High photoelectric reciprocity perovskite diode

Abstract

The invention discloses a novel high-reciprocity perovskite diode structure with a micron-sized low-refractive-index material. According to the invention, the discontinuous porous island-shaped structure layer is arranged on one side or two sides of the perovskite to prepare the perovskite diode with high photoelectric reciprocity, so that the light extraction efficiency is remarkably improved from 18% to 40%; the open-circuit voltage (Voc) is further improved; therefore, the photoelectric conversion efficiency of the perovskite diode is improved from 24.4% to 26.6%. The perovskite diode provided by the invention has high electro-optical conversion efficiency, electroluminescent quantum efficiency and irradiation intensity at the same time; meanwhile, due to the openings between the islands and the porosity of the material, the device also has roll-off and turn-on voltage of electroluminescent quantum efficiency under low large current.

Description

Technical Field

[0001] This invention relates to the field of device structure design technology, and more specifically, to a novel highly reciprocal perovskite diode structure made of a low-refractive-index material with a micrometer-sized diameter. Background Technology

[0002] Solar cells and light-emitting diodes (LEDs) theoretically possess a certain degree of reciprocity because, physically, solar cells convert light into electricity, while LEDs convert electricity into light. Theoretically, an ideal solar cell will necessarily be an ideal LED. Therefore, when designing solar cells and LEDs with high reciprocity, it is essential to ensure sufficiently low non-radiative recombination losses and high light extraction efficiency without compromising electrical performance. Perovskite is a novel photovoltaic material that exhibits excellent performance in both solar cells and LEDs.

[0003] Currently, the most efficient perovskite solar cell diodes typically employ a planar device structure with a relatively thick perovskite thin film, resulting in a low light extraction efficiency, usually 20% or lower. This device design cannot guarantee good light-emitting performance, for example, causing the electroluminescence quantum efficiency to consistently remain below 20%. More importantly, without good light extraction efficiency, the open-circuit voltage (V) of the perovskite solar cell... oc This will also result in some losses. While perovskite light-emitting diodes (LEDs) can improve their light extraction efficiency to some extent (generally around 35%) through a special perovskite island-like device structure design, this requires the perovskite to be a very thin island structure (less than 50nm thick). Perovskite of this thickness cannot fully absorb light, therefore such a device design is unfavorable for perovskite solar cell diodes. Furthermore, the current device structure's light extraction efficiency is still below 40%, leaving considerable room for improvement.

[0004] Current perovskite light-emitting diodes (LEDs) suffer from significant Joule losses and high turn-on voltages due to the use of low-conductivity two-dimensional perovskite materials for organic passivation and barrier layers, resulting in substantial energy loss in the conversion of electroluminescence into light. Consequently, current perovskite LEDs experience significant losses in electroluminescence quantum efficiency at high current densities, leading to consistently low irradiance or brightness under these conditions.

[0005] In summary, improving the light extraction efficiency of perovskite light-emitting diodes and reducing non-radiative recombination and electrical losses are urgent problems to be solved in the fabrication of perovskite diodes with high photoelectric reciprocity. Summary of the Invention

[0006] The purpose of this invention is to provide a perovskite diode with high photoelectric reciprocity. This high photoelectric reciprocity perovskite diode improves the electro-optical conversion efficiency, electroluminescence quantum efficiency, and irradiance of the device by providing a discontinuous porous island-like structure layer on one or both sides of the perovskite; it also reduces the roll-off of electroluminescence quantum efficiency and the turn-on voltage under high current.

[0007] Another object of the present invention is to provide a method for fabricating a perovskite diode with high photoelectric reciprocity.

[0008] The above-mentioned objective of the present invention is achieved by the following solution:

[0009] A perovskite diode with high photoelectric reciprocity includes at least a perovskite layer, and a discontinuous porous island structure layer is provided on one or both sides of the perovskite layer; the discontinuous porous island structure layer includes multiple independent or connected porous island structures; the average length of the porous island structure is 500-10000 nm, the average width is 500-10000 nm, and the average height is 100-1000 nm.

[0010] The refractive index of the discontinuous porous island structure layer is 1.0-2.1;

[0011] The discontinuous porous island structure layer is prepared by nanoparticles or clusters formed by positively charged and / or negatively charged molecules loaded on a carrier.

[0012] The carrier is one or more of the following: alumina, silicon oxide, magnesium oxide, nickel oxide, zirconium oxide, iron oxide, titanium oxide, zinc oxide, manganese oxide, cobalt oxide, molybdenum oxide, tungsten oxide, germanium oxide, yttrium oxide, copper oxide, zirconium oxide, Zn2GeO4, NiCo2O4, CoMn2O4, lanthanum strontium cobalt iron, barium strontium cobalt iron, lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, polymethyl methacrylate, polystyrene, silicon carbide, and aerogel materials;

[0013] The positively charged molecules are one or more of the following: piperazine monohydroiodate, piperazine dihydroiodate, phenylammonium iodide, benzyl ammonium bromide, phenethylamine hydroiodate, phenethylammonium iodide, phenethylammonium bromide, p-fluorophenethylamine hydroiodate, m-fluorophenethylamine hydroiodate, 4-trifluoromethylphenethylamine hydroiodate, octylamine hydroiodate, octylamine hydrobromide, ethylenediamine chloride, mercaptoethylamine hydroiodate, 4-pyridinemethylamine iodide, m-phenylenediamine iodide, phenethylamine chloride, p-fluorophenethylamine chloride, decanediamine iodide, propylenediamine iodide, butylenediamine iodide, 1,6-hexamethylenediamine hydroiodate, 1,8-octyldiamine hydroiodate, 1,8-octyldiamine hydrobromide, guanidinohydrochloride, 1,4-phenylenediamine bromide, 1,4-phenylenediamine iodide, 1,3-bis(diphenylphosphine), 2-(2-pyridyl)ethylamine propane, oleylamine, and oleic acid;

[0014] Negatively charged molecules include [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]phosphonic acid, 2-(9H-carbazole-9-yl)ethyl)phosphonic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid, phosphoric acid, hypophosphonic acid, potassium phosphate, potassium dihydrogen phosphate, sodium phosphate, decyl phosphoric acid, minophosphate, cardiolipin, ammonium chloride, diphenyl phosphate, dibenzyl phosphate, ammonium dihydrogen phosphate, guanidine phosphate, potassium phosphite, sodium hypophosphite, and methylphosphonic acid. Acids, phenylphosphoric acid, potassium sulfate, ammonium sulfate, sodium sulfate, aminosulfuric acid, hydrazine sulfate, ammonium persulfate, hydroxylamine sulfate, sodium thiosulfate, ammonium thiosulfate, benzenesulfonic acid, taurine, methanesulfonic acid, aminosulfonic acid, linolenic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)sulfonic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]sulfonic acid, 2-(9H-carbazole-9-yl)ethyl)sulfonic acid, 2-naphthalenesulfonic acid, 3-amino Benzenesulfonic acid, sodium 3-nitrobenzenesulfonate, sodium 2-naphthalenesulfonate, boric acid, methylboric acid, 9-phenanthroline boric acid, butylboric acid, 3-nitrobenzeneboric acid, phenylboric acid, 2,4-dichlorophenylboric acid, disodium tetraborate, 9-anthraboric acid, lithium tetrafluoroborate, potassium tetrafluoroborate, ammonium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoroboric acid, triphenylamine boric acid, dimethyltriphenylamine boric acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)boric acid, [n-(3,6-dimethyl)boric acid [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]boronic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]carboxylic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)carboxylic acid, formic acid, acetic acid, propionic acid, 4-pyridinecarboxylic acid, 4-thiazolidinecarboxylic acid, anthraquinone-2-carboxylic acid, fluorene-9-carboxylic acid, proanthridinecarboxylic acid, 4-pyrazolecarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, where n is an integer greater than or equal to 1.

[0015] Preferably, the coverage of the discontinuous porous island structure layer is 1-99%.

[0016] Preferably, the coverage of the discontinuous porous island structure layer is 40-99%.

[0017] Preferably, the coverage of the discontinuous porous island structure layer is 60-90%.

[0018] Preferably, the coverage of the discontinuous porous island structure layer is 60%, 70%, 80%, or 90%.

[0019] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.8.

[0020] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.5.

[0021] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.3.

[0022] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.2.

[0023] Preferably, the mass ratio of the carrier to the positively charged molecule is 1:0.01 to 0.15.

[0024] Preferably, the mass ratio of the carrier to the negatively charged molecule is 1:0.01 to 0.15.

[0025] Preferably, the pores in the discontinuous porous island structure layer can be voids of any shape.

[0026] Preferably, the pores in the discontinuous porous island structure layer are hollow cavities that penetrate the island structure.

[0027] Preferably, the preparation process of nanoparticles or clusters is as follows: mixing a carrier, positively charged molecules and / or negatively charged molecules in a solvent to obtain the nanoparticle or cluster solution;

[0028] The solvent is water, ethanol, isopropanol, acetone, dimethyl sulfoxide, or dimethylamide.

[0029] Preferably, the nanoparticle or cluster solution is deposited on one or both sides of the perovskite layer by magnetron sputtering, atomic layer deposition, chemical vapor deposition, chemical bath deposition, screen printing or spraying.

[0030] Preferably, the carrier is one or more of the following: alumina, silicon oxide, magnesium oxide, nickel oxide, zirconium oxide, iron oxide, titanium oxide, zinc oxide, manganese oxide, cobalt oxide, molybdenum oxide, tungsten oxide, and aerogel material.

[0031] Preferably, the positively charged molecule is one or more of piperazine monohydroiodate, piperazine dihydroiodate, phenyl ammonium iodide, benzyl ammonium bromide, phenethylamine hydroiodate, phenethyl ammonium iodide, phenethyl ammonium bromide, p-fluorophenethylamine hydroiodate, m-fluorophenethylamine hydroiodate, 4-trifluoromethylphenethylamine hydroiodate, octylamine hydroiodate, and octylamine hydrobromic acid.

[0032] Preferably, the negatively charged molecule is one or more of the following: [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]phosphonic acid, 2-(9H-carbazole-9-yl)ethyl)phosphonic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid, phosphoric acid, hypophosphonic acid, potassium phosphate, potassium dihydrogen phosphate, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)boric acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]boric acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]carboxylic acid, and (2,7-dimethoxy-9H-carbazole-9-yl)methyl)carboxylic acid, where n is an integer greater than or equal to 1.

[0033] Preferably, the structure of the high photoelectric reciprocity perovskite diode is: an electrode, a hole blocking layer, an electron injection layer, a perovskite layer, a discontinuous porous island structure layer, a hole injection layer, and a conductive substrate.

[0034] Preferably, the structure of the high photoelectric reciprocity perovskite diode is as follows: electrode, hole blocking layer, electron injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, hole injection layer, and conductive substrate.

[0035] Preferably, the structure of the high photoelectric reciprocity perovskite diode is as follows: electrode, electron injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, hole injection layer, and conductive substrate.

[0036] Preferably, the structure of the high photoelectric reciprocity perovskite diode is: an electrode, a hole injection layer, a perovskite layer, a discontinuous porous island structure layer, an electron injection layer, and a conductive substrate.

[0037] Preferably, the structure of the high photoelectric reciprocity perovskite diode is as follows: electrode, hole injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, electron injection layer, and conductive substrate.

[0038] Preferably, the hole injection layer is a p-type hole injection layer.

[0039] Preferably, the electron injection layer is an n-type electron injection layer.

[0040] Preferably, the conductive substrate is a rigid TCO substrate, a flexible substrate, or a metal substrate.

[0041] Preferably, the rigid TCO substrate is: ITO, IZO, FTO, AZO, IWO, IMO, IGZO, ITiO, or GZO.

[0042] Preferably, the flexible substrate is PET, PEN, PI, PAN, PTH, or PPy.

[0043] Preferably, the metal substrate is Mo, Pt, Pd, NiCr, or Al.

[0044] This invention also protects the aforementioned method for fabricating a high photoelectric reciprocity perovskite diode, comprising the following steps:

[0045] S11. Prepare a hole injection layer on a clean conductive substrate;

[0046] S12. Prepare a discontinuous porous island structure layer on the layer prepared in step S11;

[0047] S13. Deposit a perovskite layer on the layer prepared in the previous step;

[0048] S14. Prepare a discontinuous porous island structure layer on the perovskite layer;

[0049] S15. Sequentially fabricate an electron injection layer, a hole blocking layer, and an electrode on the layer prepared in the previous step;

[0050] Step S14 can be omitted.

[0051] Preferably, the aforementioned method for fabricating a high photoelectric reciprocity perovskite diode includes the following steps:

[0052] S21. Electron injection layers are sequentially prepared on a clean conductive substrate;

[0053] S22. Prepare a discontinuous porous island structure layer on the layer prepared in step S21;

[0054] S23. Deposit a perovskite layer on the layer prepared in the previous step;

[0055] S24. Prepare a discontinuous porous island structure layer on the perovskite layer;

[0056] S25. Sequentially prepare a hole injection layer and an electrode on the layer prepared in the previous step;

[0057] Step S24 can be omitted.

[0058] Preferably, the discontinuous porous island structure layer comprises multiple independent or connected porous island structures; the average length of the porous island structure is 500-10000 nm, the average width is 500-10000 nm, and the average height is 100-1000 nm.

[0059] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-2.1.

[0060] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.8.

[0061] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.5.

[0062] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.3.

[0063] Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.2.

[0064] Preferably, the discontinuous porous island structure layer is prepared by nanoparticles or clusters formed by positively charged molecules and / or negatively charged molecules loaded on a carrier.

[0065] Preferably, the carrier is one or more of the following: alumina, silicon oxide, magnesium oxide, nickel oxide, zirconium oxide, iron oxide, titanium oxide, zinc oxide, manganese oxide, cobalt oxide, molybdenum oxide, tungsten oxide, germanium oxide, yttrium oxide, copper oxide, zirconium oxide, Zn2GeO4, NiCo2O4, CoMn2O4, lanthanum strontium cobalt iron, barium strontium cobalt iron, lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, polymethyl methacrylate, polystyrene, silicon carbide, and aerogel materials.

[0066] Preferably, the positively charged molecule is one or more of piperazine monohydroiodate, piperazine dihydroiodate, phenylammonium iodide, benzylammonium bromide, phenethylamine hydroiodate, phenethylammonium iodide, phenethylammonium bromide, p-fluorophenethylamine hydroiodate, m-fluorophenethylamine hydroiodate, 4-trifluoromethylphenethylamine hydroiodate, octylamine hydroiodate, octylamine hydrobromide, ethylenediamine chloride, mercaptoethylamine hydroiodate, 4-pyridinemethylamine iodide, m-phenylenediamine iodide, phenethylamine chloride, p-fluorophenethylamine chloride, decanediamine iodide, propylenediamine iodide, butylenediamine iodide, 1,6-hexamethylenediamine hydroiodate, 1,8-octyldiamine hydroiodate, 1,8-octyldiamine hydrobromide, guanidinohydrochloride, 1,4-phenylenediamine bromide, 1,4-phenylenediamine iodide, 1,3-bis(diphenylphosphine), 2-(2-pyridyl)ethylamine propane, oleylamine, and oleic acid.

[0067] Preferably, the negatively charged molecule is [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]phosphonic acid, 2-(9H-carbazole-9-yl)ethyl)phosphonic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid, phosphoric acid, hypophosphonic acid, potassium phosphate, potassium dihydrogen phosphate, sodium phosphate, decyl phosphoric acid, minophosphate, cardiolipin, ammonium chloride, diphenyl phosphate, dibenzyl phosphate, ammonium dihydrogen phosphate, guanidine phosphate, potassium phosphite, sodium hypophosphite, etc. Methylphosphonic acid, phenylphosphonic acid, potassium sulfate, ammonium sulfate, sodium sulfate, aminosulfuric acid, hydrazine sulfate, ammonium persulfate, hydroxylamine sulfate, sodium thiosulfate, ammonium thiosulfate, benzenesulfonic acid, taurine, methanesulfonic acid, aminosulfonic acid, linolenic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)sulfonic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]sulfonic acid, 2-(9H-carbazole-9-yl)ethyl)sulfonic acid, 2-naphthalenesulfonic acid, 3- Aminobenzenesulfonic acid, sodium 3-nitrobenzenesulfonate, sodium 2-naphthalenesulfonate, boric acid, methylboric acid, 9-phenanthroline boric acid, butylboric acid, 3-nitrobenzeneboric acid, phenylboric acid, 2,4-dichlorophenylboric acid, disodium tetraborate, 9-anthraboric acid, lithium tetrafluoroborate, potassium tetrafluoroborate, ammonium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoroboric acid, triphenylamine boric acid, dimethyltriphenylamine boric acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)boric acid, [n-(3,6-dimethyl) [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]boronic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]carboxylic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)carboxylic acid, formic acid, acetic acid, propionic acid, 4-pyridinecarboxylic acid, 4-thiazolidinecarboxylic acid, anthraquinone-2-carboxylic acid, fluorene-9-carboxylic acid, proanthraquinone tricarboxylic acid, 4-pyrazolecarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, where n is an integer greater than or equal to 1.

[0068] Preferably, the coverage of the discontinuous porous island structure layer is 1-99%.

[0069] Preferably, the coverage of the discontinuous porous island structure layer is 40-99%.

[0070] Preferably, the coverage of the discontinuous porous island structure layer is 60-90%.

[0071] Preferably, the coverage of the discontinuous porous island structure layer is 60%, 70%, 80%, or 90%.

[0072] Preferably, the mass ratio of the carrier to the positively charged molecule is 1:0.01 to 0.15.

[0073] Preferably, the mass ratio of the carrier to the negatively charged molecule is 1:0.01 to 0.15.

[0074] Preferably, the deposition methods for the above-mentioned layers include physical deposition and chemical deposition methods.

[0075] Preferably, the physical deposition method includes, but is not limited to, vacuum evaporation, sputtering, ion beam deposition, pulsed laser deposition, etc.

[0076] Preferably, the chemical deposition method includes, but is not limited to, chemical vapor deposition, atomic layer deposition, sol-gel spin coating, etc.

[0077] Compared with the prior art, the present invention has the following beneficial effects:

[0078] This invention prepares a perovskite diode with high photoelectric reciprocity by providing a discontinuous porous island structure layer on one or both sides of the perovskite. This not only significantly improves the light extraction efficiency from 18% to 40%, but also further increases the open-circuit voltage (Voc), thereby increasing the photoelectric conversion efficiency of the perovskite diode from 24.4% to 26.6%.

[0079] The perovskite diode of the present invention simultaneously possesses high electro-optical conversion efficiency, electroluminescence quantum efficiency, and irradiance; furthermore, due to the openings between the islands and the porosity of the material, the device also exhibits low roll-off of electroluminescence quantum efficiency and low turn-on voltage under high current. Attached Figure Description

[0080] Figure 1 This is a schematic diagram of a perovskite diode device.

[0081] Figure 2 This invention relates to the chemisorption mechanism and aggregation mechanism of nanoparticles modified with chemical molecules of different charges.

[0082] Figure 3 (a) Scanning electron microscope image of a porous island structure with micrometer-sized low refractive index on ITO in Embodiment 2 of the present invention, and (b) Scanning electron microscope image of perovskite on a porous island structure with micrometer-sized low refractive index.

[0083] Figure 4 The graph shows the electroluminescence external quantum efficiency versus injection current density curves of the devices in Example 1 and Comparative Example 1.

[0084] Figure 5 The irradiance-voltage curves are for the devices in Example 1 and Comparative Example 1.

[0085] Figure 6 The current density-voltage curves of the solar cells of Example 1 and Comparative Example 1 are shown.

[0086] Figure 7The curves show the coverage of micron-sized low-refractive-index agglomerates on ITO after spin coating with different concentrations as a function of concentration.

[0087] Figure 8 The graph shows the variation of external quantum efficiency in electroluminescence with the coverage of the discontinuous porous island structure.

[0088] Figure 9 The graph shows the variation in light extraction efficiency of porous island structure devices with different refractive indices.

[0089] Figure 10 The graph shows the changes in light extraction efficiency of devices with different island sizes and coverage rates compared to the control example 1 with a full-planar structure device, obtained through FDTD simulation calculations.

[0090] Figure 11 The graph shows the change in light extraction efficiency as a function of refractive index for the devices corresponding to different island structures in Examples 6 and 7, obtained through FDTD simulation calculations. Detailed Implementation

[0091] To better understand the present invention, the following detailed description is provided in conjunction with specific embodiments. These embodiments are used to illustrate the main reactions and basic features of the present invention and are not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to specific requirements. Implementation conditions not specified are generally those in conventional experiments.

[0092] Example 1

[0093] The perovskite diode device 1 has the following structural schematic diagram: Figure 1 As shown, the specific preparation process is as follows:

[0094] Preparation of nanoparticle or cluster solutions: The support is alumina (AO) with a size of 30 nm, dispersed in isopropanol, and positively charged molecules and negatively charged molecules are added respectively to obtain nanoparticle solutions with positive and negative charges on the surface.

[0095] The negatively charged molecule is 2-(9H-carbazole-9-yl)ethylphosphonic acid (2-PACz) (carrier: 2-PACz mass ratio is 1:0.1), such as Figure 2 As shown in Figure a, negatively charged phosphate groups are chemically adsorbed onto the aluminum-rich surface of alumina to obtain nanoparticles (AOP).

[0096] The positively charged molecule is 1,8-octanediamine hydroiodate (ODADI) (carrier: 1,8-octanediamine hydroiodate mass ratio is 1:0.1), such as... Figure 2 As shown in b, positively charged amine salts are chemically adsorbed onto the oxygen-rich surface of alumina to obtain nanoparticles (AOA).

[0097] Positively charged nanoparticle solutions and negatively charged nanoparticle solutions are mixed in a certain ratio (mass ratio 1:2), such as... Figure 2 As shown in c, AOP and AOA mixed and aggregated to obtain large micron clusters (APA).

[0098] 1) Prepare a layer of (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2-PACz) of about 1 nm on a cleaned ITO substrate as a hole injection layer;

[0099] 2) APA clusters at a concentration of 8 mg / mL were spin-coated onto the prepared hole injection layer, achieving a coverage of 80%. The island-like structures had an average height of 500 nm, an average length and width of 5 μm, and a refractive index of 1.1. The specific morphology of the nanoparticles is as follows: Figure 3 a;

[0100] 3) A perovskite layer with a band gap of 1.53 eV and a thickness of approximately 700 nm was spin-coated onto the prepared layer. The specific morphology of the perovskite is as follows: Figure 3 b;

[0101] 4) Spin-coat 1 mg / mL propylenediamine hydroiodate onto the prepared perovskite;

[0102] 5) A layer of fullerene (C) was prepared by thermal evaporation. 60 As an electron injection layer, its thickness is approximately 25 nm;

[0103] 6) A layer of copper bath (BCP) with a thickness of 5 nm was grown on C60 using thermal evaporation;

[0104] 7) The electrode is made of Ag by thermal evaporation, with a thickness of 100 nm.

[0105] The light extraction efficiency of perovskite diode device 1 was simulated and calculated. The specific calculation process is as follows:

[0106] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD). For the specific calculation process, please refer to the following references: C. Cho, B. Zhao, G.D. Taner, J.-Y.

[0107] Lee, RH Friend, D. Di, F. Deschler, NC Greenham, Nat. Commun. 2020, 11, 611.

[0108] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0109] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index of 1.1 and 80% coverage having micron dimensions (5 μm long and wide, 500 nm high) / 1.54-eV perovskite (800 nm,

[0110] n = 2.50) / C 60 (30nm, n=2.06) / ALD SnO x (20nm, n=1.94) / Ag(150)

[0111] nm, n=0.14+5.37i)

[0112] iv. The emission wavelength is set to 805 nm. The emission source is located in the middle of the perovskite or the center of the island.

[0113] Example 2

[0114] The perovskite diode device 2 has the following structural schematic diagram: Figure 1 As shown, the specific preparation process is as follows:

[0115] The preparation of the nanoparticle or cluster solution is the same as in Example 1.

[0116] 1) Prepare a layer of 2-(9H-carbazole-9-yl)ethylphosphonic acid (2-PACz) of about 1 nm on a cleaned ITO substrate as a hole injection layer;

[0117] 2) Spin-coat the prepared hole injection layer with the aforementioned locally micron-sized, low-refractive-index (refractive-index n = 1.1) island-like structure material at concentrations of 1, 2, 4, 12, and 20 mg / mL. The coverage varies with concentration. Figure 7 ;

[0118] 3) A perovskite layer with a band gap of 1.53 eV and a thickness of approximately 700 nm was spin-coated onto the prepared layer. The specific morphology of the perovskite is as follows: Figure 3 b;

[0119] 4) Spin-coat 1 mg / mL propylenediamine hydroiodate onto the prepared perovskite;

[0120] 5) A layer of fullerene (C) was prepared by thermal evaporation. 60 As an electron injection layer, its thickness is approximately 25 nm;

[0121] 6) A layer of copper bath (BCP) with a thickness of 5 nm was grown on C60 using thermal evaporation;

[0122] 7) The electrode is made of Ag by thermal evaporation, with a thickness of 100 nm.

[0123] By comparing Examples 1 and 2, it was found that 80% coverage was the optimal coverage, at which point the electroluminescence quantum efficiency was highest. Figure 7 and Figure 8 .

[0124] Example 3

[0125] The perovskite diode device 3 was prepared according to Example 1, except that in step 2), only AOP nanoparticle solution was used for deposition. The porous island structure layer has an island length and width of 500 nm, an island height of 100 nm, a coverage of 80%, and a refractive index of 1.1.

[0126] The simulation calculation of the light extraction efficiency of the perovskite diode device 3 was performed with reference to Example 1. The specific calculation process is as follows:

[0127] i. The light extraction efficiency of perovskite diode structures is calculated using the finite-difference time-domain (FDTD) method.

[0128] The calculation method is the same as in Example 1.

[0129] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0130] III. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index of 1.1 and 80% coverage, having a size of 100 nm (500 nm long and wide, 100 nm high) / 1.54-eV perovskite (800 nm,

[0131] n = 2.50) / C 60 (30nm, n=2.06) / ALD SnO x (20nm, n=1.94) / Ag(150nm,

[0132] n = 0.14 + 5.37i).

[0133] iv. The emission wavelength is set to 805 nm. The emission source is located in the middle of the perovskite or the center of the island.

[0134] By comparing perovskite diode device 1 and perovskite diode device 3, it was found that the size of the island structure affects the light extraction efficiency, such as... Figure 9 As shown, an island structure with a refractive index of 1.1 and a coverage of 80% with a size of 100 nanometers (500 nm in length and width, and 100 nm in height) is not as good as an island structure with a refractive index of 1.1 and a coverage of 80% with a size of micrometers (5 μm in length and width, and 500 nm in height).

[0135] Example 4

[0136] The perovskite diode device 4 was fabricated according to Example 1, except that in step 2), the islands in the porous island structure layer are 5 μm in length and width, 500 nm in height, have a coverage of 20%, and a refractive index of 1.1.

[0137] The simulation calculation of the light extraction efficiency of the perovskite diode device 4 was performed with reference to Example 1. The specific calculation process is as follows:

[0138] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD), and the calculation method is the same as in Example 1.

[0139] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0140] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index of 1.1 and 80% coverage having a size of 100 nm (5 μm long and wide, 500 nm high) / 1.54-eV perovskite (800 nm,

[0141] n = 2.50) / C 60 (30nm, n=2.06) / ALD SnO x (20nm, n=1.94) / Ag(150nm,

[0142] n = 0.14 + 5.37i).

[0143] iv. The emission wavelength is set to 805 nm. The emission source is located in the middle of the perovskite or the center of the island.

[0144] By comparing perovskite diode device 1 and perovskite diode device 4, it was found that the coverage of the island structure affects the light extraction efficiency. The light extraction efficiency of the device with a 20% coverage is not as high as that of the island structure with an 80% coverage.

[0145] Example 5

[0146] The perovskite diode device 5 was fabricated according to Example 1, except that in step 2), the islands in the porous island structure layer were 5 μm in length and width, 500 nm in height, 80% in coverage, and 1.0, 1.1, 1.2, 1.3, 1.4 and 1.5 respectively.

[0147] The simulation calculation of the light extraction efficiency of the perovskite diode device 5 was performed with reference to Example 1. The specific calculation process is as follows:

[0148] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD), and the calculation method is the same as in Example 1.

[0149] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0150] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index varying from 1.1 to 1.5 and a coverage of 80% having a size of 100 nm (5 μm long and wide, 500 nm high) / 1.54-eV perovskite (800 nm, n = 2.50) / C 60 (30nm, n=2.06) / ALDSnO x (20nm, n=1.94)

[0151] / Ag(150nm, n=0.14+5.37i).

[0152] iv. The emission wavelength is set to 805 nm. The emission source is located in the middle of the perovskite or the center of the island.

[0153] By comparing the changes in device light extraction efficiency corresponding to the refractive index of the porous island structure in Example 5, the test results are as follows: Figure 9 As shown, it was found that the lower the refractive index of the island structure, the better.

[0154] Example 6

[0155] The fabrication process of perovskite diode device 6 is as follows:

[0156] Preparation of nanoparticle or cluster solutions: The support is alumina (AO) with a size of 30 nm, dispersed in isopropanol, and positively charged molecules and negatively charged molecules are added respectively to obtain nanoparticle solutions with positive and negative charges on the surface.

[0157] The negatively charged molecule is 2-(9H-carbazole-9-yl)ethylphosphonic acid (2-PACz) (carrier: 2-PACz mass ratio is 1:0.1), such as Figure 2 As shown in Figure a, negatively charged phosphate groups are chemically adsorbed onto the aluminum-rich surface of alumina to obtain nanoparticles (AOP).

[0158] The positively charged molecule is 1,8-octanediamine hydroiodate (ODADI) (carrier: 1,8-octanediamine hydroiodate mass ratio is 1:0.1), such as... Figure 2 As shown in b, positively charged amine salts are chemically adsorbed onto the oxygen-rich surface of alumina to obtain nanoparticles (AOA).

[0159] Positively charged nanoparticle solutions and negatively charged nanoparticle solutions are mixed in a certain ratio (mass ratio 2:1) to obtain large micron clusters (APA).

[0160] 1) Prepare a layer of (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2-PACz) of about 1 nm on a cleaned ITO substrate as a hole injection layer;

[0161] 2) APA clusters of 8 mg / mL were spin-coated onto the prepared hole injection layer, with a coverage of 80%, an average height of 500 nm for the island structure, an average length and width of 5 μm, and a refractive index of 1.1.

[0162] 3) A layer of perovskite with a band gap of 1.53 eV and a thickness of about 700 nm was spin-coated onto the prepared layer;

[0163] 4) Spin-coat 1 mg / mL propylenediamine hydroiodate onto the prepared perovskite;

[0164] 5) A layer of fullerene (C) was prepared by thermal evaporation. 60 As an electron injection layer, its thickness is approximately 25 nm;

[0165] 6) A layer of copper bath (BCP) with a thickness of 5 nm was grown on C60 using thermal evaporation;

[0166] 7) The electrode is made of Ag by thermal evaporation, with a thickness of 100 nm.

[0167] The difference lies in step 2), where the ratio of positively charged nanoparticle solution to negatively charged nanoparticles is adjusted to 2:1, resulting in a porous island structure layer with islands of 5 μm in length and width, 500 nm in height, and 80% coverage. The porous structure within the islands forms a hollow cavity structure, as illustrated in the schematic diagram below. Figure 11 a. The hollow structure is a channel with a length and width of 30 nm and a height of 200 nm, leading to a hollow island-like structure with a length and width of 1 μm and a height of 300 nm. The hollow parts are all filled with perovskite with refractive indices of 1.0, 1.1, 1.3 and 1.5, respectively.

[0168] The simulation calculation of the light extraction efficiency of the perovskite diode device 6 was performed with reference to Example 1. The specific calculation process is as follows:

[0169] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD), and the calculation method is the same as in Example 1.

[0170] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0171] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index varying from 1.1 to 1.5 and a coverage of 80% filled with perovskite in a 100 nm size (5 μm long and wide, 500 nm high) / 1.54-eV perovskite (800 nm, n = 2.50) / C 60 (30nm, n=2.06) / ALD

[0172] SnO x (20nm, n=1.94) / Ag(150nm, n=0.14+5.37i).

[0173] iv. The emission wavelength is set to 805 nm. The emission source is located at the center of the hollow island in the perovskite.

[0174] By comparing the changes in device light extraction efficiency corresponding to the refractive index of the porous island structure in Example 6, the test results are as follows: Figure 11 As shown in c, it was found that the lower the refractive index of the island structure, the better.

[0175] Example 7

[0176] The fabrication process of perovskite diode device 7 is as follows:

[0177] Preparation of nanoparticle or cluster solutions: The support is alumina (AO) with a size of 30 nm, dispersed in isopropanol, and positively charged molecules and negatively charged molecules are added respectively to obtain nanoparticle solutions with positive and negative charges on the surface.

[0178] The negatively charged molecule is 2-(9H-carbazole-9-yl)ethylphosphonic acid (2-PACz) (carrier: 2-PACz mass ratio is 1:0.1), such as Figure 2 As shown in Figure a, negatively charged phosphate groups are chemically adsorbed onto the aluminum-rich surface of alumina to obtain nanoparticles (AOP).

[0179] The positively charged molecule is 1,8-octanediamine hydroiodate (ODADI) (carrier: 1,8-octanediamine hydroiodate mass ratio is 1:0.1), such as... Figure 2 As shown in b, positively charged amine salts are chemically adsorbed onto the oxygen-rich surface of alumina to obtain nanoparticles (AOA).

[0180] Positively charged nanoparticle solutions and negatively charged nanoparticle solutions are mixed in a certain ratio (mass ratio 1:1) to obtain large micron clusters (APA).

[0181] 1) Prepare a layer of (2-(9H-carbazole-9-yl)ethyl)phosphonic acid (2-PACz) of about 1 nm on a cleaned ITO substrate as a hole injection layer;

[0182] 2) APA clusters of 8 mg / mL were spin-coated onto the prepared hole injection layer, with a coverage of 80%, an average height of 500 nm for the island structure, an average length and width of 5 μm, and a refractive index of 1.1.

[0183] 3) A layer of perovskite with a band gap of 1.53 eV and a thickness of about 700 nm was spin-coated onto the prepared layer;

[0184] 4) Spin-coat 1 mg / mL propylenediamine hydroiodate onto the prepared perovskite;

[0185] 5) A layer of fullerene (C) was prepared by thermal evaporation. 60 As an electron injection layer, its thickness is approximately 25 nm;

[0186] 6) A layer of copper bath (BCP) with a thickness of 5 nm was grown on C60 using thermal evaporation;

[0187] 7) The electrode is made of Ag by thermal evaporation, with a thickness of 100 nm.

[0188] The difference lies in step 2), where the porous island structure layer has islands with dimensions of 5 μm and height of 500 nm, achieving a coverage of 80%. The porous structure within the islands forms a hollow cavity structure, as illustrated in the schematic diagram below. Figure 11 As shown in b, the hollow structure is a channel with a length and width of 30 nm and a height of 500 nm. The hollow part is filled with perovskite with refractive indices of 1.0, 1.1, 1.3 and 1.5, respectively.

[0189] The simulation calculation of the light extraction efficiency of the perovskite diode device 7 was performed with reference to Example 1. The specific calculation process is as follows:

[0190] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD), and the calculation method is the same as in Example 1.

[0191] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0192] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / islands with a refractive index varying from 1.1 to 1.5 and a coverage of 80% filled with perovskite in a 100 nm size (5 μm long and wide, 500 nm high) / 1.54-eV perovskite (800 nm, n = 2.50) / C60 (30nm, n=2.06) / ALD

[0193] SnO x (20nm, n=1.94) / Ag(150nm, n=0.14+5.37i).

[0194] iv. The emission wavelength is set to 805 nm. The emission source is located at the center of the hollow perovskite channel.

[0195] By comparing the changes in device light extraction efficiency corresponding to the refractive index of the porous island structure in Example 7, the test results are as follows: Figure 11 As shown in c, it was found that the lower the refractive index of the island structure, the better.

[0196] Compared with the data of Example 5, it was found that when the porous structure in the island structure forms a hollow cavity structure and is filled with perovskite, i.e. Example 6 and Example 7, the light extraction efficiency of the prepared device structure is higher.

[0197] Compare with Example 1

[0198] The specific fabrication process for a perovskite diode with a discontinuous porous island-like structure layer featuring a pin structure is as follows:

[0199] 1) Prepare a layer of 2-(9H-carbazole-9-yl)ethylphosphonic acid (2-PACz) of about 1 nm on a cleaned ITO substrate as a hole injection layer;

[0200] 2) A layer of perovskite with a band gap of 1.53 eV and a thickness of about 700 nm was spin-coated onto the prepared layer;

[0201] 3) A layer of fullerene (C) was prepared by thermal evaporation. 60 As an electron injection layer, its thickness is approximately 25 nm;

[0202] 4) Using thermal evaporation at C 60 A layer of copper bath (BCP) with a thickness of 5 nm was grown on it;

[0203] 5) The electrode is made of Ag by thermal evaporation, with a thickness of 100 nm.

[0204] By comparing the electroluminescence external quantum efficiency and irradiance of the perovskite diode devices in Comparative Example 1 and Example 1, such as... Figure 4 and Figure 5 It was found that the perovskite diode device 1 with a low refractive index micron porous island structure layer has better light-emitting diode performance than the perovskite diode device with a full planar structure in the control example 1.

[0205] By comparing the photovoltaic performance of the perovskite diode devices in Comparative Example 1 and Example 1 under illumination conditions, such as... Figure 6 The results showed that the perovskite diode device 1 with a low refractive index micron porous island structure layer had better solar cell performance, higher open-circuit voltage, and higher photoelectric conversion efficiency than the perovskite diode device with a full planar structure in Comparative Example 1.

[0206] Compare with Example 2

[0207] The light extraction efficiency was simulated and calculated using the perovskite diode device with a completely planar, island-free structure as described in Example 1. The specific calculation process is as follows:

[0208] i. The light extraction efficiency of the perovskite diode structure is calculated using the finite-difference time-domain method (FDTD), and the calculation method is the same as in Example 1.

[0209] ii. Use periodic boundary conditions to form a semi-elliptical periodic array.

[0210] iii. Device structures for optical simulation include glass (refractive index (n) = 1.53) / ITO (100 nm, n = 1.65) / Me-4PACz (2 nm, n = 1.2) / 1.54-eV perovskite (800 nm, n = 2.50) / C 60 (30nm, n=2.06) / ALDSnO x (20nm, n=1.94) / Ag(150nm, n=0.14+5.37i).

[0211] iv. The emission wavelength is set to 805 nm. The emission source is located in the middle of the perovskite or the center of the island.

[0212] By comparing the light extraction efficiency of the devices prepared in Comparative Example 1 and Examples 1, 3, and 4, such as... Figure 10 As shown, Examples 1, 3 and 4 with low refractive index micron-sized island structures have better light extraction efficiency than Control Example 1 with a full-planar structure.

[0213] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description and ideas, and it is neither necessary nor possible to exhaustively describe all implementation methods here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A perovskite diode with high photoelectric reciprocity, comprising at least a perovskite layer, characterized in that, A discontinuous porous island structure layer is provided on one or both sides of the perovskite layer; the discontinuous porous island structure layer contains multiple independent or connected porous island structures; the average length of the porous island structure is 500-10000 nm, the average width is 500-10000 nm, and the average height is 100-1000 nm. The refractive index of the discontinuous porous island structure layer is 1.0-2.1; The discontinuous porous island structure layer is prepared by nanoparticles or clusters formed by positively charged molecules and / or negatively charged molecules loaded on a carrier. The carrier is one or more of the following: alumina, silicon oxide, magnesium oxide, nickel oxide, zirconium oxide, iron oxide, titanium oxide, zinc oxide, manganese oxide, cobalt oxide, molybdenum oxide, tungsten oxide, germanium oxide, yttrium oxide, copper oxide, zirconium oxide, Zn2GeO4, NiCo2O4, CoMn2O4, lanthanum strontium cobalt iron, barium strontium cobalt iron, lithium lanthanum titanium oxide, lithium lanthanum zirconium oxide, polymethyl methacrylate, polystyrene, silicon carbide, and aerogel materials. The positively charged molecule is one or more of the following: piperazine monohydroiodate, piperazine dihydroiodate, phenylammonium iodide, benzyl ammonium bromide, phenethylamine hydroiodate, phenethylammonium iodide, phenethylammonium bromide, p-fluorophenethylamine hydroiodate, m-fluorophenethylamine hydroiodate, 4-trifluoromethylphenethylamine hydroiodate, octylamine hydroiodate, octylamine hydrobromide, ethylenediamine chloride, mercaptoethylamine hydroiodate, 4-pyridinemethylamine iodide, m-phenylenediamine iodide, phenethylamine chloride, p-fluorophenethylamine chloride, decanediamine iodide, propylenediamine iodide, butylenediamine iodide, 1,6-hexamethylenediamine hydroiodate, 1,8-octyldiamine hydroiodate, 1,8-octyldiamine hydrobromide, guanidinohydrochloride, 1,4-phenylenediamine bromide, 1,4-phenylenediamine iodide, 1,3-bis(diphenylphosphine), 2-(2-pyridyl)ethylamine propane, oleylamine, and oleic acid. The negatively charged molecules are [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]phosphonic acid, 2-(9H-carbazole-9-yl)ethyl)phosphonic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid, phosphoric acid, hypophosphonic acid, potassium phosphate, potassium dihydrogen phosphate, sodium phosphate, decyl phosphoric acid, minophosphate, cardiolipin, ammonium chloride, diphenyl phosphate, dibenzyl phosphate, ammonium dihydrogen phosphate, guanidine phosphate, potassium phosphite, sodium hypophosphite, and methyl Phosphonic acid, phenylphosphonic acid, potassium sulfate, ammonium sulfate, sodium sulfate, aminosulfuric acid, hydrazine sulfate, ammonium persulfate, hydroxylamine sulfate, sodium thiosulfate, ammonium thiosulfate, benzenesulfonic acid, taurine, methanesulfonic acid, aminosulfonic acid, linolenic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)sulfonic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]sulfonic acid, 2-(9H-carbazole-9-yl)ethyl)sulfonic acid, 2-naphthalenesulfonic acid, 3-amino Sodium 3-nitrobenzenesulfonate, sodium 2-naphthalenesulfonate, boric acid, methylboric acid, 9-phenanthroline boric acid, butylboric acid, 3-nitrobenzeneboric acid, phenylboric acid, 2,4-dichlorophenylboric acid, disodium tetraborate, 9-anthraboric acid, lithium tetrafluoroborate, potassium tetrafluoroborate, ammonium tetrafluoroborate, sodium tetrafluoroborate, tetrafluoroboric acid, triphenylamine boric acid, dimethyltriphenylamine boric acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)boric acid, [n-(3,6-dimethyl) [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]boronic acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]carboxylic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)carboxylic acid, formic acid, acetic acid, propionic acid, 4-pyridinecarboxylic acid, 4-thiazolidinecarboxylic acid, anthraquinone-2-carboxylic acid, fluorene-9-carboxylic acid, proanthridinecarboxylic acid, 4-pyrazolecarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, where n is an integer greater than or equal to 1.

2. The high photoelectric reciprocity perovskite diode according to claim 1, characterized in that, The refractive index of the discontinuous porous island structure layer is 1.0-1.8; Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.5; Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.3; Preferably, the refractive index of the discontinuous porous island structure layer is 1.0-1.

2.

3. The high photoelectric reciprocity perovskite diode according to claim 2, characterized in that, The coverage of the discontinuous porous island structure layer is 1-99%; Preferably, the coverage of the discontinuous porous island structure layer is 40-99%; Preferably, the coverage of the discontinuous porous island structure layer is 60-90%.

4. The high photoelectric reciprocity perovskite diode according to claim 3, characterized in that, The pores in the discontinuous porous island structure layer are hollow cavities that penetrate the island structure.

5. The high photoelectric reciprocity perovskite diode according to any one of claims 1 to 3, characterized in that, The mass ratio of the carrier to the positively charged molecule is 1:0.01 to 0.15; the mass ratio of the carrier to the negatively charged molecule is 1:0.01 to 0.

15.

6. The high photoelectric reciprocity perovskite diode according to claim 5, characterized in that, The preparation process of the nanoparticles or clusters is as follows: the carrier, positively charged molecules and / or negatively charged molecules are mixed in a solvent to obtain the nanoparticles or clusters solution; The solvent is water, ethanol, isopropanol, acetone, dimethyl sulfoxide, or dimethylamide.

7. The high photoelectric reciprocity perovskite diode according to claim 6, characterized in that, The nanoparticle or cluster solution is deposited on one or both sides of the perovskite layer by magnetron sputtering, atomic layer deposition, chemical vapor deposition, chemical bath deposition, screen printing or spraying.

8. The high photoelectric reciprocity perovskite diode according to claim 5, characterized in that, The carrier is one or more of the following: alumina, silicon dioxide, magnesium oxide, nickel oxide, zirconium oxide, iron oxide, titanium oxide, zinc oxide, manganese oxide, cobalt oxide, molybdenum oxide, tungsten oxide, and aerogel material; The positively charged molecule is one or more of piperazine monohydroiodate, piperazine dihydroiodate, phenylammonium iodide, benzylammonium bromide, phenethylamine hydroiodate, phenethylammonium iodide, phenethylammonium bromide, p-fluorophenethylamine hydroiodate, m-fluorophenethylamine hydroiodate, 4-trifluoromethylphenethylamine hydroiodate, octylamine hydroiodate, and octylamine hydrobromic acid. The negatively charged molecule is one or more of the following: [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]phosphonic acid, 2-(9H-carbazole-9-yl)ethyl)phosphonic acid, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)phosphonic acid, phosphoric acid, hypophosphonic acid, potassium phosphate, potassium dihydrogen phosphate, (2,7-dimethoxy-9H-carbazole-9-yl)methyl)boric acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]boric acid, [n-(3,6-dimethyl-9-hydro-carbazole-9-yl)butyl]carboxylic acid, and (2,7-dimethoxy-9H-carbazole-9-yl)methyl)carboxylic acid, where n is an integer greater than or equal to 1.

9. The high photoelectric reciprocity perovskite diode according to claim 5, characterized in that, The structure of the high photoelectric reciprocity perovskite diode is as follows: electrode, hole blocking layer, electron injection layer, perovskite layer, discontinuous porous island structure layer, hole injection layer, and conductive substrate. The structure may be: electrode, hole blocking layer, electron injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, hole injection layer, and conductive substrate. The structure may be: electrode, electron injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, hole injection layer, and conductive substrate. The structure may be: electrode, hole injection layer, perovskite layer, discontinuous porous island structure layer, electron injection layer, and conductive substrate. Alternatively, the structure may be: electrode, hole injection layer, discontinuous porous island structure layer, perovskite layer, discontinuous porous island structure layer, electron injection layer, and conductive substrate.

10. A method for fabricating a high photoelectric reciprocity perovskite diode according to any one of claims 1 to 9, characterized in that, Includes the following steps: S11. Prepare a hole injection layer on a clean conductive substrate; S12. Prepare a discontinuous porous island structure layer on the layer prepared in step S11; S13. Deposit a perovskite layer on the layer prepared in the previous step; S14. Prepare a discontinuous porous island structure layer on the perovskite layer; S15. Sequentially fabricate an electron injection layer, a hole blocking layer, and an electrode on the layer prepared in the previous step; Step S14 can be omitted; Or it may include the following steps: S21. Sequentially fabricate electron injection layers on a clean conductive substrate; S22. Prepare a discontinuous porous island structure layer on the layer prepared in step S21; S23. Deposit a perovskite layer on the layer prepared in the previous step; S24. Prepare a discontinuous porous island structure layer on the perovskite layer; S25. Sequentially prepare a hole injection layer and an electrode on the layer prepared in the previous step; Step S24 can be omitted.

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