Hole transport layer, preparation method of hole transport layer, perovskite solar cell and preparation method of perovskite solar cell
By preparing a high-purity NiO layer on the substrate surface and depositing doped NiXO on it, and then using magnetron sputtering to achieve epitaxial growth, the lattice mismatch problem of the NiOx-based hole transport layer was solved, thereby improving the conductivity and photoelectric conversion efficiency of perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-11
- Publication Date
- 2026-03-10
AI Technical Summary
NiOx-based hole transport layers are prone to lattice mismatch in perovskite solar cells, leading to increased scattering and trapping of charge carriers during transport, affecting conductivity and film uniformity, and thus reducing photoelectric conversion efficiency.
A high-purity NiO layer was prepared on the substrate surface using magnetron sputtering as a seed layer. Subsequently, NiXO doped with heteroatoms such as Li, Zn, Cu, and Mg was deposited on the surface of the NiO layer. A well-crystallized NiXO crystal layer was formed by epitaxial growth, thus solving the lattice mismatch problem.
This improved the conductivity and hole transport capability of the hole transport layer, thereby enhancing the stability and photoelectric conversion efficiency of perovskite solar cells.
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Figure CN121646246A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of perovskite solar cell technology, and in particular to a hole transport layer and its preparation method, as well as a perovskite solar cell and its preparation method. Background Technology
[0002] Lead halide perovskite solar cells (perovskite solar cells) have developed to efficiencies of >27% in just a few decades. This impressive power conversion efficiency (PCE) is comparable to that of crystalline silicon solar cells and even surpasses that of cadmium telluride (CdTe) cells. In recent years, due to the emergence of self-assembled monolayer (SAM) molecules, the development of inverted perovskite (pin) cells has far surpassed that of conventional perovskite (nip) cells, making them the most promising perovskite cells for industrial production.
[0003] In inverted perovskite solar cells, adding a layer of NiO (nickel oxide) before the SAM layer is a key structural design, mainly aimed at improving the device's performance, efficiency, and stability. Simply put, the NiO layer acts as a "multifunctional protective layer and performance enhancement layer," while the SAM layer performs more refined interface energy level tuning and passivation on top of it.
[0004] In the process of preparing NiOx-based hole transport layers, in order to finely control the electrical, optical, and structural properties of the NiO layer and make it better meet the stringent requirements of hole transport layers in perovskite solar cells, elements such as Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper) are usually doped. However, the introduction of heteroatoms may cause problems such as "lattice mismatch" in the crystallinity of NiO. Although heteroatom doping is intended to improve conductivity, if the crystallinity is too poor and there are too many grain boundaries, the carriers will encounter more scattering and trapping during transport, which may offset the benefits of increased carrier concentration brought about by doping. Ultimately, the conductivity may decrease instead of increase. Moreover, uneven grain size and phase separation will lead to microscopic inhomogeneity of the film, affecting the subsequent growth of the perovskite layer. Summary of the Invention
[0005] The main objective of this invention is to provide a hole transport layer and its preparation method, as well as a perovskite solar cell and its preparation method, thereby solving the technical problem that NiOx-based hole transport layers in perovskite solar cells are prone to lattice mismatch.
[0006] To achieve the above objectives, the present invention provides a method for preparing a hole transport layer, comprising the following steps: A NiO layer is prepared on the surface of the substrate; A hole transport layer is obtained by depositing NiXO on the surface of the NiO layer away from the substrate, wherein the X in NiXO includes at least one of Li, Zn, Cu, and Mg.
[0007] In some embodiments of the present invention, the method for preparing a NiO layer on the surface of the substrate includes magnetron sputtering; and / or, the method for depositing NiXO on the surface of the NiO layer away from the substrate includes magnetron sputtering.
[0008] In some embodiments of the present invention, the method for preparing the NiO layer on the surface of the substrate is magnetron sputtering, defined as the first magnetron sputtering: The atmosphere for the first magnetron sputtering is Ar and O2, with the ratio of Ar to O2 being (20~100):(5~20). And / or, the gas pressure of the first magnetron sputtering is 0.1 Pa to 2 Pa; And / or, the target material for the first magnetron sputtering is a Ni target; And / or, the power supply for the first magnetron sputtering is 50W~400W; And / or, the duration of the first magnetron sputtering is 10s to 60s.
[0009] In some embodiments of the present invention, the method for depositing NiO on the surface of the NiO layer away from the substrate is magnetron sputtering, defined as a second magnetron sputtering: The atmosphere for the second magnetron sputtering is Ar and O2, with an Ar to O2 ratio of (20~100):(0.2~1.0). And / or, the gas pressure of the second magnetron sputtering is 2 Pa to 5 Pa; And / or, the target material for the second magnetron sputtering is a NiXO target; And / or, the power supply for the second magnetron sputtering is 150W~400W; And / or, the second magnetron sputtering time is 300s~600s.
[0010] In some embodiments of the present invention, when NiXO is deposited on the surface of the NiO layer away from the substrate, the substrate containing the NiO layer is heated to 100°C to 300°C.
[0011] In some embodiments of the present invention, the thickness of the NiO layer is 0.5 nm to 1 nm.
[0012] The present invention also provides a hole transport layer for use in perovskite solar cells, wherein the hole transport layer is prepared by the preparation method described above.
[0013] The present invention also provides a perovskite solar cell, wherein the perovskite solar cell includes the hole transport layer as described above.
[0014] In some embodiments of the present invention, the perovskite solar cell includes, in sequence, the substrate, the hole transport layer, the perovskite active layer, the electron transport layer, and the back electrode layer. Alternatively, the perovskite solar cell may comprise the substrate, the hole transport layer, the perovskite active layer, the electron transport layer, the hole blocking layer, and the back electrode layer, which are stacked sequentially.
[0015] The present invention also provides a method for fabricating a perovskite solar cell, the method comprising the following steps: fabricating a hole transport layer, wherein the process for fabricating the hole transport layer comprises the steps in the hole transport layer fabrication method described above.
[0016] The beneficial effects that this invention can achieve are: The hole transport layer of the present invention is a NiOx (nickel oxide) based hole transport layer, and is doped with at least one heteroatom selected from Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper). This can effectively control the electrical properties, optical properties, and structure of the NiOx-based hole transport layer, thereby improving the photoelectric conversion efficiency of perovskite solar cells.
[0017] Furthermore, this invention first prepares a NiO layer on the surface of a substrate, and then deposits a NiXO layer containing at least one heteroatom selected from Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper) on the surface of the NiO layer away from the substrate to obtain a hole transport layer. The high-purity NiO layer prepared first has a relatively perfect crystal structure with neatly arranged atoms and few defects. It can serve as a seed layer for crystal growth, providing a perfect template for subsequent atomic deposition. This allows the subsequently deposited NiXO to easily find the correct lattice position, achieving epitaxial growth and thus continuing to grow into an ordered structure. Ultimately, it forms a large crystal with good crystallinity, growing a NiXO crystal layer with good crystallinity. This solves the problem of lattice mismatch caused by the doping of heteroatoms on the crystallinity of NiO, thereby improving the conductivity and hole transport capability of the hole transport layer, and further improving the stability and photoelectric conversion efficiency of perovskite solar cells. Attached Figure Description
[0018] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.
[0019] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell according to an embodiment of the present invention; Figure 2This is a schematic diagram of the structure of a perovskite solar cell according to another embodiment of the present invention; Figure 3 The X-ray diffraction (XRD) patterns of the hole transport layer in experimental group-1 and control group-1 of this invention are shown. Figure 4 This is a comparison of the IV curves of perovskite solar cells in experimental group-1 and control group-1 of this invention. Figure 5 This is a comparison of the IV curves of perovskite solar cells in experimental group-2 and control group-2 of this invention. Figure 6 This is a comparison of the IV curves of the perovskite solar cells in experimental group-3 and control group-3 of this invention. Figure 7 This is a comparison of the IV curves of perovskite solar cells in experimental group-4 and control group-4 of this invention. Explanation of icon numbers: 100. Perovskite solar cell; 10. Substrate; 20. Hole transport layer; 30. Perovskite active layer; 40. Electron transport layer; 50. Hole blocking layer; 60. Back electrode layer.
[0020] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation
[0021] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0023] In this invention, descriptions involving "first," "second," etc., are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. Furthermore, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. If the combination of technical solutions is contradictory or impossible to implement, such a combination should be considered non-existent and not within the scope of protection claimed by this invention.
[0024] In the process of preparing NiOx-based hole transport layers, in order to finely control the electrical, optical, and structural properties of the NiO layer and make it better meet the stringent requirements of hole transport layers in perovskite solar cells, elements such as Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper) are usually doped. However, the introduction of heteroatoms may cause problems such as "lattice mismatch" in the crystallinity of NiO. Although heteroatom doping is intended to improve conductivity, if the crystallinity is too poor and there are too many grain boundaries, the carriers will encounter more scattering and trapping during transport, which may offset the benefits of increased carrier concentration brought about by doping. Ultimately, the conductivity may decrease instead of increase. Moreover, uneven grain size and phase separation will lead to microscopic inhomogeneity of the film, affecting the subsequent growth of the perovskite layer.
[0025] In view of this, the present invention provides a method for preparing a hole transport layer, comprising the following steps: A NiO layer is prepared on the surface of the substrate; A hole transport layer is obtained by depositing NiXO on the surface of the NiO layer away from the substrate, wherein the X in NiXO includes at least one of Li, Zn, Cu, and Mg.
[0026] The hole transport layer of the present invention is a NiOx-based hole transport layer, and is doped with at least one heteroatom selected from Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper). This can effectively control the electrical properties, optical properties, and structure of the NiOx-based hole transport layer, thereby improving the photoelectric conversion efficiency of perovskite solar cells.
[0027] Furthermore, this invention first prepares a NiO layer on the surface of a substrate, and then deposits a NiXO layer containing at least one heteroatom selected from Mg (magnesium), Zn (zinc), Li (lithium), and Cu (copper) on the surface of the NiO layer away from the substrate to obtain a hole transport layer. The high-purity NiO layer prepared first has a relatively perfect crystal structure with neatly arranged atoms and few defects. It can serve as a seed layer for crystal growth, providing a perfect template for subsequent atomic deposition. This allows the subsequently deposited NiXO to easily find the correct lattice position, achieving epitaxial growth and thus continuing to grow into an ordered structure. Ultimately, it forms a large crystal with good crystallinity, growing a NiXO crystal layer with good crystallinity. This solves the problem of lattice mismatch caused by the doping of heteroatoms on the crystallinity of NiO, thereby improving the conductivity and hole transport capability of the hole transport layer, and further improving the stability and photoelectric conversion efficiency of perovskite solar cells.
[0028] It is understandable that the NiO layer refers to a film containing NiO. NiO can be deposited directly on the surface of the substrate, or it can be formed on the surface of the substrate through a chemical reaction.
[0029] In some embodiments, the method for preparing a NiO layer on the surface of a substrate includes magnetron sputtering (PVD). Magnetron sputtering can deposit a very uniform film thickness on a large-area substrate, controlling the thickness deviation within a small range, even within 5%. This results in a NiO layer with a good crystal structure, orderly atomic arrangement, and few defects, providing a perfect template for subsequent NiXO deposition. This allows the subsequently deposited NiXO to easily find the correct lattice position, achieving epitaxial growth and continuing its long-range ordered structure, ultimately forming a large crystal with good crystalline polarity, and growing a NiXO crystal layer with good crystallinity. In addition, the high-energy particles of magnetron sputtering bombard the substrate surface to a certain extent, which has a certain cleaning and activation effect, enhancing the adhesion between the deposited NiO film and the substrate, and reducing the risk of detachment. Furthermore, as a dry process, magnetron sputtering does not use solvents, dispersants, or binders, avoiding the potential harm of organic residual impurities to the performance and stability of perovskite devices from the source.
[0030] In some embodiments, the method for preparing a NiO layer on the surface of a substrate is magnetron sputtering, which is defined as the first magnetron sputtering.
[0031] In some embodiments, the atmosphere for the first magnetron sputtering is Ar and O2.
[0032] In some embodiments, the ratio of Ar to O2 in the atmosphere of the first magnetron sputtering is (20~100):(5~20), which can be 20:20, 20:5, 100:20, 100:10, 100:5, 50:20, 80:20, 80:10, etc.
[0033] In some embodiments, the gas pressure of the first magnetron sputtering is 0.1 Pa to 2 Pa, which can be 0.1 Pa, 0.5 Pa, 0.8 Pa, 1 Pa, 1.3 Pa, 1.5 Pa, 1.8 Pa, 2 Pa, etc.
[0034] In some embodiments, the target material for the first magnetron sputtering is a Ni target, which can grow a NiO layer with good crystallinity in an oxygen-rich environment.
[0035] In some embodiments, the power supply for the first magnetron sputtering is 50W to 400W, and can be 50W, 60W, 70W, 80W, 90W, 100W, etc.
[0036] In some embodiments, the time for the first magnetron sputtering is 10s to 60s, which can be 30s, 35s, 40s, 45s, 50s, 55s, 60s, etc.
[0037] In some embodiments, the thickness of the NiO layer is 0.5nm to 1nm, and can be 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, etc.
[0038] This invention, by controlling the atmosphere, pressure, power supply, and magnetron sputtering time during the first magnetron sputtering, facilitates the preparation of a high-purity NiO layer. This NiO layer possesses a relatively perfect crystal structure with well-organized atoms and few defects, serving as a seed layer for crystal growth. It provides a near-perfect template for subsequent atomic deposition, allowing the deposited NiO to easily find the correct lattice positions for epitaxial growth, thus continuing to grow into an ordered structure. Ultimately, this results in a large crystal with excellent crystallinity, producing a NiO crystal layer with good crystallinity. This solves the problem of lattice mismatch caused by doping with heteroatoms, thereby improving the conductivity and hole transport capability of the hole transport layer, further enhancing the stability and photoelectric conversion efficiency of perovskite solar cells.
[0039] In some embodiments, the second magnetron sputtering includes magnetron sputtering (PVD). Preparing a NiXO crystalline layer by magnetron sputtering is beneficial for sputtering and depositing a thin film with uniform thickness and good crystal structure. Moreover, it is compatible with NiO layers prepared by the same magnetron sputtering method, which facilitates the atoms in NiXO to easily find the correct lattice positions, achieve epitaxial growth, grow a structurally ordered crystal, and finally form a large crystal with good crystal polarity, thus growing a NiXO crystalline layer with good crystallinity.
[0040] In some embodiments, the method of depositing NiXO on the surface of the NiO layer away from the substrate includes magnetron sputtering, and the magnetron sputtering step is defined as a second magnetron sputtering.
[0041] In some embodiments, the atmosphere for the second magnetron sputtering is Ar and O2, and the ratio of Ar to O2 is (20~100):(0.2~1.0), which can be 20:0.2, 20:0.5, 20:1.0, 50:0.2, 50:0.5, 50:1.0, 100:0.2, 100:0.5, 100:1.0, etc.
[0042] In some embodiments, the gas pressure of the second magnetron sputtering is 2 Pa to 5 Pa, which can be 2 Pa, 2.5 Pa, 3 Pa, 3.5 Pa, 4 Pa, 4.5 Pa, 5 Pa, etc.
[0043] In some embodiments, the target material for the second magnetron sputtering is a NiXO target, wherein the X in NiXO includes at least one of Li, Zn, Cu, and Mg.
[0044] In some embodiments, the power supply for the second magnetron sputtering is 150W~400W, and can be 150W, 160W, 180W, 200W, 220W, 250W, 280W, 300W, 320W, 350W, 380W, 400W, etc.
[0045] In some embodiments, the time for the second magnetron sputtering is 300s to 600s, which can be 300s, 350s, 400s, 450s, 500s, 550s, 600s, etc.
[0046] This invention enables NiXO to form a uniform thin film deposited on the surface of the NiO layer by controlling the atmosphere, gas pressure, power supply, and magnetron sputtering time during the second magnetron sputtering, thus helping NiXO to easily find the correct lattice position and achieve epitaxial growth.
[0047] In some embodiments, when NiXO is deposited on the surface of the NiO layer away from the substrate, the substrate containing the NiO layer is heated to 100°C to 300°C, or 200°C. By heating the substrate, sufficient kinetic energy is provided to the sputtered atoms, enabling them to align and migrate in an orderly manner along the pre-deposited NiO nuclei, thereby achieving high-quality epitaxial growth from the nuclei to the NiXO layer.
[0048] In some embodiments, the substrate includes conductive glass, and a hole transport layer is prepared on the surface of the conductive glass.
[0049] In some embodiments, the conductive glass includes TCO glass (transparent conductive oxide glass), and a NiO layer is prepared on the surface of the TCO glass.
[0050] In some embodiments, TCO glass includes at least one of FTO (fluorine-doped tin oxide) glass and AZO (aluminum-doped zinc oxide) glass.
[0051] The present invention also provides a perovskite solar cell, which includes the hole transport layer as described above and has at least all the beneficial effects of the hole transport layer described above.
[0052] In some embodiments, refer to Figure 1 The perovskite solar cell 100 includes a substrate 10, a hole transport layer 20, a perovskite active layer 30, an electron transport layer 40, and a back electrode layer 60 stacked sequentially.
[0053] In some embodiments, the perovskite solar cell further includes a modification layer in the art. The modification layer may be disposed between the substrate and the hole transport layer, between the hole transport layer and the perovskite active layer, between the perovskite active layer and the electron transport layer, and between the electron transport layer and the back electrode layer. The modification layer is used to improve interfacial contact and improve the electrochemical performance of the perovskite solar cell.
[0054] In some embodiments, a modification layer is further provided between the electron transport layer and the back electrode layer. The modification layer is a hole blocking layer. Figure 2 The titanium dioxide solar cell 100 includes a substrate 10, a hole transport layer 20, a perovskite active layer 30, an electron transport layer 40, a hole blocking layer 50, and a back electrode layer 60, which are stacked sequentially.
[0055] The present invention also provides a method for fabricating a perovskite solar cell, comprising the following steps: fabricating a hole transport layer, wherein the process for fabricating the hole transport layer includes the steps in the hole transport layer fabrication method described above.
[0056] In some embodiments, the method for fabricating a perovskite solar cell includes: To prepare the hole transport layer described above: a NiO layer is prepared on the surface of a substrate; NiXO is deposited on the surface of the NiO layer away from the substrate to obtain the hole transport layer, wherein the X in NiXO includes at least one of Li, Zn, Cu, and Mg; Preparation of perovskite active layer; Fabrication of an electron transport layer; Prepare the back electrode layer.
[0057] In some embodiments, the substrate is conductive glass, including TCO glass, and the following step is further included before preparing the hole transport layer: cleaning the conductive glass.
[0058] In some embodiments, the steps for cleaning conductive glass are as follows: the conductive glass is placed on a glass holder for cleaning, and then dried with a nitrogen air gun for later use. In order to improve the wettability of the conductive glass surface, the cleaned conductive glass is placed face up in an ultraviolet ozone instrument for 5 to 30 minutes. The grease and organic matter on the surface of the conductive glass are oxidized and removed by ultraviolet light and ozone, thereby improving the wettability of the surface.
[0059] In some embodiments, a perovskite active layer is prepared by coating a perovskite solution onto the surface of the hole transport layer away from the substrate.
[0060] In some embodiments, the perovskite solution includes perovskite material and a solvent, wherein the perovskite material is dissolved in the solvent to obtain the perovskite solution.
[0061] In some embodiments, the perovskite material comprises ABX3, wherein the A-site comprises at least one of an organic cation and an inorganic cation, and the organic cation comprises methylammonium ion (CH3NH4+). +3 MA (abbreviated as MA) + ), formamidinium ion (HC(NH2)) 2+ FA (abbreviated as FA) + At least one of the following, the inorganic cations including cesium ions (Cs) +), rubidium ions (Rb + At least one of the following: B-site includes a cation, which includes at least one of lead ion, tin ion, and germanium ion; X-site includes a halide ion, which includes Cl- ion. - ,Br - I - At least one of them.
[0062] In some embodiments, the solvents for dissolving perovskite materials include DMF and DMSO.
[0063] In some embodiments, the solvent is DMF and DMSO, with a volume ratio of DMF to DMSO of 4:1.
[0064] In some embodiments, the perovskite active layer is prepared by spin coating, and the spin coating conditions are as follows: the spin coating speed is 2500 rpm to 3500 rpm, which can be 3000 rpm; the spin coating time is 25 s to 35 s, which can be 30 s; and the spin coating acceleration is 280 pm / s to 330 pm / s, which can be 300 rpm / s.
[0065] In some embodiments, after the perovskite solution is spin-coated onto the surface of the hole transport layer away from the substrate, an annealing treatment is performed. The annealing temperature is 140°C to 160°C, or 150°C, and the annealing time is 8 min to 12 min, or 10 min.
[0066] In some embodiments, an electron transport layer is prepared on the surface of the perovskite active layer away from the hole transport layer, and the preparation method includes vapor deposition, magnetron sputtering, etc.
[0067] In some embodiments, the electron transport material includes C 60 .
[0068] In some embodiments, the thickness of the electron transport layer is 25 nm to 35 nm.
[0069] In some embodiments, a back electrode layer is prepared on the surface of the electron transport layer opposite to the perovskite active layer.
[0070] In some embodiments, the method for preparing the back electrode layer includes magnetron sputtering, vapor deposition, etc.
[0071] In some embodiments, the back electrode layer includes at least one of Au, Ag, Cu, and MoO3.
[0072] In some embodiments, the thickness of the back electrode layer is 90nm~110nm, and can be 100nm.
[0073] In some embodiments, the fabrication method of perovskite solar cells further includes the fabrication of a functional layer. The functional layer may be disposed between the substrate and the hole transport layer, between the hole transport layer and the perovskite active layer, between the perovskite active layer and the electron transport layer, and between the electron transport layer and the back electrode layer. The functional layer is used to improve interfacial contact and improve the electrochemical performance of the perovskite solar cell.
[0074] For example, in some embodiments, the method for fabricating a perovskite solar cell further includes the fabrication of a hole blocking layer, wherein a hole blocking layer is fabricated on the surface of the electron transport layer away from the perovskite active layer, and a back electrode layer is fabricated on the surface of the hole blocking layer away from the electron transport layer.
[0075] In some embodiments, the hole-blocking layer includes BCP (Bath Copper Powder).
[0076] In some embodiments, the thickness of the hole blocking layer is 15nm~25nm, and can be 20nm.
[0077] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention and are not intended to limit the present invention.
[0078] Example 1 Example 1: The fabrication method of perovskite solar cells is as follows: Substrate cleaning: Place 20 pieces of 2×2 cm FTO glass in a glass holder, then put them into a 400 mL beaker. Add 150 mL of detergent solution, deionized water, ethanol, and IPA sequentially. Sonicate each for 5 minutes at room temperature, then remove and dry with an N2 air gun. Perform UVO treatment on the cleaned FTO glass substrate: Place the FTO glass substrate in a UVO cleaning machine and clean for 30 minutes.
[0079] Preparation of the hole transport layer: The treated FTO glass was placed in the PVD chamber, the chamber door was closed, and a vacuum of 1×10⁻⁶ was applied. - 4 Add Ar and O2 in a 1:1 ratio as the process gas, set the sputtering pressure to 0.3 Pa, open the Ni target baffle, and sputter for 30 seconds using a 100W DC power supply to complete the first magnetron sputtering and obtain the NiO layer. Then, turn off the baffle and the DC power supply, and change the magnetron sputtering process as follows: use Ar and O2 in a 40:0.2 ratio as the process gas, set the sputtering pressure to 2.0 Pa, open the NiMgO target baffle, heat the FTO glass to 150°C, and sputter for 10 minutes using a 250W RF power supply to complete the second magnetron sputtering and obtain the NiMgO crystal layer. Then, turn off the baffle and the RF power supply, turn off the process gas, and break the cavity to complete the deposition of the hole transport layer.
[0080] Preparation of the perovskite active layer: 1.4 M FAI, 1.54 M PbI2, 0.5 M MACl and 0.05 M CsCl were dissolved in a mixed solution of DMF:DMSO = 4:1 (v / v) to obtain a perovskite solution. A hole transport layer of 120 μL of the perovskite solution was spin-coated onto the surface of the FTO glass away from the glass (spin-coating conditions: 3000 rpm, 30 s, 300 rpm / s). During this process, 150 μL of ethyl acetate was added dropwise, and then the solution was annealed on a hot plate at 150 °C for 10 min to obtain the perovskite active layer.
[0081] Fabrication of the electron transport layer: A 30 nm thick C layer was deposited on the surface of the perovskite active layer away from the hole transport layer using a vapor deposition method. 60 An electron transport layer was obtained.
[0082] Preparation of hole blocking layer: A hole blocking layer with a thickness of 20 nm is obtained by vapor deposition of BCP (bath copper spirit) on the surface of the electron transport layer away from the hole transport layer.
[0083] Preparation of back electrode layer: An Ag metal back electrode layer with a thickness of 100 nm was deposited by magnetron sputtering.
[0084] The perovskite solar cells prepared are referred to as Experimental Group-1.
[0085] Comparative Example 1 Comparative Example 1 prepared a complete perovskite solar cell device using the same method as in Example 1, but the preparation of the hole transport layer was different: Place the processed FTO glass into the PVD chamber, close the chamber door, and evacuate to 1×10⁻⁶. -4 Ar and O2 in a ratio of 40:0.2 were added as process gases. The sputtering pressure was set to 2.0 Pa. The substrate was heated to 150°C. The NiMgO target baffle was opened. Sputtering was performed for 10 minutes using an RF power supply of 250W. Then the baffle and RF power supply were turned off, the process gas was turned off, and the chamber was vented to complete the deposition of the hole transport layer.
[0086] The control group-1 is used to refer to the perovskite solar cells prepared.
[0087] Example 2 Example 2 prepared a complete perovskite solar cell device according to the preparation method of Example 1. However, the difference is that the target material for doping heteroatoms in Example 2 is NiLiO. The perovskite solar cell prepared by Experiment Group-2 is referred to as Experiment Group-2.
[0088] Comparative Example 2 Comparative Example 2 prepared a complete perovskite solar cell device using the same method as in Example 2, but the preparation of the hole transport layer was different: Place the processed FTO glass into the PVD chamber, close the chamber door, and evacuate to 1×10⁻⁶. -4 Ar and O2 in a ratio of 40:0.2 were added as process gases. The sputtering pressure was set to 2.0 Pa. The substrate was heated to 150°C. The NiLiO target baffle was opened. Sputtering was performed for 10 minutes using an RF power supply of 250W. Then the baffle and RF power supply were turned off, the process gas was turned off, and the chamber was vented to complete the deposition of the hole transport layer.
[0089] The control group-2 is used to refer to the perovskite solar cells prepared.
[0090] Example 3 Example 3 describes the preparation of a complete perovskite solar cell device using the same method as Example 1. However, the target material for doping heteroatoms in Example 3 is NiMgLiO. The terms "Control Group-3" and "Experimental Group-3" refer to the perovskite solar cells prepared in this example.
[0091] Comparative Example 3 Comparative Example 3 prepared a complete perovskite solar cell device using the same method as in Example 3, but the preparation of the hole transport layer was different: Place the processed FTO glass into the PVD chamber, close the chamber door, and evacuate to 1×10⁻⁶. -4 Ar and O2 in a ratio of 40:0.2 were added as process gases. The sputtering pressure was set to 2.0 Pa. The substrate was heated to 150°C. The NiMgLiO target baffle was opened. Sputtering was performed for 10 minutes using an RF power supply of 250W. Then the baffle and RF power supply were turned off, the process gas was turned off, and the chamber was vented to complete the deposition of the hole transport layer.
[0092] The perovskite solar cell prepared by the control group-3 is used as a substitute.
[0093] Example 4 Example 4 describes the fabrication of a complete perovskite solar cell device using the same method as Example 1. However, in Example 4, Cu was used as the back electrode layer, with a film thickness of 100 nm. The terms "Control Group-4" and "Experimental Group-4" refer to the perovskite solar cells fabricated.
[0094] Comparative Example 4 Comparative Example 4 prepared a complete perovskite solar cell device using the same method as in Example 4, but the preparation of the hole transport layer was different: Place the processed FTO glass into the PVD chamber, close the chamber door, and evacuate to 1×10⁻⁶. -4Ar and O2 in a ratio of 40:0.2 were added as process gases. The sputtering pressure was set to 2.0 Pa. The substrate was heated to 150°C. The NiMgO target baffle was opened. Sputtering was performed for 10 minutes using an RF power supply of 250W. Then the baffle and RF power supply were turned off, the process gas was turned off, and the chamber was vented to complete the deposition of the hole transport layer.
[0095] The perovskite solar cell prepared using the control group-4 as a substitute.
[0096] Performance testing 1. The hole transport layer of experimental group-1 and control group-1 was characterized using X-ray diffraction, and the results were obtained. Figure 3 , Figure 3 The XRD patterns of experimental group-1 and control group-1 are shown below. Figure 3 It can be seen that the diffraction peak intensity of the hole transport layer in Experimental Group-1 is significantly higher by sputtering NiO first and then NiMgO. This indicates that the NiMgO thin film grown by NiO nuclei has better crystallinity, more regular atomic arrangement, and larger and more complete crystal particles.
[0097] 2. The solar perovskite cells of the examples and comparative examples were subjected to IV tests using a solar simulator to test their power generation performance under standard conditions. Figure 4 This is a comparison of the IV curves of perovskite solar cells in experimental group-1 and control group-1. Figure 5 This is a comparison of the IV curves of perovskite solar cells in experimental group-2 and control group-2 of this invention. Figure 6 This is a comparison of the IV curves of the perovskite solar cells in experimental group-3 and control group-3 of this invention. Figure 7 This is a comparison chart of the IV curves of the perovskite solar cells of experimental group-4 and control group-4 in this invention. The specific data are recorded in Table 1.
[0098] Table 1
[0099] As can be seen from Table 1, all experimental groups -1 to -4 obtained hole transport layers by first sputtering a NiO layer and then sputtering NiXO on the surface of the NiO layer. The photoelectric conversion efficiency of the perovskite solar cells obtained in this way was higher than that of the perovskite solar cells of control groups -1 to -4 that directly sputtered NiXO.
[0100] The above are merely preferred embodiments of the present invention and do not limit the scope of the patent. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.
Claims
1. A method for producing a hole transport layer, characterized by, The method comprises the following steps: preparing a NiO layer on a surface of a substrate; depositing NiXO on a surface of the NiO layer away from the substrate to obtain a hole transport layer, X in NiXO comprising at least one of Li, Zn, Cu, and Mg.
2. The method for producing a hole transport layer according to claim 1, wherein The method for preparing the NiO layer on the surface of the substrate comprises a magnetron sputtering method; and / or the method for depositing NiXO on the surface of the NiO layer away from the substrate comprises a magnetron sputtering method.
3. The method of claim 2, wherein the hole transport layer is prepared by a method comprising: The method for preparing the NiO layer on the surface of the substrate is a magnetron sputtering method, which is defined as a first magnetron sputtering. The atmosphere of the first magnetron sputtering is Ar and O2, and the ratio of Ar to O2 is (20-100):(5-20). The gas pressure of the first magnetron sputtering is 0.1 Pa-2 Pa. The target material of the first magnetron sputtering is a Ni target. The power of the first magnetron sputtering is 50 W-400 W. The time of the first magnetron sputtering is 10 s-60 s.
4. The method of claim 3, wherein the hole transport layer is prepared by a method comprising: The method for depositing NiXO on the surface of the NiO layer away from the substrate is a magnetron sputtering method, which is defined as a second magnetron sputtering. The atmosphere of the second magnetron sputtering is Ar and O2, and the ratio of Ar to O2 is (20-100):(0.2-1.0). The gas pressure of the second magnetron sputtering is 2 Pa-5 Pa. The target material of the second magnetron sputtering is a NiXO target. The power of the second magnetron sputtering is 150 W-400 W. The time of the second magnetron sputtering is 300 s-600 s.
5. The method of claim 1, wherein the hole transport layer is prepared by a method comprising: When the NiXO is deposited on the surface of the NiO layer away from the substrate, the substrate containing the NiO layer is heated to 100°C-300°C.
6. The method of claim 1, wherein the hole transport layer is prepared by a method comprising: The thickness of the NiO layer is 0.5 nm-1 nm.
7. A hole transport layer applied to a perovskite solar cell, characterized in that, The hole transport layer is prepared by the preparation method according to any one of claims 1-6.
8. A perovskite solar cell, characterized by, The perovskite solar cell comprises the hole transport layer according to claim 7.
9. The perovskite solar cell according to claim 8, characterized in that, The perovskite solar cell comprises the substrate, the hole transport layer, a perovskite active layer, an electron transport layer, and a back electrode layer which are sequentially stacked, or the perovskite solar cell comprises the substrate, the hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and a back electrode layer which are sequentially stacked.
10. A method of producing a perovskite solar cell, characterized by, The method for preparing the perovskite solar cell comprises the following steps: preparing a hole transport layer, and the process for preparing the hole transport layer comprises the steps in the method for preparing the hole transport layer according to any one of claims 1-6.