Organic-inorganic hybrid perovskite solar cell and preparation method thereof

Abstract

The invention belongs to the technical field of solar cells, and particularly provides an organic-inorganic hybrid perovskite solar cell and a preparation method thereof. Comprising 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 hole transport layer, wherein the hole transport layer and the hole transport layer are formed by using allicin decomposition product molecules (diallyl sulfide, diallyl disulfide, 3-vinyl-1, 2-dithiocyclohexane-4-ene and 3-vinyl-1, 2-dithiocyclohexane-4-ene). According to the perovskite solar cell prepared from a molecular modifier and a molecular passivator which are respectively prepared from 1, 2-dithiocyclohexane-5-ene, vinyl diphenylphosphine, stilbene phosphine oxide and diphenyl p-styryl phosphine molecules, the transport and exchange efficiency of charges at the surface interface of a perovskite light absorption layer is improved; and the overall photoelectric conversion efficiency and stability of the device are effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar cells, and in particular relates to an organic-inorganic hybrid perovskite solar cell and a preparation method thereof. Background Art

[0002] Organic-inorganic hybrid perovskite materials have received widespread attention in the photovoltaic field due to their excellent photoelectric properties, low cost and wide sources. After more than ten years of technological development, the photoelectric conversion efficiency of organic-inorganic hybrid perovskite perovskite solar cells has soared from 3.8% in 2009 to 26.1% in 2023, catching up with the level of crystalline silicon solar cells on the market. It is considered to be the third-generation solar cell with the most commercial potential.

[0003] However, there are still many problems inside the perovskite solar cells prepared by low-temperature spin coating. For example, too many internal defects will lead to non-radiative recombination of carriers, reducing the photoelectric conversion efficiency of the device. Not only that, external factors such as water and oxygen will cause the perovskite material to decompose, greatly reducing the performance of the device. These are major challenges currently faced by perovskite solar cells in achieving commercial applications.

[0004] At present, in order to solve these problems, a multifunctional molecular strategy can be used to regulate the perovskite film, improve the quality of the perovskite film and optimize the contact with the transport layer material, thereby improving the photoelectric conversion efficiency and stability of the perovskite solar cell. What kind of multifunctional molecular strategy should be used to comprehensively improve the photoelectric conversion efficiency and stability of perovskite solar cells is an urgent problem to be solved. Summary of the invention

[0005] In view of the deficiencies of the above-mentioned prior art, the present invention utilizes decomposition products of allicin (a total 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), vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine molecules to improve the perovskite crystallization process, and forms a corresponding polymer molecule cross-linked grid through heat treatment polymerization, thereby improving the transport efficiency of carriers at the surface interface of the perovskite light-absorbing layer; at the same time, the decomposition products of allicin, vinyl diphenylphosphine and diphenyl p-styryl phosphine molecules have multifunctional molecules with improved conductivity and passivation effects, thereby improving the overall photoelectric conversion efficiency of the device and the stability of the device.

[0006] In order to solve the problems existing in the prior art, the present invention proposes an organic-inorganic hybrid perovskite solar cell, the structure of which includes: 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 passivator 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 a molecular passivator is added to the perovskite light absorbing layer;

[0008] The molecular modifier and the molecular deactivator both contain one or more of allicin decomposition products, vinyl diphenyl phosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine.

[0009] Furthermore, the molecular modifier also includes a first organic solvent, and the first organic solvent is one or more of methanol, isopropanol, 2-methoxypropanol and chlorobenzene.

[0010] Furthermore, the molecular passivator also contains a second organic solvent, and the second organic solvent is at least one of acetonitrile, isopropanol, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.

[0011] Furthermore, the decomposition product of allicin is one or more of four product molecules including diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-disulfide cyclohex-4-ene and 3-vinyl-1,2-disulfide cyclohex-5-ene.

[0012] The present invention also provides a method for preparing the above-mentioned organic-inorganic hybrid perovskite solar cell, the preparation method comprising the following steps:

[0013] S1. Prepare a perovskite precursor solution; dissolve the perovskite precursor in a third organic solvent in a nitrogen glove box without water or oxygen to prepare a perovskite precursor solution with a concentration of 1.3-1.8M, and heat and stir at a temperature of 20-80°C for 2-12h; the third organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and when there are multiple solvents, the volume ratio of the mixed solvent is 6:1-2:1;

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

[0015] S3, spin coating a hole transport layer solution on the pretreated conductive substrate, and annealing to obtain a hole transport layer; the spin coating time of the hole transport layer solution is 40 seconds, and the annealing temperature is 110° C.;

[0016] 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;

[0017] 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 the electron blocking layer to obtain an organic-inorganic hybrid perovskite solar cell.

[0018] Further, 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, and 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;

[0019] The molecular modifier is spin-coated on the hole transport layer at a spin-coating speed of 2000-4000 rpm / min and a spin-coating time of 10-40 s; the annealing temperature is 100-150° C. and the treatment time is 10-20 min.

[0020] Further, 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, and 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;

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

[0022] Furthermore, 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 having a hole transport layer, and the perovskite light-absorbing layer with the added molecular passivator is obtained after annealing and heat treatment;

[0023] Wherein, when the molecular passivator and the perovskite precursor solution are mixed, the added amount of the molecular passivator is 2.5 μL-15 μL.

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

[0025] Furthermore, the concentration of the added molecular passivator is 0.01-0.5 mg / mL.

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

[0027] 1. The present invention utilizes allicin decomposition product molecules, distyryl phosphine oxide, vinyl diphenyl phosphine and diphenyl p-phenylyl phosphine molecules as interface modifiers to modify the surface of perovskite. After annealing and heat treatment, the molecules undergo cross-linking polymerization to form a dense molecular network above the perovskite, thereby hindering the invasion of external water and oxygen, preventing the perovskite from decomposing, and improving 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; in addition, the S atoms and P atoms in the allicin decomposition product molecules, distyryl phosphine oxide, vinyl diphenyl phosphine and diphenyl p-phenylyl phosphine molecules can interact with the defects on the surface of the perovskite film, thereby inhibiting the 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, distyryl phosphine oxide, vinyl diphenyl phosphine and diphenyl p-styryl phosphine 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 the performance.

[0029] 3. The present invention utilizes allicin decomposition products, vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl p-phenylyl phosphine molecules to mix into a 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-phenylyl phosphine molecules can coordinate with Pb+ in the perovskite precursor solution, reduce defects in the perovskite bulk phase, and further improve performance.

[0030] 4. The molecular protection effect of the present invention is not limited 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, but are not intended to limit the present disclosure, wherein:

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

[0033] Figure 2 The present invention provides a molecular structure before and after heat treatment, wherein (a) is the structure of diallyl disulfide molecule before and after heat treatment, (b) is the structure of diallyl sulfide before and after heat treatment, (c) is the structure of 3-vinyl-1,2-dithiocyclohex-4-ene before and after heat treatment, (d) is the structure of 3-vinyl-1,2-dithiocyclohex-5-ene before and after heat treatment, (e) is the structure of vinyl diphenylphosphine before and after heat treatment, (f) is the structure of distyryl phosphine oxide before and after heat treatment, and (g) is the structure of diphenyl p-styryl phosphine before and after heat treatment;

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

[0035] Figure 4 This is a current-voltage curve of the interface-modified perovskite solar cell under the diallyl sulfide molecule prepared in Example 2 of the present invention;

[0036] Figure 5 This is a current-voltage curve of the interface-modified perovskite solar cell of the 3-vinyl-1,2-disulfide cyclohex-4-ene molecule prepared in Example 3 of the present invention;

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

[0038] Figure 7 The current-voltage curve of the interface-modified perovskite solar cell prepared under the vinyl diphenylphosphine molecule according to Example 5 of the present invention (a) and the SEM image of the perovskite layer according to Example 5 (b);

[0039] Figure 8 This is a current-voltage curve of the interface-modified perovskite solar cell prepared in Example 6 of the present invention under the distyrylphosphine oxide molecule;

[0040] Fig. 9 The current-voltage curve of the interface-modified perovskite solar cell prepared in Example 7 of the present invention is (a) and the SEM image of the perovskite layer of Example 7 is (b);

[0041] Fig.10 The current-voltage curve of the interface-modified perovskite solar cell on the diallyl disulfide molecule prepared in Example 8 of the present invention and the SEM image of the perovskite layer in Example 8 (b);

[0042] Fig.11 This is a current-voltage curve of the interface-modified perovskite solar cell on the diallyl sulfide molecule prepared in Example 9 of the present invention;

[0043] Fig.12 This is a current-voltage curve of the perovskite solar cell with interface modification on the 3-vinyl-1,2-disulfide cyclohex-5-ene molecule prepared in Example 10 of the present invention;

[0044] Fig.13 This is a current-voltage curve of the perovskite solar cell with interface modification on the 3-vinyl-1,2-dithiocyclohex-5-ene molecule prepared in Example 11 of the present invention;

[0045] Fig.14 The current-voltage curve of the interface-modified perovskite solar cell on the vinyl diphenylphosphine molecule prepared in Example 12 of the present invention and the SEM image of the perovskite layer in Example 12 (b);

[0046] Fig.15 This is a current-voltage curve of the interface-modified perovskite solar cell on the distyrylphosphine oxide molecule prepared in Example 13 of the present invention;

[0047] Fig.16 The current-voltage curve of the interface-modified perovskite solar cell on the diphenyl-p-phenylvinylphosphine molecule prepared in Example 14 of the present invention and the SEM image of the perovskite layer in Example 14 (b);

[0048] Fig.17 The current-voltage curve of the perovskite solar cell doped with diallyl disulfide molecules prepared in Example 15 of the present invention (a) and the SEM image of the perovskite layer of Example 15 (b);

[0049] Fig.18 This is a current-voltage curve of a perovskite solar cell doped with diallyl sulfide molecules prepared in Example 16 of the present invention;

[0050] Fig.19 This is a current-voltage curve of a perovskite solar cell doped with 3-vinyl-1,2-disulfide cyclohex-4-ene molecules prepared in Example 17 of the present invention;

[0051] Fig. 20 This is a current-voltage curve of a perovskite solar cell doped with 3-vinyl-1,2-disulfide cyclohex-5-ene molecules prepared in Example 18 of the present invention;

[0052] Fig.21The current-voltage curve of the perovskite solar cell infiltrated with bulk vinyl diphenylphosphine molecules prepared in Example 19 of the present invention and the SEM image of the perovskite layer in Example 19 (b);

[0053] Fig. 22 This is a current-voltage curve of a perovskite solar cell in which bulk phase infiltration of distyrylphosphine oxide molecules is carried out according to Example 20 of the present invention;

[0054] Fig.23 The current-voltage curve of the perovskite solar cell doped with diphenyl-p-phenylphenylphosphine molecules prepared in Example 21 of the present invention and the SEM image of the perovskite layer of Example 21 (b);

[0055] Fig.24 The current-voltage curve diagram of the perovskite solar cell prepared in Comparative Example 1 of the present invention (a) and the SEM image of the perovskite layer of Comparative Example 1 (b);

[0056] Fig.25 This is a stability curve comparison diagram of the perovskite solar cells with interface modification on diallyl disulfide, vinyl diphenylphosphine and diphenyl p-phenylvinylphosphine molecules prepared respectively under the conditions of Examples 1, 5 and 7 of the present invention and the perovskite solar cell prepared in Comparative Example 1. DETAILED DESCRIPTION

[0057] In order to make the purpose, technical solution and advantages of the embodiments of the present disclosure clearer, the technical solution of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by those skilled in the art without creative work also fall within the scope of protection 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 those skilled in the art to which the subject matter of the 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 consistent with their meaning in the context of the specification and the relevant art, and will not be interpreted in an idealized or overly formal form unless otherwise explicitly defined herein.

[0059] The present invention provides an organic-inorganic hybrid perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell structure is sequentially stacked and arranged as 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 also includes a molecular modifier and a molecular passivator prepared from a decomposition product of allicin (mainly diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-disulfide cyclohex-4-ene and 3-vinyl-1,2-disulfide cyclohex-5-ene), a distyryl phosphine oxide molecule, a vinyl diphenyl phosphine molecule and a diphenyl p-phenyl phosphine molecule; wherein the distyryl phosphine oxide molecule, the vinyl diphenyl phosphine molecule and the diphenyl p-phenyl phosphine molecule can be used separately or in combination. For the above molecules, the substituent functional groups at different positions include one or more of halogen (Cl, Br, I, etc.), methoxy, hydroxyl, carboxyl, methyl, phosphonic acid, sulfonic acid, nitro, etc.

[0060] The following is a specific description through examples.

[0061] Example 1

[0062] Diallyl disulfide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

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

[0064] S2: Preparation of perovskite precursor solution: In a nitrogen-filled environment, firstly, N,N-dimethylformamide and dimethyl sulfoxide mixed solvent were mixed at a volume ratio of 4:1, and then CsI, MAI, FAI and PbI2 were dissolved therein 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 1.6 M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0065] S3: Preparation of hole transport layer: Place the ITO conductive glass in a UV cleaning machine for 25 minutes, and then transfer it to a dry nitrogen glove box; Dissolve [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) in a dimethoxyethanol solution to prepare a hole transport layer solution, draw 50 μL of the hole transport layer solution, drop it on the center of the ITO glass, spin coat for 40 seconds, and heat treat at 110°C to obtain a hole transport layer substrate;

[0066] S4: preparing the lower interface modification layer: taking 50 μL of the molecular modifier solution prepared in S1 and dropping it on the hole transport layer-lower interface modification layer, rotating at a speed of 2000-4000 rpm / min for 30 seconds, and then heat treating at 100° C. for 10 minutes to obtain the lower interface modification layer;

[0067] S5: Preparation of perovskite light-absorbing layer: Pipette 50 μL of perovskite precursor solution and drop it in the center of the hole transport layer-lower interface modification layer substrate, rotate at 4000 rpm / min for 50 seconds, anneal and heat treat at 140°C for 30 minutes to form a perovskite film, and place it in a dry place for cooling.

[0068] S6: preparing an electron transport layer: dissolving [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM) in chlorobenzene to prepare an electron transport layer solution, taking 40 μL of the electron transport layer solution and spin coating it on the perovskite interface modification layer, and preparing the electron transport layer after heat treatment;

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

[0070] S8: Prepare a metal electrode layer: Use thermal evaporation to evaporate 120 nm of silver on the electron blocking layer.

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

[0072] Example 2

[0073] Diallyl sulfide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0074] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving diallyl sulfide molecules using 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 those in Example 1.

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

[0077] Embodiment 3:

[0078] The perovskite solar cell was prepared by using 3-vinyl-1,2-dithiocyclohex-4-ene molecules as interface modifiers, and isopropanol was used as solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0079] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving 3-vinyl-1,2-dithiocyclohex-4-ene molecules using 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 those in Example 1.

[0081] like Figure 5 As shown in the figure, the photoelectric conversion efficiency of the final prepared perovskite solar cell is as high as 23.19%, and the effective area is 0.05cm 2 .

[0082] Embodiment 4:

[0083] The perovskite solar cell was prepared by using 3-vinyl-1,2-dithiocyclohex-5-ene molecule as an interface modifier, and isopropanol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0084] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving 3-vinyl-1,2-dithiocyclohex-5-ene molecules using 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 those in Example 1.

[0086] like Figure 6 As shown in the figure, the photoelectric conversion efficiency of the final perovskite solar cell is as high as 23.31%, and the effective area is 0.05cm 2 .

[0087] Embodiment 5:

[0088] Vinyl diphenylphosphine molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0089] S1: preparing a molecular additive solution: dissolving an appropriate amount of vinyl diphenylphosphine molecules using isopropanol in an anhydrous and oxygen-free environment to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0090] Steps S2-S8 are the same as those 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] Embodiment 6:

[0093] The distyrylphosphine oxide molecule was used as an interface modifier to prepare the perovskite solar cell. Isopropanol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0094] S1: preparing a molecular additive solution: dissolving an appropriate amount of distyrylphosphine oxide molecules using 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 those 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] Embodiment 7:

[0098] The diphenyl-p-phenylphenylphosphine molecule was used as an interface modifier to prepare the perovskite solar cell. Isopropanol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0099] S1: preparing a molecular additive solution: dissolving an appropriate amount of diphenyl styrylphosphine molecules using 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 those in Example 1.

[0101] like Fig. 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] Embodiment 8:

[0103] Diallyl disulfide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0104] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving diallyl disulfide molecules using isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL;

[0105] Step S2: preparing the perovskite precursor solution and step S3: preparing the 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 dripped 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.

[0107] S5: preparing the upper interface modification layer: taking 50 μL of the molecular modifier solution prepared in S1 and dropping it on the perovskite light absorbing layer, rotating at a speed of 2000-4000 rpm / min for 30 seconds, and then heat treating at 100°C for 10 minutes to obtain the upper interface modification layer;

[0108] Step S6: preparing the electron transport layer, step S7: preparing the electron blocking layer and step S8: preparing the metal electrode layer are the same as in Example 1.

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

[0110] Embodiment 9:

[0111] Diallyl sulfide molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0112] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving diallyl sulfide molecules using isopropanol as a 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] like Fig.11 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.22% and the effective area was 0.05 cm 2 .

[0115] Embodiment 10:

[0116] The perovskite solar cell was prepared by using 3-vinyl-1,2-dithiocyclohex-4-ene molecules as interface modifiers, and isopropanol was used as solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0117] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving 3-vinyl-1,2-dithiocyclohex-4-ene molecules using 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] like Fig.12 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.17% and the effective area was 0.05 cm 2 .

[0120] Embodiment 11:

[0121] The perovskite solar cell was prepared by using 3-vinyl-1,2-dithiocyclohex-5-ene molecule as an interface modifier, and isopropanol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0122] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving 3-vinyl-1,2-dithiocyclohex-5-ene molecules using 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] like Fig.13 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.22% and the effective area was 0.05 cm 2 .

[0125] Embodiment 12:

[0126] Vinyl diphenylphosphine molecules were used as interface modifiers to prepare perovskite solar cells. Isopropanol was used as a solvent to dissolve the molecules. The concentration of the prepared molecular modifiers was 0.5 mg / mL:

[0127] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving vinyl diphenylphosphine molecules using 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] like Fig.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] Embodiment 13:

[0131] The distyrylphosphine oxide molecule was used as an interface modifier to prepare the perovskite solar cell. Isopropanol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0132] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving a distyrylphosphine oxide molecule using 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 Fig.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] Embodiment 14:

[0136] The diphenyl-p-phenylphenylphosphine molecule was used as an interface modifier to prepare the perovskite solar cell. Isopropyl alcohol was used as a solvent to dissolve the molecule. The concentration of the prepared molecular modifier was 0.5 mg / mL:

[0137] S1: preparing a molecular modifier: in a nitrogen glove box, dissolving diphenyl phenylphosphine molecules using isopropanol 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 Fig.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] Embodiment 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: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at 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 molecular passivation-perovskite precursor solution: In a nitrogen-filled environment, firstly, N,N-dimethylformamide and dimethyl sulfoxide mixed solvent were mixed in a volume ratio of 4:1, and then CsI, MAI, FAI and PbI2 were dissolved in it in a molar ratio of 0.025:0.025:0.95:1, and then 5 μL of the molecular passivator solution prepared in S1 was added to the perovskite precursor solution, and then stirred at 40 ° C for 6 hours, and finally filtered through a filter head to obtain a 1.6 M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0144] S3: Preparation of hole transport layer: Place the ITO conductive glass in a UV cleaning machine for 25 minutes, and then transfer it to a dry nitrogen glove box; Dissolve [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) in a dimethoxyethanol solution to prepare a hole transport layer solution, draw 50 μL of the hole transport layer solution, drop it on the center of the ITO glass, spin coat for 40 seconds, and heat treat at 110°C to obtain a hole transport layer substrate;

[0145] S4: Preparation of molecular passivation-perovskite light-absorbing layer: Pipette 50 μL of molecular passivation-perovskite precursor solution and drop it in the center of the hole transport layer substrate, rotate at 4000 rpm / min for 50 seconds, anneal and heat treat at 140°C for 30 minutes to form a perovskite film, and place it in a dry place for cooling.

[0146] Step S5: preparing the electron transport layer, step S6: preparing the electron blocking layer and step S7: preparing the metal electrode layer are the same as in Example 1.

[0147] like Fig.17 As shown in Figure 2, 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] Embodiment 16:

[0149] Diallyl sulfide 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.

[0150] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at a volume ratio of 4:1, and an appropriate amount of diallyl sulfide molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

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

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

[0153] Embodiment 17:

[0154] 3-vinyl-1,2-dithiocyclohex-4-ene 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.

[0155] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at a volume ratio of 4:1, and an appropriate amount of 3-vinyl-1,2-dithiocyclohex-4-ene molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

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

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

[0158] Embodiment 18:

[0159] 3-vinyl-1,2-dithiocyclohex-5-ene 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.

[0160] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at 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 passivation agent solution with a concentration of 0.05 mg / mL;

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

[0162] like Fig. 20 As shown in Figure 2, 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] Embodiment 19:

[0164] Vinyl diphenylphosphine 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.

[0165] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at a volume ratio of 4:1, and an appropriate amount of vinyl diphenylphosphine molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

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

[0167] like Fig.21 As shown in Figure 2, 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] Embodiment 19:

[0169] 3-vinyl-1,2-dithiocyclohex-5-ene 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.

[0170] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at 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 passivation agent solution with a concentration of 0.05 mg / mL;

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

[0172] like Fig.21 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 .

[0173] Embodiment 20:

[0174] Distyrylphosphine oxide 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.

[0175] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at a volume ratio of 4:1, and an appropriate amount of distyrylphosphine oxide molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

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

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

[0178] Embodiment 21:

[0179] Diphenyl p-phenylphenylphosphine 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.

[0180] S1: preparing a molecular passivation agent solution: in a nitrogen glove box, N,N-dimethylformamide and dimethyl sulfoxide were mixed at a volume ratio of 4:1, and an appropriate amount of diphenyl p-phenylphenylphosphine molecules were dissolved to obtain a molecular passivation agent solution with a concentration of 0.05 mg / mL;

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

[0182] like Fig.23 As shown in Figure 2, the photoelectric conversion efficiency of the perovskite solar cell was measured to be 23.51%, and the effective area was 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-phenylphenyl phosphine molecules as interface modifiers and molecular passivators.

[0185] S1: Preparation of perovskite precursor solution: In a nitrogen-filled environment, firstly, N,N-dimethylformamide and dimethyl sulfoxide mixed solvent were mixed at a volume ratio of 4:1, and then CsI, MAI, FAI and PbI2 were dissolved therein 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 1.6 M perovskite precursor solution Cs 0.025 MA 0.025 FA 0.95 PbI3;

[0186] S2: Preparation of hole transport layer: Place the ITO conductive glass in a UV cleaning machine for 25 minutes, and then transfer it to a dry nitrogen glove box; Dissolve [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) in a dimethoxyethanol solution to prepare a hole transport layer solution, draw 50 μL of the hole transport layer solution, drop it on the center of the ITO glass, spin coat for 40 seconds, and heat treat at 110°C to obtain a hole transport layer substrate;

[0187] S3: Preparation of perovskite light-absorbing layer: Pipette 50 μL of perovskite precursor solution and drop it in the center of the hole transport layer substrate, rotate at 4000 rpm / min for 50 seconds, anneal and heat treat at 140°C for 30 minutes to form a perovskite film, and place it 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, taking 40 μL of the electron transport layer solution and spin coating it on the perovskite layer, and preparing the electron transport layer after heat treatment;

[0189] S5: preparing an electron blocking layer: dissolving 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol to prepare an electron blocking layer solution, and applying 100 μL of the solution to the electron transport layer by spin coating, and preparing an electron blocking layer 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 Fig.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] Comparative Example 1 and Figure 3-23 By comparing the data in, 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 allicin decomposition product molecules (diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-disulfide cyclohex-4-ene and 3-vinyl-1,2-disulfide cyclohex-5-ene), vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine molecules respectively, and then heat-treated, the cross-linked polymerized molecular network can improve the transport of carriers. After the above-mentioned multifunctional molecular modification, the photoelectric conversion efficiency of perovskite solar cells can be effectively improved.

[0193] like Fig.25 As shown, compared with the perovskite devices modified with allicin decomposition product molecules (diallyl disulfide), vinyl diphenylphosphine and diphenyl p-phenylphenylphosphine molecules, the stability of comparative example 1 is poor; according to Figure 3 As shown in (b), 7(b), 9(b), 10(b), 14(b), 16(b), 17(b), 21(b), and 23(b), the surface quality of the perovskite film after interface modification and bulk incorporation of allicin decomposition product molecules (diallyl disulfide), vinyl diphenylphosphine and diphenyl-p-phenylylphosphine molecules is improved, the grain size becomes larger, and even PbI2 (white spots) disappears, indicating that allicin decomposition product molecules, vinyl diphenylphosphine, diphenylphosphine oxide and diphenyl-p-phenylylphosphine molecules can reduce the ion defects on the perovskite surface interface, thereby improving the film quality;

[0194] The above results show that the allicin decomposition product molecules (mainly diallyl sulfide, diallyl disulfide, 3-vinyl-1,2-disulfide cyclohex-4-ene and 3-vinyl-1,2-disulfide cyclohex-5-ene), vinyl diphenylphosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine molecules of the present invention can effectively improve the photoelectric conversion efficiency and stability of perovskite solar cells, and have high commercial application potential.

[0195] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An organic-inorganic hybrid perovskite solar cell, characterized in that: The perovskite solar cell structure 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 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 deactivator both contain one or more of allicin decomposition products, vinyl diphenyl phosphine, distyryl phosphine oxide and diphenyl p-styryl phosphine.

2. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that: The molecular modifier further comprises a first organic solvent, which is one or more of methanol, isopropanol, 2-methoxypropanol and chlorobenzene.

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

4. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that: 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.

5. The method for preparing the organic-inorganic hybrid perovskite solar cell according to any one of claims 1 to 4, 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 the electron blocking layer to obtain an organic-inorganic hybrid perovskite solar cell.

6. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that: 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 a hole transport layer having a lower interface modification to obtain a perovskite light absorbing layer-lower interface modification layer.

7. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that: 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, and 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.

8. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that: 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, and the perovskite light absorbing layer with the added molecular passivator is obtained after annealing and heat treatment.

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

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

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