-vinyl-1,2-dithiocyclohex-4-ene before and after heat treatment, (d) is a structural formula of 3-vinyl-1,2-dithiocyclohex-5-ene before and after heat treatment, (e) is a structural formula of vinyl diphenyl phosphine before and after heat treatment, (f) is a structural formula of diphenyl styryl phosphine oxide before and after heat treatment, and (g) is a structural formula of diphenyl p-styryl phosphine before and after heat treatment;

[0034] Figure 3 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of diallyl disulfide molecules prepared in Example 1 of the present application (a) and a SEM image of a perovskite layer of Example 1 (b);

[0035] Figure 4 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of diallyl sulfide molecules prepared in Example 2 of the present application;

[0036] Figure 5 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of 3-vinyl-1,2-dithiocyclohex-4-ene molecules prepared in Example 3 of the present application;

[0037] Figure 6 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared in Example 4 of the present application;

[0038] Figure 7 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of vinyl diphenyl phosphine molecules prepared in Example 5 of the present application (a) and a SEM image of a perovskite layer of Example 5 (b);

[0039] Figure 8 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of diphenyl styryl phosphine oxide molecules prepared in Example 6 of the present application;

[0040] Figure 9 is a current-voltage curve diagram of a perovskite solar cell modified by a lower interface of diphenyl p-styryl phosphine molecules prepared in Example 7 of the present application (a) and a SEM image of a perovskite layer of Example 7 (b);

[0041] Figure 10 is a current-voltage curve diagram of a perovskite solar cell modified by an upper interface of diallyl disulfide molecules prepared in Example 8 of the present application and a SEM image of a perovskite layer of Example 8 (b);

[0042] Figure 11 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0043] Figure 12 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0044] Figure 13 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0045] Figure 14 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0046] Figure 15 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0047] Figure 16 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0048] Figure 17 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0049] Figure 18 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0050] Figure 19 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0051] Figure 20 Current-voltage curve of the perovskite solar cell modified by interfacial modification of 3-vinyl-1,2-dithiocyclohex-5-ene molecules prepared for the present application Example 11;

[0052] Figure 21The current-voltage curve diagram of the perovskite solar cell prepared by molecular phase penetration of the vinyl diphenyl phosphine prepared for the present embodiment 19, and the SEM image (b) of the perovskite layer of the embodiment 19;

[0053] Figure 22 The current-voltage curve diagram of the perovskite solar cell prepared by molecular phase penetration of the diphenyl styryl oxygen phosphine prepared for the present embodiment 20;

[0054] Figure 23 The current-voltage curve diagram of the perovskite solar cell prepared by molecular phase penetration of the diphenyl styryl oxygen phosphine prepared for the present embodiment 20;

[0055] Figure 24 The current-voltage curve diagram (a) of the perovskite solar cell prepared for the present comparative example 1, and the SEM image (b) of the perovskite layer of the comparative example 1;

[0056] Figure 25 The stability curve comparison diagram of the perovskite solar cells prepared by interfacial modification of the perovskite solar cells prepared by molecular phase penetration of the diphenyl styryl oxygen phosphine, the vinyl diphenyl phosphine and the diphenyl styryl oxygen phosphine under the conditions of the present embodiment 1, 5 and 7, and the perovskite solar cell prepared for the present comparative example 1. DETAILED DESCRIPTION

[0057] In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure clearer, the technical solutions of the embodiments of the present disclosure will be described clearly and completely below with reference to the drawings. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the protection scope of the present disclosure.

[0058] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this present disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0059] The application provides an organic-inorganic hybrid perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell is sequentially stacked with a conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a charge buffer layer and a back electrode layer, and further comprises a molecular modifier and a molecular passivator prepared from alliin decomposition products (mainly diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiocyclohex-4-ene and 3-vinyl-1,2-dithiocyclohex-5-ene), a diphenyl styryl phosphine molecule, a vinyl diphenyl phosphine molecule and a diphenyl p-styryl phosphine molecule; wherein the diphenyl styryl phosphine molecule, the vinyl diphenyl phosphine molecule and the diphenyl p-styryl phosphine molecule can be used separately or mixedly; and the substituent functional groups at different positions of the above molecules include one or more of halogen (Cl, Br, I, etc.), methoxy, hydroxyl, carboxyl, methyl, phosphonic acid group, sulfonic acid group and nitro.

[0060] The application will be described in detail below through examples.

[0061] Example 1

[0062] The diallyl disulfide molecule is used as an interface modifier to prepare the perovskite solar cell, isopropanol is used as a solvent for dissolution, and the concentration of the prepared molecular modifier is 0.5 mg / mL.

[0063] S1: preparing a molecular modifier: in a nitrogen glove box, the diallyl disulfide molecule is dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0064] S2: preparing a perovskite precursor solution: in a nitrogen-filled environment, first, N,N-dimethylformamide and dimethyl sulfoxide mixed solvents are mixed at a volume ratio of 4:1, then CsI, MAI, FAI and PbI2 are dissolved in the mixed solvents at a molar ratio of 0.025:0.025:0.95:1, stirred at 40°C for 6 h, and finally filtered through a filter head to obtain a 1.6M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0065] S3: preparing a hole transport layer: the ITO conductive glass is placed in a UV cleaning machine for 25 min, and then transferred to a dry nitrogen glove box; [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) is dissolved in a dimethoxyethanol solution to prepare a hole transport layer solution, 50 μL of the hole transport layer solution is taken and dropped in the center of the ITO glass, and after spin coating for 40 s, a hole transport layer substrate is obtained by heat treatment at 110°C.

[0066] S4: Preparation of lower interface modification layer: 50 μL of S1 prepared molecular modifier solution is added to the hole transport layer-lower interface modification layer, and is rotated at a speed of 2000-4000 rpm / min for 30 s, and then is heat treated at 100°C for 10 min to obtain the lower interface modification layer;

[0067] S5: Preparation of perovskite light absorption layer: 50 μL of perovskite precursor solution is added to the center of the hole transport layer-lower interface modification layer substrate, and is rotated at a speed of 4000 rpm / min for 50 s, and then is annealed and heat treated at 140°C for 30 min to form a perovskite film, and is placed in a dry place for cooling.

[0068] S6: Preparation of electron transport layer: [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is dissolved in chlorobenzene to prepare an electron transport layer solution, 40 μL of the electron transport layer solution is spin-coated on the perovskite interface modification layer, and an electron transport layer is prepared after heat treatment;

[0069] S7: Preparation of electron blocking layer: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) is dissolved in isopropanol to prepare an electron blocking layer solution, and 100 μL of the electron blocking layer solution is spin-coated on the electron transport layer, and an electron blocking layer is prepared after heat treatment;

[0070] S8: Preparation of metal electrode layer: 120 nm of silver is evaporated above the electron blocking layer by using a thermal evaporation method.

[0071] As shown in Figure 3 , the highest photoelectric conversion efficiency of the finally prepared perovskite solar cell is 23.82%, and the effective area is 0.05 cm 2 .

[0072] Example 2

[0073] The diallyl sulfide molecule is used as an interface modifier to prepare a perovskite solar cell, and isopropanol is used as a solvent for dissolution, and the concentration of the prepared molecular modifier is 0.5 mg / mL:

[0074] S1: Preparation of molecular modifier: in a nitrogen glove box, diallyl sulfide molecules are dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0075] Steps S2-S8 are the same as in Example 1.

[0076] As shown in Figure 4 , the highest photoelectric conversion efficiency of the finally prepared perovskite solar cell is 23.21%, and the effective area is 0.05 cm 2.

[0077] Example 3:

[0078] 3-vinyl-1,2-dithiocyclohex-4-ene molecules were used as interface modifiers for the preparation of perovskite solar cells, and isopropanol was used as a solvent for dissolution. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0079] S1: Preparation of molecular modifier: in a nitrogen glove box, 3-vinyl-1,2-dithiocyclohex-4-ene molecules were dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0080] Steps S2-S8 are the same as in Example 1.

[0081] As shown in Figure 5 , the highest photoelectric conversion efficiency of the finally prepared perovskite solar cell was 23.19%, and the effective area was 0.05 cm 2 .

[0082] Example 4:

[0083] 3-vinyl-1,2-dithiocyclohex-5-ene molecules were used as interface modifiers for the preparation of perovskite solar cells, and isopropanol was used as a solvent for dissolution. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0084] S1: Preparation of molecular modifier: in a nitrogen glove box, 3-vinyl-1,2-dithiocyclohex-5-ene molecules were dissolved in isopropanol as a solvent to obtain a molecular additive solution with a concentration of 0.5 mg / mL;

[0085] Steps S2-S8 are the same as in Example 1.

[0086] As shown in Figure 6 , the highest photoelectric conversion efficiency of the finally prepared perovskite solar cell was 23.31%, and the effective area was 0.05 cm 2 .

[0087] Example 5:

[0088] Vinyl diphenyl phosphine molecules were used as interface modifiers for the preparation of perovskite solar cells, and isopropanol was used as a solvent for dissolution. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0089] S1: Preparation of molecular additive solution: in anhydrous and oxygen-free environment, a proper amount of vinyl diphenyl phosphine molecules were dissolved in isopropanol to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0090] Steps S2-S8 are the same as in Example 1.

[0091] like Figure 7 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 24.34%, and the effective area was 0.05 cm 2 .

[0092] Example 6:

[0093] Distyrylphosphine oxide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropyl alcohol was used as the solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0094] S1: Prepare a molecular additive solution: Dissolve an appropriate amount of distyrylphosphine oxide molecules in isopropanol in an anhydrous and oxygen-free environment to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0095] Steps S2-S8 are the same as in Example 1.

[0096] like Figure 8 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.61%, and the effective area was 0.05 cm 2 .

[0097] Example 7:

[0098] Diphenyl-p-phenylenediphosphine molecules were used as interface modifiers to prepare perovskite solar cells. Isopropyl alcohol was used as the solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0099] S1: Prepare a molecular additive solution: Dissolve an appropriate amount of diphenyl-p-phenylenediphosphine molecules in isopropanol in an anhydrous and oxygen-free environment to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0100] Steps S2-S8 are the same as in Example 1.

[0101] like Figure 9 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 24.32%, and the effective area was 0.05 cm 2 .

[0102] Example 8:

[0103] Perovskite solar cells were prepared using diallyl disulfide molecules as interface modifiers. Isopropyl alcohol was used as the solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0104] S1: Preparation of molecular modifier: In a nitrogen glove box, the diallyl sulfide molecule was dissolved with isopropanol as solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0105] Steps S2: Preparation of perovskite precursor solution and S3: Preparation of hole transport layer are the same as in Example 1.

[0106] S4: Preparation of perovskite light-absorbing layer: 50 μL of perovskite precursor solution was dropped on the center of the hole transport layer substrate, and was rotated at a speed of 4000 rpm / min for 50 s. A perovskite film was formed after annealing heat treatment at 140°C for 30 min, and was cooled in a dry place.

[0107] S5: Preparation of upper interface modification layer: 50 μL of the molecular modifier solution prepared in S1 was dropped on the perovskite light-absorbing layer, and was rotated at a speed of 2000-4000 rpm / min for 30 s. Then, the upper interface modification layer was obtained after heat treatment at 100°C for 10 min.

[0108] Steps S6: Preparation of electron transport layer, S7: Preparation of electron blocking layer and S8: Preparation of metal electrode layer are the same as in Example 1.

[0109] As shown in FIG. 1, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.74%, and the effective area was 0.05 cm 2 . Figure 10

[0110] Example 9:

[0111] The diallyl sulfide molecule was used as an interface modifier for the preparation of a perovskite solar cell. The diallyl sulfide molecule was dissolved with isopropanol as solvent to prepare a molecular modifier solution with a concentration of 0.5 mg / mL.

[0112] S1: Preparation of molecular modifier: In a nitrogen glove box, the diallyl sulfide molecule was dissolved with isopropanol as solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0113] Steps S2-S8 are the same as in Example 8.

[0114] As shown in FIG. 1, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.74%, and the effective area was 0.05 cm 2 . Figure 11

[0115] Example 10:

[0116] ​​The 3-vinyl-1,2-dithiocyclohex-4-ene molecule is used as an interface modifier for the preparation of a perovskite solar cell. Isopropanol is used as a solvent for dissolution, and the concentration of the prepared molecular modifier is 0.5 mg / mL:

[0117] S1: Preparation of a molecular modifier: in a nitrogen glove box, the 3-vinyl-1,2-dithiocyclohex-4-ene molecule is dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0118] Steps S2-S8 are the same as in Example 8.

[0119] As shown in Figure 12 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.17%, and the effective area is 0.05 cm 2 .

[0120] Example 11:

[0121] The 3-vinyl-1,2-dithiocyclohex-5-ene molecule is used as an interface modifier for the preparation of a perovskite solar cell. Isopropanol is used as a solvent for dissolution, and the concentration of the prepared molecular modifier is 0.5 mg / mL:

[0122] S1: Preparation of a molecular modifier: in a nitrogen glove box, the 3-vinyl-1,2-dithiocyclohex-5-ene molecule is dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0123] Steps S2-S8 are the same as in Example 8.

[0124] As shown in Figure 13 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.22%, and the effective area is 0.05 cm 2 .

[0125] Example 12:

[0126] The vinyl diphenyl phosphine molecule is used as an interface modifier for the preparation of a perovskite solar cell. Isopropanol is used as a solvent for dissolution, and the concentration of the prepared molecular modifier is 0.5 mg / mL:

[0127] S1: Preparation of a molecular modifier: in a nitrogen glove box, the vinyl diphenyl phosphine molecule is dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0128] Steps S2-S8 are the same as in Example 8.

[0129] As shown in Figure 14As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.66%, and the effective area was 0.05 cm 2 .

[0130] Example 13:

[0131] Distyrylphosphine oxide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropyl alcohol was used as the solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0132] S1: Preparation of molecular modifier: In a nitrogen glove box, dissolve distyrylphosphine oxide molecules in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0133] Steps S2-S8 are the same as in Example 8.

[0134] like Figure 15 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.53%, and the effective area was 0.05 cm 2 .

[0135] Example 14:

[0136] Diphenyl-p-phenylenediphosphine molecules were used as interface modifiers to prepare perovskite solar cells. Isopropyl alcohol was used as the solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0137] S1: Preparation of molecular modifier: In a nitrogen glove box, dissolve diphenyl 4-phenylphosphine molecules in isopropyl alcohol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0138] Steps S2-S8 are the same as in Example 8.

[0139] like Figure 16 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.67%, and the effective area was 0.05 cm 2 .

[0140] Example 15:

[0141] Diallyl disulfide molecules are doped into a perovskite precursor solution to prepare a perovskite solar cell. The solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and the solution concentration is 0.05 mg / mL.

[0142] S1: Preparation of a molecular passivation agent solution: In a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed in a volume ratio of 4:1, and an appropriate amount of diallyl disulfide molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

[0143] S2: Preparation of a molecular passivation-perovskite precursor solution: In a nitrogen-filled environment, N,N-dimethylformamide and dimethyl sulfoxide mixed solvents were first mixed in a volume ratio of 4:1, and then CsI, MAI, FAI, and PbI2 were dissolved in a molar ratio of 0.025:0.025:0.95:1. Subsequently, 5 μL of the molecular passivation agent solution prepared in S1 was added dropwise into the perovskite precursor solution, and then stirred at 40°C for 6 h. Finally, a 1.6 M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0144] S3: Preparation of a hole transport layer: ITO conductive glass was placed in a UV cleaning machine for 25 min, and then transferred to a dry nitrogen glove box. [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl] phosphonic acid (MeO-2PACz) was dissolved in a dimethoxyethanol solution to prepare a hole transport layer solution. 50 μL of the hole transport layer solution was taken and added dropwise to the center of the ITO glass. After spin coating for 40 s, the hole transport layer substrate was obtained after heat treatment at 110°C.

[0145] S4: Preparation of a molecular passivation-perovskite light-absorbing layer: 50 μL of the molecular passivation-perovskite precursor solution was taken and added dropwise to the center of the hole transport layer substrate. The rotation was carried out at a speed of 4000 rpm / min for 50 s. The perovskite film was formed after annealing and heat treatment at 140°C for 30 min, and then placed in a dry place for cooling.

[0146] Steps S5: Preparation of an electron transport layer, step S6: Preparation of an electron blocking layer, and step S7: Preparation of a metal electrode layer are the same as in Example 1.

[0147] As Figure 17 shown, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.52%, and the effective area was 0.05 cm 2 .

[0148] Example 16:

[0149] The diallyl sulfide molecules are doped into the perovskite precursor solution to prepare the perovskite solar cell, the solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration is 0.05 mg / mL.

[0150] S1: Prepare the molecular passivator solution: in the environment of the nitrogen glove box, mix N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, and dissolve an appropriate amount of diallyl sulfide molecules to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0151] Steps S2-S7 are the same as in Example 15.

[0152] As shown in Figure 18 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.08%, and the effective area is 0.05 cm 2 .

[0153] Example 17:

[0154] The 3-vinyl-1,2-dithiocyclohex-4-ene molecules are doped into the perovskite precursor solution to prepare the perovskite solar cell, the solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration is 0.05 mg / mL.

[0155] S1: Prepare the molecular passivator solution: in the environment of the nitrogen glove box, mix N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, and dissolve an appropriate amount of 3-vinyl-1,2-dithiocyclohex-4-ene molecules to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0156] Steps S2-S7 are the same as in Example 15.

[0157] As shown in Figure 19 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 22.99%, and the effective area is 0.05 cm 2 .

[0158] Example 18:

[0159] The 3-vinyl-1,2-dithiocyclohex-5-ene molecules are doped into the perovskite precursor solution to prepare the perovskite solar cell, the solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration is 0.05 mg / mL.

[0160] S1: Preparation of a molecular passivator solution: In the environment of a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed in a volume ratio of 4:1, and an appropriate amount of 3-vinyl-1,2-dithiocyclohex-5-ene molecules were dissolved to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0161] Steps S2-S7 are the same as in Example 15.

[0162] As shown in Figure 20 , the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.33%, and the effective area was 0.05 cm 2 .

[0163] Example 19:

[0164] Vinyl diphenyl phosphine molecules were doped into the perovskite precursor solution to prepare a perovskite solar cell, and the solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration was 0.05 mg / mL.

[0165] S1: Preparation of a molecular passivator solution: In the environment of a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed in a volume ratio of 4:1, and an appropriate amount of vinyl diphenyl phosphine molecules were dissolved to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0166] Steps S2-S7 are the same as in Example 15.

[0167] As shown in Figure 21 , the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.73%, and the effective area was 0.05 cm 2 .

[0168] Example 19:

[0169] 3-vinyl-1,2-dithiocyclohex-5-ene molecules were doped into the perovskite precursor solution to prepare a perovskite solar cell, and the solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration was 0.05 mg / mL.

[0170] S1: Preparation of a molecular passivator solution: In the environment of a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed in a volume ratio of 4:1, and an appropriate amount of 3-vinyl-1,2-dithiocyclohex-5-ene molecules were dissolved to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0171] Steps S2-S7 are the same as in Example 15.

[0172] As shown in Figure 21 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 24.32%, and the effective area is 0.05 cm 2 .

[0173] Example 20:

[0174] The stilbene-based phosphine oxide molecule is doped into the perovskite precursor solution to prepare the perovskite solar cell, the solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration is 0.05 mg / mL.

[0175] S1: Prepare the molecular passivator solution: in the environment of the nitrogen glove box, mix N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, and dissolve an appropriate amount of stilbene-based phosphine oxide molecule to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0176] Steps S2-S7 are the same as in Example 15.

[0177] As shown in Figure 22 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.31%, and the effective area is 0.05 cm 2 .

[0178] Example 21:

[0179] The stilbene-based phosphine oxide molecule is doped into the perovskite precursor solution to prepare the perovskite solar cell, the solvent of the molecular passivator solution is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone, and the solution concentration is 0.05 mg / mL.

[0180] S1: Prepare the molecular passivator solution: in the environment of the nitrogen glove box, mix N,N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1, and dissolve an appropriate amount of stilbene-based phosphine oxide molecule to obtain a molecular passivator solution with a concentration of 0.05 mg / mL;

[0181] Steps S2-S7 are the same as in Example 15.

[0182] As shown in Figure 23 , the photoelectric conversion efficiency of the perovskite solar cell is measured to be 23.51%, and the effective area is 0.05 cm 2 .

[0183] Comparative Example 1:

[0184] The perovskite solar cell is prepared without adding allicin decomposition product molecules, vinyl diphenyl phosphine and diphenyl p-phenylyl phosphine molecules as interface modifiers and molecular passivators.

[0185] S1: Preparation of perovskite precursor solution: In a nitrogen-filled environment, first mix N,N-dimethylformamide and dimethyl sulfoxide mixed solvent according to a volume ratio of 4:1, then dissolve CsI, MAI, FAI and PbI2 according to a molar ratio of 0.025:0.025:0.95:1, stir at 40 ° C for 6 hours, and finally filter through a filter to obtain a 1.6M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0186] S2: Preparation of hole transport layer: ITO conductive glass was placed in a UV cleaner for 25 min and then transferred to a dry nitrogen glove box; [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz) was dissolved in dimethoxyethanol to prepare a hole transport layer solution. 50 μL of the hole transport layer solution was pipetted and dropped onto the center of the ITO glass. After spin coating for 40 s, the solution was heat-treated at 110°C to obtain a hole transport layer substrate.

[0187] S3: Preparation of perovskite light-absorbing layer: 50 μL of perovskite precursor solution was dropped on the center of the hole transport layer substrate, and the substrate was rotated at 4000 rpm / min for 50 seconds. After annealing at 140°C for 30 minutes, a perovskite film was formed, and the film was placed in a dry place for cooling.

[0188] S4: preparing an electron transport layer: dissolving [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM) in chlorobenzene to prepare an electron transport layer solution, aspirating 40 μL of the electron transport layer solution and spin-coating it on the perovskite layer, and then heat-treating the layer to obtain an electron transport layer;

[0189] S5: preparing an electron blocking layer: dissolving 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropyl alcohol to prepare an electron blocking layer solution, and applying 100 μL of the solution to the electron transport layer by spin coating. The electron blocking layer is then prepared after heat treatment.

[0190] S6: Prepare a metal electrode layer: Use thermal evaporation to evaporate 120 nm of silver on the electron blocking layer.

[0191] like Figure 12 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 19.38%, and the effective area was 0.05 cm 2 ;

[0192] Comparing the data in Comparative Example 1 with Figures 3-23 , it can be found that after molecular modification, the open-circuit voltage and short-circuit current of the device are improved, indicating that after adding the molecules of alliin decomposition product (diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiocyclohexane-4-ene and 3-vinyl-1,2-dithiocyclohexane-5-ene), vinyl diphenyl phosphine, diphenyl styloxy phosphine and diphenyl p-styloxy phosphine, and then heat treatment, the molecular network cross-linked and polymerized can improve the carrier transport, and after the above-mentioned multifunctional molecular modification, the photoelectric conversion efficiency of the perovskite solar cell can be effectively improved.

[0193] As shown in Figure 25 , compared with the perovskite device modified by the molecules of alliin decomposition product (diallyl disulfide), vinyl diphenyl phosphine and diphenyl p-styloxy phosphine, the stability of Comparative Example 1 is poor; according to Figure 3 (b), 7(b), 9(b), 10(b), 14(b), 16(b), 17(b), 21(b), 23(b), the surface quality of the perovskite film after interface modification and bulk incorporation by the molecules of alliin decomposition product (diallyl disulfide), vinyl diphenyl phosphine and diphenyl p-styloxy phosphine is improved, the crystal grain becomes larger, and even PbI2 (white spot) disappears, indicating that the molecules of alliin decomposition product, vinyl diphenyl phosphine, diphenyl styloxy phosphine and diphenyl p-styloxy phosphine can reduce the ion defects of the perovskite surface interface, thereby improving the film quality;

[0194] The above results show that the molecules of alliin decomposition product (mainly diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-dithiocyclohexane-4-ene and 3-vinyl-1,2-dithiocyclohexane-5-ene), vinyl diphenyl phosphine, diphenyl styloxy phosphine and diphenyl p-styloxy phosphine can effectively improve the photoelectric conversion efficiency and stability of the perovskite solar cell, and have high commercial application potential.

[0195] The above only describes the preferred embodiments of the present application, and it should be pointed out that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. An organic-inorganic hybrid perovskite solar cell, characterized in that The perovskite solar cell structure includes: a conductive substrate, a hole transport layer, a perovskite light absorbing layer, an electron transport layer, a charge blocking layer, a back electrode layer; and a molecular modifier and a molecular passivator for modifying the perovskite solar cell; Wherein, the upper interface or the lower interface of the perovskite light absorbing layer is coated with a molecular modifier, or a molecular passivator is added to the perovskite light absorbing layer; The molecular modifier and the molecular passivator both contain one or more of allicin decomposition products, vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine; The molecular modifier further comprises a first organic solvent, wherein the first organic solvent is one or more of methanol, isopropanol, 2-methoxypropanol and chlorobenzene; The decomposition products of allicin are one or more of four product molecules, namely diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-disulfide cyclohex-4-ene and 3-vinyl-1,2-disulfide cyclohex-5-ene.

2. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that The molecular deactivator further comprises a second organic solvent, which is at least one of acetonitrile, isopropyl alcohol, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.

3. The method for preparing an organic-inorganic hybrid perovskite solar cell according to any one of claims 1 to 2, characterized in that: The preparation method comprises the following steps: S1, preparing a perovskite precursor solution; S2. Pre-treating the conductive substrate; S3, spin coating a hole transport layer solution on the pretreated conductive substrate, and annealing to obtain a hole transport layer; S4. Preparing a molecularly modified perovskite light-absorbing layer on the hole transport layer to obtain a perovskite light-absorbing layer-upper interface modification layer or a perovskite light-absorbing layer-lower interface modification layer or a perovskite light-absorbing layer with a molecular passivator added; S5. Sequentially spin-coating an electron transport layer and an electron blocking layer on the molecularly modified perovskite light-absorbing layer, and thermally evaporating a metal electrode layer on top of the electron blocking layer to obtain an organic-inorganic hybrid perovskite solar cell.

4. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 3, wherein: When step S4 is to prepare a perovskite light absorbing layer-lower interface modification layer, the molecular modifier is first spin-coated on the hole transport layer obtained in step S3. After annealing, the perovskite precursor solution of step S1 is spin-coated on the conductive substrate with the hole transport layer having the lower interface modification to obtain the perovskite light absorbing layer-lower interface modification layer.

5. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 3, wherein: When step S4 is to prepare a perovskite light absorbing layer-upper interface modification layer, the perovskite precursor solution of step S1 is first spin-coated on the hole transport layer obtained in step S3, and the perovskite light absorbing layer is obtained after annealing and heat treatment. Then, the molecular modifier is spin-coated or scraped on the perovskite light absorbing layer, and the perovskite light absorbing layer-upper interface modification layer is obtained after annealing and heat treatment.

6. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 3, wherein: When step S4 is to add a molecular passivator to the perovskite light-absorbing layer, the molecular passivator is mixed with the perovskite precursor solution of step S1 and then spin-coated on a conductive substrate with a hole transport layer. After annealing and heat treatment, the perovskite light-absorbing layer with the added molecular passivator is obtained.

7. The method for preparing an organic-inorganic hybrid perovskite solar cell according to any one of claims 5 to 6, characterized in that: The concentration of the spin-coated molecular modifier was 0.1-5 mg / mL.

8. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 7, characterized in that: The concentration of the added molecular passivating agent is 0.01-0.5 mg / mL.

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