Method for passivating the surface of a semiconductor functional layer in a semiconductor device and use thereof

Abstract

The application relates to the technical field of semiconductor devices, and discloses a surface passivation method for a semiconductor functional layer in a semiconductor device and application thereof. The surface passivation method comprises arranging a blending layer; the material of the blending layer comprises at least one charge transport material and at least one defect passivation material; and the position of the blending layer is selected from any one of the following: directly contacting the semiconductor functional layer; being located between a passivation layer on the surface of the semiconductor functional layer and a charge transport layer; or being located between two charge transport layers on one side of the semiconductor functional layer. The blending layer realizes efficient surface passivation by using the chemical interaction between the passivation material and the surface defects of the semiconductor, and inhibits non-radiative recombination; meanwhile, the charge transport material in the blending layer constructs a continuous seepage network, guarantees efficient extraction and directional transmission of carriers, and overcomes the fundamental contradiction between efficient passivation and efficient carrier transmission in the prior art.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor devices, in particular to a surface passivation method of a semiconductor functional layer in a semiconductor device and application thereof. BACKGROUND

[0002] In semiconductor devices, especially optoelectronic devices (such as solar cells, light-emitting diodes, photodetectors), the performance limit of the device is largely restricted by the defects in the active layer material, especially the defects at the surface and interface. These defects, which are caused by atomic arrangement mismatch, stoichiometric deviation or environmental degradation during crystal growth, introduce deep or shallow level trap states in the energy gap. When photo-generated carriers (electrons and holes) or electrically injected carriers are captured by these trap states, their energy is consumed through non-radiative recombination, which not only reduces the carrier lifetime and diffusion length, but also directly leads to the deterioration of key performance indicators of the device: in photovoltaic devices, it manifests as open-circuit voltage loss, fill factor drop and ultimately photovoltaic conversion efficiency reduction; in light-emitting devices, it manifests as a sharp decrease in light-emitting efficiency and an increase in efficiency roll-off. Therefore, effective passivation treatment of the surface of the semiconductor functional layer is the key to obtaining high-performance semiconductor devices.

[0003] However, there is a fundamental contradiction between efficient passivation and efficient carrier transport: the intrinsic conductivity of the passivation material is low, and excessive passivation will reduce the transport efficiency of the carriers. Conversely, if a purely conductive transport layer is used to pursue high current, insufficient passivation will prevent the voltage potential from being released, and defect recombination will become a performance bottleneck. The existing technology usually adopts a compromise solution, such as using an extremely thin passivation layer or finding a passivation agent with certain transport capacity, but the passivation effect is often not complete or the transport capacity is still restricted. Therefore, how to achieve full and complete passivation of the semiconductor surface without sacrificing or even enhancing the transport of carriers is a major scientific problem and technical challenge that needs to be solved in the current field. SUMMARY

[0004] The present application aims to at least solve one of the above-mentioned technical problems in the prior art. To this end, one of the objects of the present application is to provide a surface passivation method of a semiconductor functional layer in a semiconductor device.

[0005] A second object of the present application is to provide an application of the surface passivation method of the semiconductor functional layer in the semiconductor device.

[0006] A third object of the present application is to provide a perovskite photo-electric conversion device.

[0007] To achieve the above-mentioned objects, the technical solution adopted by the present application is as follows:

[0008] The first aspect of the present application provides a method for passivating the surface of a semiconductor functional layer in a semiconductor device, comprising providing a blend layer; the material of the blend layer comprises at least one charge transport material and at least one defect passivation material; The position of the blend layer is selected from any one of the following: a. being in direct contact with the semiconductor functional layer; b. being between a passivation layer on the surface of the semiconductor functional layer and a charge transport layer; c. being between two charge transport layers on one side of the semiconductor functional layer.

[0009] In some embodiments of the present application, the material of the blend layer is composed of at least one charge transport material and at least one defect passivation material.

[0010] In some embodiments of the present application, the charge transport layer is selected from an electron transport layer or a hole transport layer.

[0011] In some embodiments of the present application, the semiconductor functional layer comprises a semiconductor material; the semiconductor material comprises at least one of silicon, gallium nitride, cadmium selenide, indium phosphide, perovskite.

[0012] In some embodiments of the present application, the thickness of the blend layer is 0.5-100 nm.

[0013] In some preferred embodiments of the present application, the thickness of the blend layer is 5-50 nm.

[0014] In some embodiments of the present application, the deposition method of the blend layer is selected from any one of the following: solution spin coating, vacuum thermal evaporation, magnetron sputtering, atomic layer deposition, electron beam deposition, chemical vapor deposition.

[0015] In some embodiments of the present application, the mass fraction of the defect passivation material in the blend layer is 0.1%-99.9%.

[0016] In some embodiments of the present application, the defect passivation material is selected from a compound containing a passivation functional group; the passivation functional group is selected from at least one of sulfonic acid group, phosphoric acid group, carboxyl group, amino group, pyridyl group, ammonium ion, organic amine cation, alkali metal cation.

[0017] In some preferred embodiments of the present invention, the defect passivation material is selected from 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 2,4,6-tris[3-(diphenylphosphino)phenyl]-1,3,5-triazine (PO-T2T), 2,4,6-tris(1,1'-biphenyl)-1,3,5-triazine (T2T), 2,8-bis(diphenyloxyphosphino)dibenzothiophene (PO15), di[2-((oxo)diphenylphosphino)phenyl]ether (DPEPO), and 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terbiphenyl] [-3,3''-diyl]dipyridine (TMPYPB), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,7-bis(diphenyloxyphosphino)-9,9'-spirodifluorene (SPPO13), 1,3-bis(3,5-dipyridin-3-ylphenyl)benzene (B3PyPB), 4,6-bis(3,5-di(3-pyridin)ylphenyl)-2-methylpyrimidine (B3PYMPM), 4,6-bis(3,5-di(4-pyridin)ylphenyl)-2-methylpyrimidine (B4PYMPM), 4,6-bis(3,5-di(4-pyridin)ylphenyl)-2-phenylpyrimidine (B4PyPPm) Tris[2,4,6-trimethyl-3-(3-pyridyl)phenyl]borane (3TPYMB), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP), triphenylphosphine oxide (TPPO), tributylphosphine oxide (TBPO), phenethylamine iodide (PEAI), phenethylamine bromide (PEABr), phenethylamine chloride (PEACl), piperazine monohydroiodate (PI), alumina (Al2O3), [2-(9H-carbazole-9-yl)ethyl]phosphoric acid (2PACz), [4-(9H-carbazole-9-yl)butyl]phosphoric acid (4PACz), [2-(3,6-diphenyl)phenyl]phosphoric acid (4PACz), [2-(9H-carbazole-9-yl)butyl]phosphoric acid (4PACz), [2-(9H-2 ... At least one of the following: [methoxy-9H-carbazole-9-yl)ethyl]phosphoric acid (MeO-2PACz), [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphoric acid (MeO-4PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz), (2-(3,6-dibromo9H-carbazole-9-yl)ethyl)phosphonic acid (Br-2PACz), [2-(3,6-dichloro-9H-carbazole-9-yl)ethyl]phosphonic acid (Cl-2PACz), and [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB).

[0018] In some embodiments of the present invention, the charge transport material is selected from electron transport materials or hole transport materials.

[0019] In some embodiments of the present invention, the electron transport material is selected from 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, 2,4,6-tris[3-(diphenylphosphino)phenyl]-1,3,5-triazine, 2,4,6-tris(1,1'-biphenyl)-1,3,5-triazine, 2,8-bis(diphenyloxyphosphino)dibenzothiophene, di[2-((oxo)diphenylphosphino)phenyl]ether, 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-triphenyl]-3,3''-diyl]pyridine, 4,7-diphenyl-1,10-phenanthroline, 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 2,7-bis(diphenyloxyphosphino)-9,9'-spirodifluorene, 1,3-bis(3,5-dipyridin-3-ylphenyl)benzene, 4,6-bis(3,5-bis(3-pyridinylphenyl)-2-methylpyrimidine, 4,6-bis(3,5-bis(4-pyridinylphenyl)-2-methylpyrimidine, 4,6-bis(3,5-bis(4-pyridinylphenyl)-2-phenylpyrimidine, tris[2,4,6-trimethyl-3-(3-pyridinyl)phenyl]borane, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline, fullerene C 60 Fullerene C 70 At least one of the following: [6,6]-phenyl C61 butyrate methyl ester (PCBM), [6,6]-phenyl C71 butyrate methyl ester (PC71BM), 2,7-bis(3-(dimethylamino)propyl)benzo[LMN][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NDI-N), zinc oxide (ZnO), titanium dioxide (TiO2), and tin dioxide (SnO2).

[0020] In some embodiments of the present invention, the hole transport material is selected from polyethylene dioxythiophene-poly(styrene sulfonate) (PEDOT: PSS), nickel oxide, molybdenum trioxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(9-vinylcarbazole) (PVK), and poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-n-butyl)phenyl)-diphenylamine)]. (TFB), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-MeOTAD), [2-(9H-carbazole-9-yl)ethyl]phosphoric acid (2PACz), [4-(9H-carbazole-9-yl)butyl]phosphoric acid (4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphoric acid (MeO-2PACz), [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphoric acid (MeO-4PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz), (2-(3,6-dibromo ... At least one of the following: [2-(3,6-dichloro-9H-carbazole-9-yl)ethyl]phosphonic acid (Br-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid (4PADCB), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[bis(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA), and 9,9'-(1,3-phenyl)di-9H-carbazole (mCP).

[0021] In some embodiments of the present invention, when the blended layer is located between the passivation layer and the charge transport layer on the surface of the semiconductor functional layer, the position of the blended layer is selected from any of the following: a. The blended layer is located between the passivation layer and the electron transport layer on the surface of the semiconductor functional layer; b. The blended layer is located between the passivation layer and the hole transport layer on the surface of the semiconductor functional layer.

[0022] In some embodiments of the present invention, when the blended layer is located between two charge transport layers on one side of the conductor functional layer, the position of the blended layer is selected from any of the following: a. The electron transport layer on one side of the semiconductor functional layer has a multilayer composite structure composed of several electron transport layers (≥2) and a blend layer stacked together. The blend layer is located between any two electron transport layers. The electron transport materials contained in each electron transport layer that makes up the multilayer composite structure can be the same or different. b. The hole transport layer on one side of the semiconductor functional layer has a multilayer composite structure composed of several hole transport layers (≥2) and a blend layer stacked together. The blend layer is located between any two hole transport layers. The hole transport materials contained in each hole transport layer that makes up the multilayer composite structure can be the same or different.

[0023] The second aspect of the present invention provides the application of the surface passivation method of the semiconductor functional layer in the semiconductor device described in the first aspect of the present invention in the fabrication of opto-electric conversion devices.

[0024] In some embodiments of the present invention, the photoelectric conversion device includes a solar cell, a light-emitting diode, and a photodetector.

[0025] A third aspect of the present invention provides a perovskite photoelectric conversion device having a formal or inverse structure; the formal structure includes a substrate, a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked sequentially; the inverse structure includes a substrate, a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked sequentially; wherein the perovskite layer is surface passivated using the surface passivation method described in the first aspect of the present invention.

[0026] In some embodiments of the present invention, the material of the perovskite layer comprises a metal halide perovskite; the chemical formula of the metal halide perovskite is ABX3 or L2A. n-1 B n X 3n+1 n is 1-10.

[0027] Where A represents a monovalent cation, including Cs + 、Rb + MA + FA + GA + At least one of them; B represents a divalent cation, including Pb. 2+ Sn 2+ Zn 2+ Mn 2+ Ca 2+ At least one of them; X represents a monovalent anion, including I. - ,Br -Cl - At least one of them; L represents a monovalent cation, including isopropylamine ion (C3H7NH3). + ), naphthylamine ion (C 10 H7CH2NH3 + ), benzylamine ion (C7H7NH3) + ), phenylethylamine ion (C8H9NH3) + ), butylamine ion (C4H9NH3) + Isobutylamine ion ((CH3)2CHCH2NH3) + ), tert-butylamine ion ((CH3)3CNH3) + ), ethylamine ion (C2H5NH3) + ), hexylamine ion (CH3(CH2)5NH3) + ), Octylamine ion (CH3(CH2)7NH3) + ), aniline ions (C6H5NH3) + ), amphetamine ions (C9H) 11 NH3 + At least one of the following.

[0028] In some preferred embodiments of the present invention, the material of the perovskite layer includes at least one of FAPbBr3, MAPbBr3, FAPbI3, and CsPbI3.

[0029] In some embodiments of the present invention, the substrate is selected from silicon-on-insulator (SOI), silicon wafer, silicon carbide, mica, glass, quartz sheet, copper foil, and polymer substrate.

[0030] In some preferred embodiments of the present invention, the polymer substrate includes at least one of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide, vinyl chloride resin, and polyacrylic acid.

[0031] In some embodiments of the present invention, the material of the first electrode layer is selected from at least one of ITO and FTO.

[0032] In some embodiments of the present invention, the material of the second electrode layer is selected from at least one of Au, Ag, Cu, Al, Pt, Ca, and Bi.

[0033] In some embodiments of the present invention, the structure of the hole transport layer is selected from any of the following: i. A first hole structure consisting of a plurality of stacked hole transport layers, wherein the plurality of layers is ≥1; ii. A second hole structure consisting of several hole transport layers and a blending layer stacked together, wherein the number of several layers is ≥2, and the blending layer is located between any two hole transport layers; Each hole transport layer constituting the first and second hole structures independently includes at least one hole transport material; the blend layer includes at least one hole transport material and at least one defect passivation material.

[0034] In some embodiments of the present invention, the structure of the electron transport layer is selected from any of the following: i. A first electronic structure consisting of a plurality of stacked electron transport layers, wherein the plurality of layers is ≥1; ii. A second electronic structure consisting of several electron transport layers and a blending layer stacked together, wherein the number of electron transport layers is ≥2, and the blending layer is located between any two electron transport layers; Each electron transport layer constituting the first and second electronic structures independently includes at least one electron transport material; the blend layer includes at least one electron transport material and at least one defect passivation material.

[0035] In some embodiments of the present invention, the thickness of the first electrode layer is 1-200 nm.

[0036] In some embodiments of the present invention, the thickness of the hole transport layer is 0.5-200 nm.

[0037] In some preferred embodiments of the present invention, the thickness of the hole transport layer is 10-50 nm.

[0038] In some embodiments of the present invention, the thickness of the perovskite layer is 50-2000 nm.

[0039] In some preferred embodiments of the present invention, the thickness of the perovskite layer is 100-500 nm.

[0040] In some embodiments of the present invention, the thickness of the electron transport layer is 0.5-200 nm.

[0041] In some preferred embodiments of the present invention, the thickness of the electron transport layer is 10-50 nm.

[0042] In some embodiments of the present invention, the thickness of the second electrode layer is 1-200 nm.

[0043] In some preferred embodiments of the present invention, the thickness of the second electrode layer is 50-150 nm.

[0044] In some embodiments of the present invention, the perovskite photoelectric conversion device with the formal structure is prepared by a method including the following steps: sequentially depositing a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer and a second electrode layer on a substrate to obtain the perovskite photoelectric conversion device.

[0045] In some embodiments of the present invention, the inverted perovskite photoelectric conversion device is prepared by a method comprising the following steps: sequentially depositing a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer on a substrate to obtain the perovskite photoelectric conversion device.

[0046] In some embodiments of the present invention, the deposition methods of the first electrode layer, the hole transport layer, the electron transport layer and the second electrode layer are each independently selected from one of the following: solution spin coating, vacuum thermal evaporation, magnetron sputtering, atomic layer deposition, electron beam deposition and chemical vapor deposition.

[0047] In some embodiments of the present invention, the deposition method of the perovskite layer is selected from one of solution spin coating, blade coating, and vacuum thermal evaporation.

[0048] In some embodiments of the present invention, the spin coating speed of the solution is 500-8000 rpm.

[0049] In some embodiments of the present invention, the vacuum degree of the vacuum thermal evaporation is 1×10⁻⁶. -6 -1×10 -5 Pa, evaporation rate is 0.01-2 nm / s.

[0050] Compared with the prior art, the beneficial effects of the present invention are: The surface passivation method for semiconductor functional layers in semiconductor devices provided by this invention constructs a thin layer uniformly blended with charge transport materials and defect passivation materials at the nanoscale, and places it at the critical interface of the semiconductor functional layer. This blended layer utilizes the chemical interaction between the passivation material and semiconductor surface defects to achieve efficient surface passivation and suppress non-radiative recombination. At the same time, the charge transport material constructs a continuous percolation network, ensuring efficient extraction and directional transport of charge carriers, overcoming the fundamental contradiction between efficient passivation and efficient charge carrier transport in existing technologies. The blended layer structure avoids the electrical blockage caused by pure passivation layers, ensuring high current density and fill factor, and its good interface compatibility also enhances the stability of the device.

[0051] The perovskite photoelectric conversion device provided by this invention, through a blended layer strategy, achieves sufficient passivation of the perovskite layer surface while successfully maintaining efficient carrier transport capability. This strategy enables the perovskite photoelectric conversion device to simultaneously achieve excellent photovoltaic and electroluminescence performance, with the open-circuit voltage significantly increased to 1.79V, photoelectric conversion efficiency exceeding 10%, and electroluminescence external quantum efficiency simultaneously reaching over 10%. This achieves simultaneous and significant improvement in both photovoltaic and electroluminescence performance. The blended layer strategy has broad material and structural adaptability, not only applicable to perovskite but also extend to various semiconductor systems such as silicon and gallium nitride. Furthermore, it is compatible with mainstream processes such as solution spin coating and vacuum evaporation, making it easy to integrate into existing production lines. Attached Figure Description

[0052] Figure 1 This is a schematic diagram of the inverse perovskite photoelectric conversion device in Example 1; Figure 2 The images show the GIXRD patterns before and after the deposition of the B4PYMPM first electron transport layer in Example 1. Figure 3 XPS images of the perovskite layer before and after the deposition of the B4PYMPM first electron transport layer in Example 1; Figure 4 Current-voltage curves of single-electron devices containing B4PYMPM first electron transport layers of different thicknesses; Figure 5 For those containing different proportions of B4PYMPM and C 60 Current-voltage curves of single-electron devices formed in the blend layer; Figure 6 Defect-filling voltage for single-electron devices with different electron transport layer structures; Figure 7 The photovoltaic performance test results of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2 are shown. Figure 8 The brightness-current curves of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2 are shown. Figure 9 The external quantum efficiency-current curves of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2 are shown. Figure 10 The electroluminescence spectra of the perovskite photoelectric conversion device in Example 1 at different voltages are shown. Detailed Implementation

[0053] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0054] Example 1 This embodiment fabricates an inverse-structured perovskite photoelectric conversion device. Figure 1 This is a schematic diagram of the inverse perovskite photoelectric conversion device in Example 1. Figure 1 It is known that the perovskite photoelectric conversion device consists of a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer sequentially stacked on a substrate. The perovskite layer is passivated using a blended layer strategy. The electron transport layer on one side of the perovskite layer is a second electronic structure composed of three electron transport layers and one blended layer, specifically: first electron transport layer - blended layer - second electron transport layer - third electron transport layer. The hole transport layer on the other side of the perovskite layer is a first hole structure composed of a first hole transport layer and a second hole transport layer. The specific fabrication method is as follows: S1. Using glass as a substrate, deposit an ITO first electrode layer on the surface to obtain an ITO substrate with a total thickness of 180 nm; S2, Prepare 10 mg / mL NiO x The nanocrystalline aqueous solution was filtered after low-temperature ultrasonication to remove NiO. x A nanocrystalline aqueous solution was dropped onto an ITO substrate, spin-coated at 2500 rpm for 40 s, and then annealed at 150 °C to obtain NiO. x The first hole transport layer has a thickness of 15nm; S3. Prepare a 0.5 mg / mL 2PACz ethanol solution and add it dropwise to NiO. x On the first hole transport layer, spin-coating was performed at 4000 rpm for 30 s, followed by annealing at 100 °C for 10 min to obtain a 2PACz second hole transport layer with a thickness of 1 nm. S4. Accurately weigh 0.13747 g of formamidinium hydrobromide (FABr), 0.36701 g of lead bromide, 0.0044 g of 2-methacryloyloxyethyl phosphocholine, 0.84 mL of dimethyl sulfoxide, and 0.16 mL of N,N-dimethylformamide and place them in a glass bottle. Shake at room temperature for 3 h to obtain a perovskite precursor solution. After filtration, drop the solution onto the second hole transport layer of 2PACz. Spin coat at 500 rpm for 5 s, then spin coat at 4000 rpm for 20 s. 10 s before the end of the second spin coat step, add 120 μL of chlorobenzene / ethyl acetate (3:1, v / v) mixed solvent. Anneal at 90 °C for 10 min to obtain a FAPbBr3 perovskite layer with a thickness of 270 nm. S5. A 6nm thick B4PYMPM first electron transport layer is deposited layer by layer on the FAPbBr3 perovskite layer using vacuum thermal evaporation, followed by a 5nm thick B4PYMPM layer: C 60 (2:1, w / w) hybrid layer, 20nm thick C 60 The second electron transport layer and the 6nm thick BCP third electron transport layer form the second electronic structure electron transport layer; S6. A 100nm thick Ag second electrode layer is deposited on the surface of the electron transport layer by vacuum thermal evaporation to obtain a perovskite photoelectric conversion device.

[0055] In steps S5 and S6, the vacuum degree of the vacuum thermal evaporation method is 1×10⁻⁶. -6 Pa, evaporation rate is 0.5 nm / s.

[0056] Comparative Example 1 This comparative example prepares an inverse-structured perovskite photoelectric conversion device, differing from Example 1 only in the use of C. 60 The fabrication steps for the second electron transport layer and the BCP third electron transport layer are as follows: S1. Using glass as a substrate, deposit an ITO first electrode layer on the surface to obtain an ITO substrate with a total thickness of 180 nm; S2, Prepare 10 mg / mL NiO x The nanocrystalline aqueous solution was filtered after low-temperature ultrasonication to remove NiO. x A nanocrystalline aqueous solution was dropped onto an ITO substrate, spin-coated at 2500 rpm for 40 s, and then annealed at 150 °C to obtain NiO. x The first hole transport layer has a thickness of 15nm; S3. Prepare a 0.5 mg / mL 2PACz ethanol solution and add it dropwise to NiO. x On the first hole transport layer, spin-coating was performed at 4000 rpm for 30 s, followed by annealing at 100 °C for 10 min to obtain a 2PACz second hole transport layer with a thickness of 1 nm. S4. Accurately weigh 0.13747 g of formamidinium hydrobromide (FABr), 0.36701 g of lead bromide, 0.0044 g of 2-methacryloyloxyethyl phosphocholine, 0.84 mL of dimethyl sulfoxide, and 0.16 mL of N,N-dimethylformamide and place them in a glass bottle. Shake at room temperature for 3 h to obtain a perovskite precursor solution. After filtration, drop the solution onto the second hole transport layer of 2PACz. Spin coat at 500 rpm for 5 s, then spin coat at 4000 rpm for 20 s. 10 s before the end of the second spin coat step, add 120 μL of chlorobenzene / ethyl acetate (3:1, v / v) mixed solvent. Anneal at 90 °C for 10 min to obtain a FAPbBr3 perovskite layer with a thickness of 270 nm. S5. A 20nm thick C layer was deposited layer by layer on the FAPbBr3 perovskite layer using a vacuum thermal evaporation method. 60 An electron transport layer and a 6nm thick BCP electron transport layer form the first electronic structure electron transport layer; S6, at C 60 A 100 nm thick Ag second electrode layer was deposited on the surface of the electron transport layer by vacuum thermal evaporation to obtain a perovskite photoelectric conversion device.

[0057] In steps S5 and S6, the vacuum degree of the vacuum thermal evaporation method is 1×10⁻⁶. -6 Pa, evaporation rate is 0.5 nm / s.

[0058] Comparative Example 2 This comparative example prepares an inverse-structure perovskite photoelectric conversion device, differing from Example 1 only in that it uses only the B4PYMPM first electron transport layer and C 60 The fabrication steps for the second electron transport layer and the BCP third electron transport layer are as follows: S1. Using glass as a substrate, deposit an ITO first electrode layer on the surface to obtain an ITO substrate with a total thickness of 180 nm; S2, Prepare 10 mg / mL NiO x The nanocrystalline aqueous solution was filtered after low-temperature ultrasonication to remove NiO. x A nanocrystalline aqueous solution was dropped onto an ITO substrate, spin-coated at 2500 rpm for 40 s, and then annealed at 150 °C to obtain NiO. x The first hole transport layer has a thickness of 15nm; S3. Prepare a 0.5 mg / mL 2PACz ethanol solution and add it dropwise to NiO. x On the first hole transport layer, spin-coating was performed at 4000 rpm for 30 s, followed by annealing at 100 °C for 10 min to obtain a 2PACz second hole transport layer with a thickness of 1 nm. S4. Accurately weigh 0.13747 g of formamidinium hydrobromide (FABr), 0.36701 g of lead bromide, 0.0044 g of 2-methacryloyloxyethyl phosphocholine, 0.84 mL of dimethyl sulfoxide, and 0.16 mL of N,N-dimethylformamide and place them in a glass bottle. Shake at room temperature for 3 h to obtain a perovskite precursor solution. After filtration, drop the solution onto the second hole transport layer of 2PACz. Spin coat at 500 rpm for 5 s, then spin coat at 4000 rpm for 20 s. 10 s before the end of the second spin coat step, add 120 μL of chlorobenzene / ethyl acetate (3:1, v / v) mixed solvent. Anneal at 90 °C for 10 min to obtain a FAPbBr3 perovskite layer with a thickness of 270 nm. S5. A 6nm thick B4PYMPM first electron transport layer and a 20nm thick C layer were deposited layer by layer on the FAPbBr3 perovskite layer using vacuum thermal evaporation. 60 The second electron transport layer and the 6nm thick BCP electron transport layer form the first electronic structure electron transport layer; S6. A 100nm thick Ag second electrode layer is deposited on the surface of the electron transport layer by vacuum thermal evaporation to obtain a perovskite photoelectric conversion device.

[0059] In steps S5 and S6, the vacuum degree of the vacuum thermal evaporation method is 1×10⁻⁶. -6 Pa, evaporation rate is 0.5 nm / s.

[0060] Characterization and performance testing 1. Grazing incidence X-ray diffraction (GIXRD) tests were performed on the perovskite layers before and after the deposition of the first electron transport layer of B4PYMPM in Example 1: Figure 2 The images shown are GIXRD patterns before and after the deposition of the B4PYMPM first electron transport layer in Example 1. Figure 2 It can be seen that after the B4PYMPM first electron transport layer is deposited on the surface of the perovskite layer, the (100) diffraction peak is enhanced, indicating that the B4PYMPM thin layer can enhance the surface crystallinity of the perovskite layer.

[0061] 2. X-ray photoelectron spectroscopy (XPS) was performed on the perovskite layers before and after the deposition of the first electron transport layer of B4PYMPM in Example 1: Figure 3 These are XPS images of the perovskite layer before and after the deposition of the B4PYMPM first electron transport layer in Example 1. Figure 3 (a) in the figure is the XPS plot of the Pb 4f core energy level in perovskite. Figure 3 (b) is the XPS plot of the Br 3d core energy level in perovskite, derived from... Figure 3It can be seen that, compared with the original perovskite layer, the Pb 4f peak and Br 3d peak after B4PYMPM deposition both shift to lower binding energies, indicating that there is an interaction between B4PYMPM and perovskite, which can passivate the surface of the perovskite layer.

[0062] 3. Characterization of electron transport layer transport capability: (1) Following the method in Example 1, a mixture containing different proportions of B4PYMPM and C was prepared. 60 The steps for forming a single-electronic device with a blended layer are as follows: 1) Using glass as a substrate, an ITO first electrode layer is deposited on the surface to obtain an ITO substrate with a total thickness of 180 nm; 2) Prepare a 15 mg / mL SnO2 nanocrystal ethanol solution, shake and filter, drop the SnO2 nanocrystal ethanol solution onto an ITO substrate, spin coat at 4000 rpm for 30 s, and anneal at 150 °C to obtain a SnO2 electron transport layer with a thickness of 15 nm. 3) Accurately weigh 0.13747 g of formamidinium hydrobromide (FABr), 0.36701 g of lead bromide, 0.0044 g of 2-methacryloyloxyethyl phosphocholine, 0.84 mL of dimethyl sulfoxide, and 0.16 mL of N,N-dimethylformamide and place them in a glass bottle. Shake at room temperature for 3 h to obtain a perovskite precursor solution. After filtration, drop the solution onto the SnO2 electron transport layer. First, spin coat at 500 rpm for 5 s, then spin coat at 4000 rpm for 20 s. 10 s before the end of the second spin coat step, add 120 μL of chlorobenzene / ethyl acetate (3:1, v / v) mixed solvent. Anneal at 90 °C for 10 min to obtain a FAPbBr3 perovskite layer with a thickness of 270 nm. 4) A 6nm thick B4PYMPM first electron transport layer was deposited layer by layer on the FAPbBr3 perovskite layer using vacuum thermal evaporation, followed by a 5nm thick B4PYMPM layer: C 60 Hybrid layer, 20nm thick C 60 A second electron transport layer and a 6nm thick BCP third electron transport layer form the second electronic structure electron transport layer, wherein B4PYMPM and C are mixed in the hybrid layer. 60 The mass ratios are 1:2, 1:1, 2:1, and 3:1, respectively; 5) A 100 nm thick Ag second electrode layer was deposited on the surface of the electron transport layer by vacuum thermal evaporation to obtain a perovskite single-electron device.

[0063] In steps 4) and 5), the vacuum degree of the vacuum thermal evaporation method is 1×10⁻⁶. -6 Pa, evaporation rate is 0.5 nm / s.

[0064] (2) Referring to the method in Comparative Example 2, single-electron devices containing B4PYMPM first electron transport layers of different thicknesses were prepared, and the steps are as follows: 1) Using glass as a substrate, an ITO first electrode layer is deposited on the surface to obtain an ITO substrate with a total thickness of 180 nm; 2) Prepare a 15 mg / mL SnO2 nanocrystal ethanol solution, shake and filter, drop the SnO2 nanocrystal ethanol solution onto an ITO substrate, spin coat at 4000 rpm for 30 s, and anneal at 150 °C to obtain a SnO2 electron transport layer with a thickness of 15 nm. 3) Accurately weigh 0.13747 g of formamidinium hydrobromide (FABr), 0.36701 g of lead bromide, 0.0044 g of 2-methacryloyloxyethyl phosphocholine, 0.84 mL of dimethyl sulfoxide, and 0.16 mL of N,N-dimethylformamide and place them in a glass bottle. Shake at room temperature for 3 h to obtain a perovskite precursor solution. After filtration, drop the solution onto the SnO2 electron transport layer. First, spin coat at 500 rpm for 5 s, then spin coat at 4000 rpm for 20 s. 10 s before the end of the second spin coat step, add 120 μL of chlorobenzene / ethyl acetate (3:1, v / v) mixed solvent. Anneal at 90 °C for 10 min to obtain a FAPbBr3 perovskite layer with a thickness of 270 nm. 4) A B4PYMPM first electron transport layer and a 20nm thick C layer were deposited layer by layer on the FAPbBr3 perovskite layer using a vacuum thermal evaporation method. 60 The second electron transport layer and the 6nm thick BCP third electron transport layer form the first electronic structure electron transport layer, wherein the thicknesses of the B4PYMPM first electron transport layer are 0nm, 1nm, 3nm, 6nm, 10nm and 21nm respectively. 5) A 100 nm thick Ag second electrode layer was deposited on the surface of the electron transport layer by vacuum thermal evaporation to obtain a perovskite single-electron device.

[0065] In steps 4) and 5), the vacuum degree of the vacuum thermal evaporation method is 1×10⁻⁶. -6 Pa, evaporation rate is 0.5 nm / s.

[0066] The single-electron device prepared above was tested using the space charge-confined current method. Figure 4 The current-voltage curves of single-electron devices containing B4PYMPM first electron transport layers of varying thicknesses are given by... Figure 4 It can be seen that when the thickness of the first electron transport layer of B4PYMPM is greater than 6nm, the current drops significantly, which will seriously affect the electron transport. This indicates that the pure passivation material itself is a poor electron conductor, and its thickness will seriously hinder electron transport. Figure 5 For those containing different proportions of B4PYMPM and C 60The current-voltage curve of the single-electron device formed by the blend layer is derived from... Figure 5 It can be seen that the introduction of the blend layer and the change in the ratio of electron transport material to defect passivation material in the blend layer did not have a significant impact on the current, indicating that the introduction of the blend layer did not sacrifice electron transport capability.

[0067] The defect-filling voltage of single-electron devices with different electron transport layer structures was extracted from the space charge-confined current test results. The defect-filling voltage reflects the defect concentration in the perovskite thin film; the smaller the defect-filling voltage, the lower the defect concentration in the perovskite thin film. Figure 6 To determine the defect-filling voltage of single-electron devices with different electron transport layer structures, by Figure 6 It can be seen that the defect filling voltage decreases with increasing B4PYMPM thickness, further demonstrating the passivation effect of B4PYMPM on the perovskite layer; after introducing the blend layer, the defect filling voltage decreases with increasing proportion of B4PYMPM in the blend layer, and the voltage decreases further with increasing proportion of B4PYMPM in the blend layer. 60 When the mass ratio is 2:1, the mixture is close to saturation, indicating that the introduction of the blend layer can also passivate the perovskite layer.

[0068] The above results show that B4PYMPM can passivate the perovskite layer. However, due to its poor carrier transport capability, the thickness of the B4PYMPM layer needs to be increased to achieve sufficient passivation of the perovskite layer, which affects the carrier transport in the device. The introduction of the blend layer can achieve sufficient passivation of the perovskite surface while maintaining good carrier transport capability, which can effectively solve the contradiction between carrier transport and passivation in the device, and thus obtain a high-performance device.

[0069] 4. The photovoltaic and electroluminescence performance of the perovskite photoelectric conversion devices prepared in Example 1, Comparative Example 1 and Comparative Example 2 were tested under the conditions of a solar simulator with an illumination intensity of AM1.5G.

[0070] Figure 7 The photovoltaic performance test results of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2 are provided by [the relevant authority / organization]. Figure 7 It can be seen that the open-circuit voltage of the perovskite photoelectric conversion device in Example 1 is 1.79V, and the short-circuit current density is 8.16mA / cm². 2 The fill factor was 70.03%, and the photoelectric conversion efficiency was 10.21%. In Comparative Example 1, the open-circuit voltage of the perovskite photoelectric conversion device was 1.15V, and the short-circuit current density was 8.39mA / cm². 2 The fill factor was 71.83%, and the photoelectric conversion efficiency was 6.92%. In Comparative Example 2, the perovskite photoelectric conversion device had an open-circuit voltage of 1.69V and a short-circuit current density of 7.56mA / cm².2 The fill factor was 67.30%, and the photoelectric conversion efficiency was 8.60%. Compared with Comparative Example 1, Example 1 showed an increase in open-circuit voltage from 1.15V to 1.79V and a photoelectric conversion efficiency from 6.92% to 10.21%, indicating that the blended layer strategy brought excellent passivation effect and significantly reduced non-radiative recombination voltage loss. Compared with Comparative Example 2, Example 1 showed a further increase in open-circuit voltage from 1.69V to 1.79V and a further increase in photoelectric conversion efficiency from 8.60% to 10.21%, indicating that the blended layer, compared with the double-layer structure, can provide stronger passivation while completely avoiding current and fill factor losses caused by inserting a pure passivation layer.

[0071] Figure 8 The figures show the brightness-current curves of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2. Figure 9 The external quantum efficiency-current curves of the perovskite photoelectric conversion devices in Example 1, Comparative Example 1, and Comparative Example 2 are shown. Figure 10 The electroluminescence spectra of the perovskite photoelectric conversion device in Example 1 at different voltages are obtained from... Figures 8-10 It can be seen that the maximum electroluminescence brightness of the perovskite photoelectric conversion device in Example 1 is 365989 cd / m². 2 The maximum external quantum efficiency is 10.14%; the maximum electroluminescence luminance of the perovskite photoelectric conversion device in Comparative Example 1 is 1682 cd / m². 2 The maximum external quantum efficiency is 0.03%; the maximum electroluminescence luminance of the perovskite photoelectric conversion device in Comparative Example 2 is 161010 cd / m². 2 The maximum external quantum efficiency is 6.31%. In Example 1, the perovskite photoelectric conversion device exhibits a stable emission spectrum under different voltages, with a peak at 542 nm. The device in Example 1 achieves a high efficiency of 365989 cd / m³. 2 The brightness and external quantum efficiency of 10.14% far exceed those of the two comparative examples, proving that the blended layer structure greatly optimizes the electrical injection and radiative recombination process. Moreover, the peak position and shape of the emission spectrum are very stable under different driving voltages, proving that the introduction of the blended layer does not introduce new defects or interfaces that lead to spectral instability or phase separation, and the device works reliably.

Claims

1. A method for surface passivation of a semiconductor functional layer in a semiconductor device, characterized in that, This includes setting up a blending layer; The material of the blend layer includes at least one charge transport material and at least one defect passivation material; The location of the blend layer is selected from any of the following: a. Direct contact with the semiconductor functional layer; b. Located between the passivation layer and the charge transport layer on the surface of the semiconductor functional layer; c. Between two charge transport layers located on one side of the semiconductor functional layer.

2. The surface passivation method according to claim 1, characterized in that, The semiconductor functional layer includes a semiconductor material; the semiconductor material includes at least one of silicon, gallium nitride, cadmium selenide, indium phosphide, and perovskite.

3. The surface passivation method according to claim 1, characterized in that, The thickness of the blended layer is 0.5-100 nm.

4. The surface passivation method according to claim 3, characterized in that, The defect passivation material accounts for 0.1%-99.9% of the mass of the blend layer.

5. The surface passivation method according to claim 4, characterized in that, The defect passivation material is selected from compounds containing passivation functional groups; the passivation functional group is selected from at least one of sulfonic acid group, phosphoric acid group, carboxyl group, amino group, pyridyl group, ammonium ion, organic amine cation, and alkali metal cation. And / or, the charge transport material is selected from electron transport materials or hole transport materials.

6. The application of the surface passivation method of the semiconductor functional layer in the semiconductor device according to any one of claims 1-5 in the fabrication of optoelectronic conversion devices.

7. A perovskite photoelectric conversion device, characterized in that, The perovskite photoelectric conversion device has a formal or inverse structure; the formal structure includes a substrate, a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked sequentially; the inverse structure includes a substrate, a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked sequentially; wherein the perovskite layer is surface passivated by the surface passivation method according to any one of claims 1-5.

8. The perovskite photoelectric conversion device according to claim 7, characterized in that, The perovskite layer is made of metal halide perovskite; the chemical formula of the metal halide perovskite is ABX3 or L2A. n-1 B n X 3n+1 n is 1-10; Where A represents a monovalent cation, including Cs + 、Rb + MA + FA + GA + At least one of them; B represents a divalent cation, including Pb. 2+ Sn 2+ Zn 2+ Mn 2+ Ca 2+ At least one of them; X represents a monovalent anion, including I. - ,Br - Cl - At least one of them; L represents a monovalent cation, including at least one of isopropylamine ion, naphthylamine ion, benzylamine ion, phenethylamine ion, butylamine ion, isobutylamine ion, tert-butylamine ion, ethylamine ion, hexylamine ion, octylamine ion, aniline ion, and amphetamine ion.

9. The perovskite photoelectric conversion device according to claim 7, characterized in that, The structure of the hole transport layer is selected from any of the following: i. A first hole structure consisting of a plurality of stacked hole transport layers, wherein the plurality of layers is ≥1; ii. A second hole structure consisting of several hole transport layers and a blending layer stacked together, wherein the number of several layers is ≥2, and the blending layer is located between any two hole transport layers; Each hole transport layer constituting the first and second hole structures independently includes at least one hole transport material; the blend layer includes at least one hole transport material and at least one defect passivation material.

10. The perovskite photoelectric conversion device according to claim 7, characterized in that, The structure of the electron transport layer is selected from any of the following: i. A first electronic structure consisting of a plurality of stacked electron transport layers, wherein the plurality of layers is ≥1; ii. A second electronic structure consisting of several electron transport layers and a blending layer stacked together, wherein the number of electron transport layers is ≥2, and the blending layer is located between any two electron transport layers; Each electron transport layer constituting the first and second electronic structures independently includes at least one electron transport material; the blend layer includes at least one electron transport material and at least one defect passivation material.

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