Perovskite precursor solution additive, perovskite precursor solution, and photoelectric device

Abstract

The embodiments of the present application relate to the technical field of perovskite solar cells; and provide a perovskite precursor solution additive, a perovskite precursor solution, a photoelectric device, a perovskite solar cell, a photovoltaic module and a photovoltaic system. The perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde and a transition metal salt of a polyhydroxy ketone. As a perovskite precursor solution additive, same improves the film-forming crystallization quality of perovskite precursor solutions having different components, and also improves the film-forming crystallization quality of perovskite precursor solutions that have been subjected to different processes.

Description

Perovskite precursor solution additive, perovskite precursor solution and optoelectronic device

[0001] The present application claims priority to the Chinese patent application No. 202411300139.8, filed on September 18, 2024, and entitled “Perovskite precursor solution additive, perovskite precursor solution and optoelectronic device”, the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of solar cells, in particular to a perovskite precursor solution additive, a perovskite precursor solution and an optoelectronic device, a perovskite solar cell, a photovoltaic module and a photovoltaic system. BACKGROUND

[0003] Perovskite tandem cells have gradually become a hot direction in the field of world photovoltaic research. In the preparation process of perovskite devices, how to prepare perovskite thin films with low defect state density is the key to realize the preparation of high-efficiency perovskite devices. However, the variable degree of perovskite components is large, and different components of perovskite also have different suitable additives for auxiliary film-forming crystallization. The existing additives have different practicability for different components of perovskite, and cannot be applied to a wide range of perovskite components: the additive of long-chain ammonium salt is easy to form 2D structure perovskite in the bulk phase to improve the performance of the device, but the two-dimensional perovskite diffuses and disappears in the bulk phase during photothermal aging process, and it is difficult to maintain the high efficiency of the device. MACl additive is not suitable for FACs system perovskite. Zinc triflate (Zn(OOSCF3)2) and phosphatidylcholine additives are only suitable for components containing a large amount of MA for blade coating, and the scope of application is narrow.

[0004] It can be seen that the current additives for preparing perovskite have the following defects: poor device efficiency and stability, poor adaptability to different preparation processes, and low film-forming crystallization quality. SUMMARY

[0005] The embodiments of the present application provide a perovskite precursor solution additive, a perovskite precursor solution and an optoelectronic device, a perovskite solar cell, a photovoltaic module and a photovoltaic system to solve or alleviate the technical problems proposed above. The perovskite precursor solution additive of the embodiments of the present application can improve the film-forming crystallization quality of perovskite with different components and different preparation processes.

[0006] In a first aspect, the embodiments of the present application provide a perovskite precursor solution additive, which comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone.

[0007] Optionally, the alkaline earth metal salt of the polyhydroxy aldehyde comprises an alkaline earth metal salt of gluconic acid.

[0008] The alkaline earth metal salt of the polyhydroxy ketone comprises an alkaline earth metal salt of fructose acid.

[0009] The transition metal salt of the polyhydroxy aldehyde comprises a transition metal salt of gluconic acid.

[0010] The transition metal salt of the polyhydroxy ketone comprises a transition metal salt of fructose acid.

[0011] Optionally, the alkaline earth metal in the alkaline earth metal salt of the polyhydroxy aldehyde comprises one or more of magnesium, calcium, strontium, and barium.

[0012] The alkaline earth metal in the alkaline earth metal salt of the polyhydroxy ketone comprises one or more of magnesium, calcium, strontium, and barium.

[0013] The transition metal in the transition metal salt of the polyhydroxy aldehyde comprises one or more of cobalt, nickel, copper, and zinc.

[0014] The transition metal in the transition metal salt of the polyhydroxy ketone comprises one or more of cobalt, nickel, copper, and zinc.

[0015] In a second aspect, the embodiments of the present application provide a perovskite precursor solution, comprising the perovskite precursor solution additive as described above.

[0016] Optionally, the mass percentage of the perovskite precursor solution additive in the perovskite precursor solution is 0.001wt%-4wt%.

[0017] Optionally, the perovskite precursor solution further comprises a perovskite material and an organic solvent.

[0018] The perovskite material has an ABX3 structure, wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

[0019] In a third aspect, the embodiments of the present application provide a photoelectric device, comprising a perovskite light-absorbing layer formed by a perovskite precursor solution.

[0020] The perovskite precursor solution comprises a perovskite material, an organic solvent, and a perovskite precursor solution additive.

[0021] The perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone.

[0022] In a fourth aspect, the embodiments of the present application provide a perovskite solar cell, comprising a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is formed by a perovskite precursor solution;

[0023] The perovskite precursor solution comprises a perovskite material, an organic solvent, and a perovskite precursor solution additive;

[0024] The perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone.

[0025] In a fifth aspect, the embodiments of the present application provide a photovoltaic module, comprising:

[0026] At least one cell string, wherein the cell string comprises at least two perovskite solar cells as described above.

[0027] In a sixth aspect, the embodiments of the present application provide a photovoltaic system, comprising a photovoltaic module as described above.

[0028] The embodiments of the present application can have the following advantages:

[0029] (1) By analyzing the crystallization performance of the prepared perovskite light-absorbing layer through X-ray diffraction and fluorescence spectroscopy, it can be seen that: using one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone as an additive added to the precursor solution can significantly improve the efficiency and stability of the perovskite thin device.

[0030] (2) By analyzing the crystallization performance of the prepared perovskite light-absorbing layer through X-ray diffraction and fluorescence spectroscopy, it can also be seen that: one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone as an additive can significantly improve the film-forming and crystallization quality of perovskite with different components and perovskite prepared by different process methods. BRIEF DESCRIPTION OF DRAWINGS

[0031] In the drawings, like reference numerals refer to like elements throughout the various drawings. The drawings are not necessarily to scale, emphasis instead being placed on illustrating principles of the application. It should be understood that the drawings are merely depictions of some embodiments of the application and should not be construed as limiting the scope of the application.

[0032] FIG. 1 is a structural schematic diagram of a perovskite single-junction cell according to an embodiment of the present application;

[0033] FIG. 2 is a structural schematic diagram of a perovskite tandem cell according to an embodiment of the present application;

[0034] Fig. 3 is a schematic diagram of a crystalline silicon / perovskite stacked cell according to an embodiment of the present application;

[0035] Fig. 4 is an X-ray diffraction pattern of a FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 )3 perovskite film prepared by a spin-coating method according to an embodiment of the present application;

[0036] Fig. 5 is a fluorescence diagram of perovskite films with different additives according to an embodiment of the present application.

[0037] Legend of reference signs:

[0038] 11, first back electrode; 12, first electron transport layer; 13, first perovskite light absorption layer; 14, first hole transport layer; 15, first transparent conductive glass layer;

[0039] 21, second back electrode; 22, light absorption layer; 23, second hole transport layer; 24, second electron transport layer; 25, second perovskite light absorption layer; 26, third hole transport layer; 27, second transparent conductive glass layer. Embodiments of the present application

[0040] The embodiments of the present application are described in detail below with reference to the accompanying drawings. In the drawings, the size of layers, regions, elements and the relative sizes thereof are exaggerated for clarity. The same or similar components are denoted by the same reference numerals throughout the drawings. The embodiments described below with reference to the drawings are merely exemplary and are used to explain the present application, and should not be construed as limiting the present application. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0041] The present application aims to provide a perovskite precursor solution additive, using sugar salts of alkaline earth metals (alkaline earth metal salts of polyhydroxy aldehydes, alkaline earth metal salts of polyhydroxy ketones), sugar salts of transition metals (transition metal salts of polyhydroxy aldehydes, transition metal salts of polyhydroxy ketones) as additives, which can significantly improve the efficiency and stability of perovskite devices with different components prepared by different methods, and has a very high material selection range and process selection range.

[0042] In the following, exemplary embodiments of the present application will be described in more detail with reference to the accompanying drawings. It should be noted that these exemplary embodiments can be implemented in various different forms and should not be construed as being limited to the embodiments set forth herein.

[0043] The embodiment of the present application provides a kind of perovskite precursor solution additive, the perovskite precursor solution additive includes one or more of the alkaline earth metal salt of polyhydroxy aldehyde, the alkaline earth metal salt of polyhydroxy ketone, the transition metal salt of polyhydroxy aldehyde, the transition metal salt of polyhydroxy ketone.

[0044] The alkaline earth metal salt of polyhydroxy aldehyde, the alkaline earth metal salt of polyhydroxy ketone, the transition metal salt of polyhydroxy aldehyde, the transition metal salt of polyhydroxy ketone are added as additive into perovskite precursor solution respectively, then perovskite light-absorbing layer is prepared again;The crystallization performance of perovskite light-absorbing layer prepared is analyzed by X-ray diffraction, fluorescence spectrum, it can be seen that the sugar salt of alkaline earth metal, the sugar salt of transition metal as additive, the film crystallization quality of perovskite of different components, perovskite prepared by different process methods are all significantly improved.The performance of perovskite optoelectronic device with the sugar salt of alkaline earth metal, the sugar salt of transition metal as perovskite precursor solution additive is tested, and the performance test result shows that the efficiency and stability of perovskite optoelectronic device can be significantly improved with the sugar salt of alkaline earth metal, the sugar salt of transition metal as perovskite precursor solution additive.

[0045] It needs to be explained that the sugar salt of alkaline earth metal includes one or more of the alkaline earth metal salt of polyhydroxy aldehyde, the alkaline earth metal salt of polyhydroxy ketone;The sugar salt of transition metal includes one or more of the transition metal salt of polyhydroxy aldehyde, the transition metal salt of polyhydroxy ketone.

[0046] In optional embodiment, the alkaline earth metal salt of polyhydroxy aldehyde includes alkaline earth metal gluconate;

[0047] The alkaline earth metal salt of polyhydroxy ketone includes alkaline earth metal fructose acid;

[0048] The transition metal salt of polyhydroxy aldehyde includes transition metal gluconate;

[0049] The transition metal salt of polyhydroxy ketone includes transition metal fructose acid.

[0050] More specifically, the transition metal gluconate includes zinc gluconate etc., the alkaline earth metal gluconate includes calcium gluconate, magnesium gluconate etc., and the alkaline earth metal fructose acid includes calcium fructose acid etc.The glucose and fructose itself has certain reducibility, the crystallization performance of perovskite light-absorbing layer prepared is analyzed by X-ray diffraction, fluorescence spectrum, it can be seen that the sugar salt of alkaline earth metal, the sugar salt of transition metal based on glucose, fructose can more improve the film crystallization quality of perovskite.The structural formula of zinc gluconate, calcium gluconate, magnesium gluconate and calcium fructose acid is as follows in proper order:

[0051]

[0052] In optional embodiments, the alkaline earth metal in the alkaline earth metal salt of the polyhydroxy aldehyde comprises one or more of magnesium, calcium, strontium, and barium.

[0053] The alkaline earth metal in the alkaline earth metal salt of the polyhydroxy ketone comprises one or more of magnesium, calcium, strontium, and barium.

[0054] The transition metal in the transition metal salt of the polyhydroxy aldehyde comprises one or more of cobalt, nickel, copper, and zinc.

[0055] The transition metal in the transition metal salt of the polyhydroxy ketone comprises one or more of cobalt, nickel, copper, and zinc.

[0056] The alkaline earth metal and the transition metal are different in chemical properties, and the roles played by the two as additives are also different. By analyzing the crystallization performance of the prepared perovskite light-absorbing layer through X-ray diffraction and fluorescence spectroscopy, it can be seen that when the alkaline earth metal is magnesium, calcium, strontium, or barium, and the transition metal is cobalt, nickel, copper, or zinc, the film-forming and crystallization quality of the perovskite can be improved.

[0057] The embodiments of the present application provide a perovskite precursor solution, which comprises the perovskite precursor solution additive described above, so as to improve the film-forming and crystallization quality of the perovskite. The amount of the perovskite precursor solution additive can be adjusted according to actual needs.

[0058] In optional embodiments, in the perovskite precursor solution, the mass fraction of the perovskite precursor solution additive is 0.001wt%-4wt%. For example, the amount of the perovskite precursor solution additive is 0.001wt%, 0.005wt%, 0.1wt%, 0.5wt%, 1.5wt%, 2wt%, 3wt%, 3.5wt%, or 4wt%. In the embodiments of the present application, too little amount of the additive cannot reflect the crystallization-promoting effect of the additive, so that the perovskite precursor solution additive cannot effectively improve the crystallization effect of the perovskite. Too much amount of the additive can result in poor dissolution effect of the perovskite precursor solution additive, and also cannot effectively improve the crystallization effect of the perovskite. When the mass fraction of the perovskite precursor solution additive is 0.001wt%-4wt%, the crystallization effect of the perovskite can be effectively improved.

[0059] In some embodiments, the perovskite precursor solution further comprises a perovskite material and an organic solvent.

[0060] The perovskite material is of ABX3 structure; A is a monovalent cation; B is a divalent cation; and X is a monovalent anion. More specifically, A includes but is not limited to one or more monovalent cation mixtures of cesium (Cs), rubidium (Rb), methylamine (CH3NH3), formamidinium (CH2(NH2)2); B includes but is not limited to one or more divalent cation mixtures of lead (Pb), copper (Cu), zinc (Zn), gallium (Ga), tin (Sn), calcium (Ca); and X includes but is not limited to one or more monovalent anion mixtures of iodine (I), bromine (Br), chlorine (Cl), fluorine (F), thiocyanate ion (SCN). More specifically, the perovskite material encompasses perovskite materials of FACs system, perovskite materials of 2D structure, and perovskite materials prepared by different process methods. The organic solvent includes one or more of N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), diphenyl sulfoxide (DPSO), dimethyl formamide (DMF), acetonitrile (ACN), dimethylacetamide (DMAc), N,N'-dimethylpropylene urea (DMPU), 1,4-butyrolactone.

[0061] Embodiments of the present application provide a photoelectric device, including a perovskite light-absorbing layer formed from a perovskite precursor solution.

[0062] The perovskite precursor solution includes a perovskite material, an organic solvent, and a perovskite precursor solution additive.

[0063] The perovskite precursor solution additive includes one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone. The perovskite light-absorbing layer can be applied not only to the field of solar cell devices, but also to the fields of light-emitting devices, detectors, etc., and has strong practicality. The thickness of the perovskite light-absorbing layer can be 400-1500 nm (e.g., 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1500 nm).

[0064] Embodiments of the present application provide a perovskite solar cell, including a perovskite light-absorbing layer formed from a perovskite precursor solution.

[0065] The perovskite precursor solution includes a perovskite material, an organic solvent, and a perovskite precursor solution additive.

[0066] The perovskite precursor solution additive includes one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, and a transition metal salt of a polyhydroxy ketone.

[0067] It should be noted that the perovskite solar cell can include a perovskite single-junction cell, a stacked cell, etc. Among them, the stacked cell can include a perovskite / perovskite stacked cell, a crystalline silicon / perovskite stacked cell, a perovskite / copper indium gallium selenide stacked cell, a perovskite / gallium arsenide stacked cell, a perovskite / cadmium telluride stacked cell, a perovskite / organic stacked cell, a perovskite / quantum dot stacked cell. It should be noted that other cells containing a perovskite layer can also be included.

[0068] The perovskite single-junction cell and the stacked cell are both provided with a perovskite light-absorbing layer.

[0069] In the perovskite single-junction cell, a first perovskite light-absorbing layer 13 (Figure 1) can be provided.

[0070] In the stacked cell, two light-absorbing layers can be provided, i.e. a second perovskite light-absorbing layer 25 (Figure 2) and a light-absorbing layer 22 (Figure 2).

[0071] As shown in Figure 1, the perovskite single-junction cell includes a first back electrode 11, a first electron transport layer 12, a first perovskite light-absorbing layer 13, a first hole transport layer 14, and a first transparent conductive glass layer 15, which are sequentially stacked.

[0072] As shown in Figure 2, the perovskite stacked cell includes a second back electrode 21, a light-absorbing layer 22, a second hole transport layer 23, a second electron transport layer 24, a second perovskite light-absorbing layer 25, a third hole transport layer 26, and a second transparent conductive glass layer 27, which are sequentially stacked. The light-absorbing layer 22 can be a crystalline silicon layer / perovskite layer / copper indium gallium selenide layer / cadmium telluride layer / organic layer.

[0073] As shown in Figure 3, the crystalline silicon / perovskite stacked cell includes a silver electrode (Ag), an ITO (transparent electrode), an a-Si:H(i / p) (first amorphous silicon passivation layer), a C-Si(n) (crystalline silicon bottom cell absorption layer), an a-Si:H(i / n (second amorphous silicon passivation layer), an ITO (tunneling layer), a MeO-2PACZ (perovskite hole transport layer), a PVSK (perovskite light-absorbing layer), a C 60 (a perovskite electron transport layer), SnO2 (a buffer layer), IZO (a transparent electrode layer), MgF2 (an anti-reflection layer), and Ag (a silver grid electrode). Other layers can also be provided according to actual needs.

[0074] Some layers are described by way of example below.

[0075] The back electrode can be made of gold, palladium, silver, titanium, chromium, nickel, aluminum, copper, indium tin oxide (ITO), indium zinc oxide (IZO), etc. The thickness of the back electrode can be 60-100 nm (e.g. 60 nm, 80 nm, 100 nm).

[0076] Electron transport layer: One or more n-type semiconductor materials such as titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), fullerene (C 60 ), graphene, fullerene derivatives (PCBM), etc. can be used. The electron transport layer can be prepared by deposition methods including but not limited to electron beam evaporation, thermal evaporation, magnetron sputtering, atomic layer deposition, spin coating, blade coating, etc. The thickness of the electron transport layer can be 20-40 nm (e.g., 20 nm, 30 nm, 40 nm).

[0077] Perovskite light-absorbing layer: formed from the perovskite precursor solution described above. The preparation method of the perovskite light-absorbing layer is one or more of spin coating, blade coating, evaporation, printing, spraying, spray pyrolysis, slot coating; that is, a perovskite light-absorbing layer is formed on the surface of the electron transport layer by spin coating, blade coating, etc. Different preparation methods will have some influence on the crystallization of the perovskite light-absorbing layer, and the corresponding preparation method can be selected according to actual needs. When the perovskite light-absorbing layer is coated on the surface of the electron transport layer by one-step spin coating or slot coating, the coating speed can be 4000-5000 rpm / min (e.g., 4000 rpm / min, 4500 rpm / min, 5000 rpm / min), and the coating time can be 30-40 s (e.g., 30 s, 35 s, 40 s). The band gap of the perovskite light-absorbing layer can be 1.66-3.0 eV.

[0078] Hole transport layer: One or more inorganic transport materials such as nickel oxide (NiO), cuprous oxide (Cu2O), molybdenum trioxide (MoO3), copper iodide (CuI), and one or more organic p-type semiconductor materials such as redox graphene, poly[ bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA, poly(triaryl amine)), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS), poly[bis(4-phenyl)(4-butylphenyl)amine] (Ploy-TPD), [2-(9H-carbazol-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, etc. can be used. The thickness of the hole transport layer can be 20-40 nm (e.g., 20 nm, 30 nm, 40 nm).

[0079] Transparent conductive glass layer: can be made of indium tin oxide (ITO) substrate, fluorine-doped tin oxide (FTO) substrate, indium zinc oxide (IZO) substrate, etc. The thickness of the transparent conductive glass layer can be 60-200nm (e.g., 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm).

[0080] The following specific embodiments provide a more detailed description of this application, but should not be construed as limiting the application. Any modifications or substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are within the scope of this application.

[0081]

Example 1

[0082] The specific fabrication process of a perovskite single-junction solar cell is as follows:

[0083] Step S1: Provide a cleaned transparent conductive glass layer, which is an ITO substrate with a thickness of 80nm;

[0084] Step S2: Deposit a layer of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACZ) as a hole transport layer with a thickness of 40 nm on the cleaned transparent conductive glass layer;

[0085] Step S3: Dissolve the perovskite material and perovskite precursor solution additive in an organic solvent to prepare a perovskite precursor solution; wherein, the perovskite material is FAMACs perovskite, with the chemical formula FA 0.9 MA 0.05 Cs 0.05 The concentration of zinc gluconate in the PbI3 perovskite precursor solution was 1 mg / mL.

[0086] Step S4: Using a one-step spin coating method, the perovskite precursor solution is coated onto the electron transport layer to form a perovskite light-absorbing layer with a thickness of 1000 nm.

[0087] Step S5: Deposit a layer of fullerene (C) onto the perovskite light-absorbing layer using a thermal evaporation deposition apparatus. 60 ), fullerene (C 60 The thickness of the layer is 25 nm; then, atomic layer deposition is used to deposit a layer of fullerene (C4N2) on the fullerene (C4N2) layer. 60 A layer of tin dioxide (SnO2) is deposited on the fullerene (C) layer, with a thickness of 20 nm; 60 An electron transport layer is formed by combining a 45nm layer and a tin dioxide (SnO2) layer.

[0088] Step S6: A layer of copper metal is deposited on the electron transport layer as an electrode by thermal evaporation to form a back electrode, and the thickness of the back electrode is 80 nm.

[0089] Examples 2-8

[0090] The perovskite single-junction cells of Examples 2-8 are prepared according to the preparation method of Example 1, except that the formula of the perovskite precursor solution prepared in Step S3 is different, and the formula of the perovskite precursor solution in Examples 2-8 is shown in Table 1.

[0091] Example 9

[0092] The specific preparation process of a crystalline silicon / perovskite stacked cell is as follows:

[0093] Step S1: Bottom cell preparation: a silicon heterojunction (SHJ) bottom cell is prepared on an n-type double-textured silicon wafer. An intrinsic silicon layer, an n-type and a p-type hydrogenated amorphous silicon layer are deposited on both sides of the wafer at a process temperature of 200°C by plasma enhanced chemical vapor deposition (PECVD) process. The back contact of the silicon cell is prepared by stacking sputtered ITO (80 nm) and thermally evaporated Ag (150 nm). The front 20 nm ITO composite layer is sputtered through an aligned mask;

[0094] Step S2: A layer of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl] phosphonic acid is deposited on the ITO surface as a hole transport layer;

[0095] Step S3: A perovskite material, a perovskite precursor solution additive, and an organic solvent are mixed to prepare a perovskite precursor solution; wherein the chemical formula of the perovskite material is FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 )3; the concentration of zinc gluconate in the perovskite precursor solution is 1 mg / mL;

[0096] Step S4: The perovskite precursor solution is coated on the hole transport layer prepared in Step S2 by a doctor blade method, and then annealed on a hot plate at 100°C to obtain a perovskite layer with a thickness of 1500 nm;

[0097] Step S5: A layer of fullerene (C 60As the electron transport layer, the thickness is 12 nm; a layer of tin dioxide (SnO2) is prepared by atomic layer deposition as the electron transport layer, the thickness is 20 nm; a layer of IZO is prepared by PVD, the thickness is 70 nm, a layer of MgF2 is prepared by thermal evaporation as the anti-reflection layer, the thickness is about 120 nm, and finally, the silver grid lines on the surface are evaporated to complete the preparation of the entire crystalline silicon / perovskite tandem battery.

[0098] Example 10

[0099] The crystalline silicon / perovskite tandem battery of Example 10 is prepared according to the preparation method of Example 9, except that the formula of the perovskite precursor solution prepared in step S3 is different. In Example 10, the chemical formula of the perovskite material in the perovskite precursor solution is FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 )3, and the concentration of calcium fructoborate in the perovskite precursor solution is 1 mg / mL.

[0100] Example 11

[0101] The crystalline silicon / perovskite tandem battery of Example 11 is prepared according to the preparation method of Example 9, except that the formula of the perovskite precursor solution prepared in step S3 is different. In Example 11, the chemical formula of the perovskite material in the perovskite precursor solution is FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 )3, and the concentration of zinc fructoborate in the perovskite precursor solution is 1 mg / mL.

[0102] In order to more clearly illustrate the technical effects of the embodiments of the present application, the structure and preparation method of the perovskite solar cell of Comparative Example 1 are also pointed out.

[0103] Example 12-Example 13

[0104] The perovskite single-junction cells of Example 12-Example 13 are prepared according to the preparation method of Example 1, except that the formula of the perovskite precursor solution prepared in step S3 is different. The formula of the perovskite precursor solution in Example 12-Example 13 is shown in Table 1.

[0105] Comparative Example 1

[0106] The perovskite single-junction cell of Comparative Example 1 is prepared according to the preparation method of Example 1, except that the formula of the perovskite precursor solution prepared in step S3 is different. In Comparative Example 1, the chemical formula of the perovskite material in the perovskite precursor solution is FA 0.9 MA0.05 Cs 0.05 PbI3, without adding zinc gluconate.

[0107]

Comparative Example 2

[0108] The perovskite single-junction cell of Comparative Example 2 was prepared according to the preparation method of Example 1, except that the formula of the perovskite precursor solution prepared in step S3 was different, and the chemical formula of the perovskite material in the perovskite precursor solution of Comparative Example 2 was FA 0.8 Cs 0.2 PbI3, without adding zinc gluconate.

[0109]

Comparative Example 3

[0110] The crystalline silicon / perovskite tandem cell of Comparative Example 3 was prepared according to the preparation method of Example 10, except that the formula of the perovskite precursor solution prepared in step S3 was different, and zinc gluconate was not added in the perovskite precursor solution of Comparative Example 3.

[0111] Table 1 Formulas of perovskite precursor solutions of Examples 2-8

[0112] Table 1

[0113]

[0114] The perovskite solar cells provided in Examples 1-13 and Comparative Examples 1-3 of the present application were subjected to performance tests, and the test results are shown in Table 1.

[0115] Table 1 Performance test results of perovskite solar cells of Examples 1-13 and Comparative Examples 1-3

[0116]

[0117] It should be noted that AM1.5 in Table 1 above refers to the standard test reference spectrum of solar energy conversion systems.

[0118] It can be seen from the cell performance test results of Examples 1-4 and Comparative Example 1 that the use of alkaline earth metal salts of polyhydroxy aldehydes, alkaline earth metal salts of polyhydroxy ketones, transition metal salts of polyhydroxy aldehydes, and transition metal salts of polyhydroxy ketones as perovskite precursor solution additives can significantly improve the efficiency and stability of perovskite optoelectronic devices.

[0119] It can also be seen from the cell performance test results of Examples 5-8, Examples 12-13, and Comparative Example 2 that the use of alkaline earth metal salts of polyhydroxy aldehydes, alkaline earth metal salts of polyhydroxy ketones, transition metal salts of polyhydroxy aldehydes, and transition metal salts of polyhydroxy ketones as perovskite precursor solution additives can significantly improve the efficiency and stability of perovskite optoelectronic devices.

[0120] It can also be known from the battery performance test results of Examples 9-10 and Comparative Example 3 that, the addition of the alkaline earth metal salt of a polyhydroxy aldehyde, the alkaline earth metal salt of a polyhydroxy ketone, the transition metal salt of a polyhydroxy aldehyde, and the transition metal salt of a polyhydroxy ketone as a perovskite precursor solution additive can significantly improve the efficiency and stability of the perovskite optoelectronic device.

[0121] In addition, the application also provides a spin coating method for preparing a FA 0.8 Cs 0.2 Pb(I 0.8 Br 0.2 )3 perovskite thin film, as shown in FIG. 4. The peak at 14.2° represents the peak of the perovskite, and the stronger the peak, the higher the crystallinity of the perovskite. As can be seen from FIG. 4, the addition of magnesium fructoborate, zinc fructoborate, calcium fructoborate, zinc gluconate, calcium gluconate, and magnesium gluconate as a perovskite precursor solution additive can significantly improve the crystalline quality of the perovskite.

[0122] The application also provides a fluorescence diagram of the perovskite thin film with different additives, as shown in FIG. 5. The improvement of the crystalline quality of the perovskite film will eventually result in a decrease in non-radiative recombination of the thin film. The stronger the fluorescence, the lower the non-radiative recombination. As can be seen from FIG. 5, although the perovskite thin films with the addition of magnesium fructoborate, zinc fructoborate, calcium fructoborate, zinc gluconate, calcium gluconate, and magnesium gluconate have different degrees of improvement in fluorescence intensity, they can all improve the perovskite thin film to different degrees. Some sugar salts can significantly improve the fluorescence intensity, such as zinc gluconate, calcium gluconate, and zinc fructoborate. It can be seen that the salt sugar additive described in the application mainly improves the crystalline quality of the perovskite, thereby reducing the non-radiative recombination of the perovskite thin film and finally improving the performance of the device. The salt sugar additive includes one or more of the alkaline earth metal salt of a polyhydroxy aldehyde, the alkaline earth metal salt of a polyhydroxy ketone, the transition metal salt of a polyhydroxy aldehyde, and the transition metal salt of a polyhydroxy ketone.

[0123] The application provides a photovoltaic module (not shown) including at least one cell string, the cell string including at least two perovskite solar cells described above, and adjacent perovskite solar cells can be connected together by series welding.

[0124] The photovoltaic system can be applied to a photovoltaic power generation system, and can include a photovoltaic array, a combiner box, and an inverter. The photovoltaic array can be an array combination of a plurality of photovoltaic modules. For example, a plurality of photovoltaic modules can form a plurality of photovoltaic arrays. The photovoltaic array is connected to the combiner box. The combiner box can combine the current generated by the photovoltaic array. The combined current flows through the inverter to convert into alternating current required by a power grid, and then is connected to the power grid to realize solar power supply.

[0125] It should be noted that the terms "length", "width", "thickness", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like are merely intended to facilitate the description of the present application and simplify the description, and are not intended to indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. The orientation terms "inner" and "outer" refer to the inner and outer of the profile of each component itself. For example, if the device in the drawing is inverted, the device described as "above" or "above" other devices or structures will be positioned "below" or "below" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below" orientations. The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0126] It should be noted that the terms "first", "second", and the like in the specification and claims of the present application and the above drawings are used to distinguish similar objects, and do not necessarily indicate a specific order or sequence. It should be understood that the terms used in this way can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device including a series of steps or units does not necessarily limit to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0127] It is also need to be explained that the "one embodiment", "another embodiment", "embodiment" and the like mentioned in the present application refer to the specific features, structures or characteristics described in connection with the embodiment are included in at least one embodiment generally described in the present application. The same expression appearing in several places in the specification does not necessarily refer to the same embodiment. Further, when a specific feature, structure or characteristic is described in connection with any embodiment, it is claimed that the implementation of such feature, structure or characteristic in connection with other embodiments also falls within the scope of the present application.

[0128] In the above embodiments, the description of each embodiment has its own focus, and the parts not described in detail in a certain embodiment can be referred to the relevant description of other embodiments.

[0129] It is also need to be explained that the above is only the preferred embodiment of the present application, and does not limit the patent protection scope of the present application, and any equivalent structure or equivalent process transformation using the content of the present application specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A perovskite precursor solution additive, wherein, The perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, a transition metal salt of a polyhydroxy ketone. 2.The perovskite precursor solution additive of claim 1, wherein, The alkaline earth metal salt of a polyhydroxy aldehyde comprises an alkaline earth metal salt of gluconic acid; The alkaline earth metal salt of a polyhydroxy ketone comprises an alkaline earth metal salt of fructose acid; The transition metal salt of a polyhydroxy aldehyde comprises a transition metal salt of gluconic acid; The transition metal salt of a polyhydroxy ketone comprises a transition metal salt of fructose acid.

3. The perovskite precursor solution additive according to any one of claims 1 or 2, wherein, The alkaline earth metal in the alkaline earth metal salt of a polyhydroxy aldehyde comprises one or more of magnesium, calcium, strontium, barium; The alkaline earth metal in the alkaline earth metal salt of a polyhydroxy ketone comprises one or more of magnesium, calcium, strontium, barium; The transition metal in the transition metal salt of a polyhydroxy aldehyde comprises one or more of cobalt, nickel, copper, zinc; The transition metal in the transition metal salt of a polyhydroxy ketone comprises one or more of cobalt, nickel, copper, zinc. 4.A perovskite precursor solution comprising the perovskite precursor solution additive of any one of claims 1-3.

5. The perovskite precursor solution of claim 4, wherein, In the perovskite precursor solution, the perovskite precursor solution additive accounts for 0.001wt%-4wt% of the mass.

6. The perovskite precursor solution of claim 4, wherein, Further comprising a perovskite material, an organic solvent; The perovskite material has an ABX 3 structure; A is a monovalent cation; B is a divalent cation; and X is a monovalent anion. 7.A photoelectric device comprising a perovskite light-absorbing layer formed from a perovskite precursor solution; The perovskite precursor solution comprises: a perovskite material, an organic solvent, a perovskite precursor solution additive; wherein the perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, a transition metal salt of a polyhydroxy ketone. 8.A perovskite solar cell comprising a perovskite light-absorbing layer formed from a perovskite precursor solution; The perovskite precursor solution comprises: a perovskite material, an organic solvent, a perovskite precursor solution additive; wherein the perovskite precursor solution additive comprises one or more of an alkaline earth metal salt of a polyhydroxy aldehyde, an alkaline earth metal salt of a polyhydroxy ketone, a transition metal salt of a polyhydroxy aldehyde, a transition metal salt of a polyhydroxy ketone. 9.A photovoltaic module comprising: at least one string of cells, the string of cells comprising at least two perovskite solar cells as claimed in claim 8. 10.A photovoltaic system comprising a photovoltaic module as claimed in claim 9.

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