WO2023109071A1 - Perovskite solar cell containing optical micro-cavity structure - Google Patents

Perovskite solar cell containing optical micro-cavity structure Download PDF

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WO2023109071A1
WO2023109071A1 PCT/CN2022/100716 CN2022100716W WO2023109071A1 WO 2023109071 A1 WO2023109071 A1 WO 2023109071A1 CN 2022100716 W CN2022100716 W CN 2022100716W WO 2023109071 A1 WO2023109071 A1 WO 2023109071A1
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solar cell
perovskite solar
layer
film layer
preparation
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Chinese (zh)
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张赟
赵志国
赵东明
李新连
夏渊
李梦洁
刘家梁
董超
王百月
王森
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中国华能集团清洁能源技术研究院有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the technical field of batteries, in particular to a perovskite solar battery including an optical microcavity structure.
  • An optical microcavity is an optical resonant cavity that can confine the light field in the micron or even nanometer range. It uses reflection, scattering or diffraction at material interfaces with discontinuous dielectric constants to confine light energy to oscillate back and forth in a small area, thereby increasing photon lifetime.
  • the optical microcavity structure can increase the optical path of incident light through reflection and scattering at the interface, which greatly improves the absorption of incident light by the photoactive layer in the cell structure, thereby improving the photoelectric conversion efficiency of the cell. (PCE).
  • the vacuum deposition thin film process usually includes three processes: 1) the evaporation material changes from the condensed phase to the gas phase to form evaporated particles; 2) the movement of the evaporated particles between the evaporation source and the substrate; 3) the condensation of the evaporated particles after reaching the substrate, Nucleation, growth, and film formation.
  • the deposition sequence of the film on the substrate under high vacuum conditions has a clear stage (as shown in the schematic diagram 1 of each stage of film growth): 1) firstly form a three-dimensional nucleus with disordered distribution, the formation of the nucleus is disordered and isotropic, Then the evaporated particles on the surface of the substrate quickly reach the saturation density, and the three-dimensional nucleus grows slowly to form a three-dimensional island-like microstructure.
  • the shape of the island is determined by the interface energy and deposition conditions, and the entire growth process is controlled by diffusion; With further deposition, the size of the islands gradually increases, and the islands approach each other and merge into large islands, and the density of the islands decreases monotonously at a rate determined by the deposition conditions; 3) when the distribution of the islands reaches a certain critical state, the islands and islands rapidly Merge to form a Unicom network structure (the network contains a large number of empty tunnels); 4) The final stage is to evaporate particles to fill the network and tunnels between the islands and generate a continuous dense film layer.
  • the technical problem solved by the present invention is to provide a perovskite solar cell including an optical microcavity structure, which can increase the collection efficiency of incident light without affecting other performances of the cell, and finally improve the photoelectric conversion efficiency of the cell.
  • the application provides a perovskite solar cell comprising an optical microcavity structure, including a substrate, a discontinuous metallic silver thin film layer, a hole transport layer, a perovskite active layer, an electron transport layer and dense metallic silver thin film layer.
  • the thickness of the discontinuous metallic silver thin film layer is 2-10 nm, and the thickness of the dense metallic silver thin film layer is 50-200 nm.
  • the substrate is selected from a hard substrate or a flexible substrate;
  • the hole transport layer is selected from NiO x , PEDOT:PSS or poly[bis(4-phenyl)(2,4,6-trimethyl phenyl)amine];
  • the electron transport layer is selected from one or more of TiO 2 , SnO 2 , PCBM, C 60 and BCP.
  • the preparation method of the perovskite solar cell comprises the following steps: A) substrate cleaning; B) preparation of a hole transport layer; C) preparation of a discontinuous metal silver film layer; D) preparation of a perovskite active layer; E) Preparation of electron transport layer; F) Preparation of dense metallic silver thin film layer.
  • the discontinuous metal silver film layer is prepared by vacuum evaporation method, the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascal, the coating speed is 0.05nm/s ⁇ 0.5nm/s, and the film thickness is 2 ⁇ 10nm.
  • the coating speed is 0.02nm/s ⁇ 0.08nm/s.
  • the dense metal silver film layer is prepared by vacuum evaporation method, the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascal, the coating speed is 0.5nm/s ⁇ 5nm/s, and the film thickness is 50 ⁇ 200nm.
  • the application provides a perovskite solar cell comprising an optical microcavity structure, wherein a discontinuous silver thin film layer and a dense silver thin film layer are introduced as an optical microcavity, under this structure, the incident sunlight passes through calcium After being absorbed by the titanium active layer, the transmitted light is irradiated on the dense silver film, and most of the light is reflected and enters the interior of the perovskite solar cell again to be absorbed by the perovskite active layer.
  • the discontinuous silver thin film does not affect the incidence of light, while the dense silver film layer can reflect most of the incident light. Therefore, the application of the microcavity structure can greatly increase the absorption efficiency of perovskite solar cells for incident sunlight, thereby improving the photoelectric conversion efficiency of the cells.
  • Fig. 1 is the schematic diagram of each stage of the growth of vacuum deposited film in the background technology of the present invention
  • Fig. 2 is the microphotograph of discontinuous silver film layer of the present invention
  • Fig. 3 is the microphotograph of dense silver film layer of the present invention.
  • Fig. 4 is the basic structure schematic diagram of perovskite solar cell of the present invention.
  • FIG. 5 is a schematic diagram of the working principle of the microcavity structure of the perovskite solar cell of the present invention.
  • Fig. 6 is the current-voltage characteristic curve of the embodiment of the present invention and the comparative example.
  • the present invention adds an optical microcavity inside the perovskite solar cell that can improve the light collection efficiency of the perovskite solar cell.
  • This structure is organically combined with the classic perovskite solar cell (including p-i-n and n-i-p structures), increasing the The collection efficiency of incident light does not affect other characteristics of the battery, which improves the photoelectric conversion efficiency of the battery.
  • the embodiment of the present application discloses a perovskite solar cell containing an optical microcavity structure, including a substrate, a discontinuous silver metal film layer, a hole transport layer, a perovskite active layer, an electronic Transport layer and dense metallic silver film layer.
  • FIG. 4 The schematic diagram of the basic structure of the perovskite solar cell described in this application is shown in Figure 4, wherein the basic structure of the p-i-n perovskite solar cell is: 1-substrate (containing a transparent electrode layer); 2-microcavity structure layer; 3-hole transport layer; 4-perovskite active layer; 5-electron transport layer; 6-microcavity structure layer; n-i-p type perovskite solar cell basic structure is: 1-substrate (including transparent electrode layer); 2-microcavity structure layer; 3-electron transport layer; 4-perovskite active layer; 5-hole transport layer; 6-microcavity structure layer.
  • the discontinuous metallic silver thin film layer and the dense metallic silver thin film layer in the present application are used as an optical microcavity, and its working principle is specifically shown in Figure 5, and 1 in Figure 5 -substrate; 2-discontinuous silver film layer; 3-carrier transport layer (hole and electron transport layer) and perovskite active layer; 4-continuous or dense silver film layer; 5-metal electrode; 6- Reflected light; 7-reflected light; 8-incident light.
  • the described substrate (containing transparent electrode) of the perovskite solar cell described in the application is usually hard substrates such as commercial high-transmission FTO glass and ITO glass, or the flexible substrate material (PET, PEN, PI, PC film that covers ITO) wait).
  • hard substrates such as commercial high-transmission FTO glass and ITO glass
  • flexible substrate material PET, PEN, PI, PC film that covers ITO
  • the material of the hole transport layer is usually NiO x , PEDOT:PSS, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) and the like.
  • the NiO x layer is usually prepared by a magnetron sputtering method, and the thickness of the NiO x layer is 20-30 nm, preferably 25 nm.
  • the silver film layer (discontinuous layer and dense layer) is prepared by vacuum evaporation, and the thickness and microstructure of the film are prepared by adjusting the evaporation rate and evaporation time, wherein the dense layer can be used as a metal electrode at the same time.
  • the silver thin film thickness of transparent electrode side is 2 ⁇ 10nm, and the microscopic structure of silver thin film layer here is discontinuous island shape, as shown in Figure 2, the translucency performance of described discontinuous silver thin film layer is good, to light The reflection is diffuse reflection; the thickness of the silver film on the metal electrode side is 50-200nm, where the silver film layer is a dense continuous film layer, as shown in Figure 3; the light transmission of the dense silver film layer is poor, and there are mirror surfaces. Excellent reflective and conductive properties.
  • the discontinuous metallic silver thin film layer and the dense metallic silver electrode layer described in this application together constitute a microcavity structure, and the dense metallic silver thin film layer can also serve as a conductive electrode layer.
  • the material of the perovskite active layer is an ABX type 3 compound, wherein A is selected from K + , Rb + , Cs + , CH 3 NH 3 + or CH(NH 2 ) 2 + , B is Pb 2+ , and X is Cl - , Br - , I - or SCN - , the thickness of the perovskite active layer is 100-1000nm.
  • the perovskite active layer material is prepared by a solution processing film forming process from a precursor solution.
  • the electron transport layer is selected from one or more of TiO 2 , SnO 2 , PCBM, C 60 and BCP; preferably, the electron transport layer is a composite film of PCBM or C 60 and BCP.
  • the PCBM film is deposited on the perovskite active layer film by the solution film forming process, and the film thickness is 10-50nm;
  • the C 60 film is deposited on the perovskite active layer film layer by the vacuum thermal evaporation process, and the film thickness is 5-25nm ;
  • the BCP film is also deposited on the PCBM or C 60 film layer by vacuum thermal evaporation process, with a thickness of 5-10nm.
  • the PCBM thin film is prepared by a spin-coating method, and the spin-coating speed is 3000-5000 rpm/min.
  • the vapor deposition rate of the C 60 and BCP is 0.01-0.2 angstroms per second.
  • the metal electrodes are selected from one or more of gold, copper, silver, aluminum and conductive carbon material electrodes.
  • the preparation method of the perovskite solar cell according to the present invention is prepared according to methods well known to those skilled in the art, and can be divided into the following steps carried out in sequence: (1) cleaning of the substrate; (2) preparation of the hole transport layer; (3) Preparation of discontinuous metallic silver thin film layer; (4) Preparation of perovskite active layer precursor solution; (5) Preparation of perovskite active layer: (6) Preparation of electron transport layer; (7) Dense metallic silver thin film layer That is, the metal electrode layer is prepared.
  • the substrate cleaning refers to the substrate material covered with transparent conductive electrodes and flexible substrates such as glass, PET, PC, and PI, which are ultrasonically cleaned twice with surfactant, deionized water, acetone, and isopropanol in sequence, each time for 10 to 15 minutes. Minutes, then dried or blown dry with nitrogen, surface treated with ultraviolet ozone (UVO) or plasma for 10 to 20 minutes before use.
  • transparent conductive electrodes and flexible substrates such as glass, PET, PC, and PI
  • the preparation process of the discontinuous silver thin film is as follows: the degree of vacuum is less than 4*10 -4 Pascals, the coating speed is 0.02nm/s-0.5nm/s, the film thickness is 2-10nm, and the microstructure of the obtained film is discontinuous island-like Crystallization; wherein, the preferred coating speed is 0.02nm/s-0.08nm/s.
  • the preparation process of the continuous and dense silver thin film is as follows: the degree of vacuum is less than 4*10 -4 Pascal, the coating speed is 0.5nm/s-5nm/s, and the film thickness is 50-200nm, to obtain a dense and dense silver film that completely covers the carrier transport layer. Continuous silver film layer.
  • the preparation of the perovskite active layer includes two parts: precursor solution preparation and thin film deposition: the precursor solution is prepared by dissolving methyl ammonium iodide (MAI) and lead iodide (PbI 2 ) in a mixed solvent at a molar ratio of 1:1 Medium; thin film deposition chooses any one of conventional solution film-forming methods such as spin coating method, wire bar coating method, doctor blade coating method, slit extrusion coating method, screen printing, gravure printing, letterpress printing, etc. kind.
  • the mixed solvent is a mixed solvent of DMF and DMSO, the concentration of the solution is 0.5-5 mol/ml, and the volume ratio of the two solvents of DMF and DMSO is (0.2-5):1.
  • the preparation of the perovskite active layer is prepared by uniform coating method, and the high-efficiency perovskite light-absorbing layer is prepared by anti-solvent method, which can be divided into three steps: (I) the precursor liquid is added dropwise to the hole The surface of the transport layer; (II) start to spin-coat to prepare a thin film, and anti-solvent is added dropwise during the spin-coating process to obtain a high-efficiency perovskite active layer; (III) annealing.
  • the solution processing film-forming process of the perovskite active layer is preferably a film preparation process of uniform glue spin coating, doctor blade coating and slit extrusion coating.
  • the spin-coating method adopts a table-top coating machine to spin the film, and the preferred film coating speed is 1000-6000 rpm/min (rev/min).
  • the blade coating method adopts a flat coater to coat the film, the coating speed is 0.02-1 m/min (meter/min), and the coating width is 0.2-5 cm.
  • the solution supply speed is 5-500 microliters/minute
  • the coating speed is 0.2-2m/min
  • the substrate temperature is 25-100°C during coating
  • the coating width is 0.2-5 cm
  • the preparation of the active layer by spin coating is divided into two stages, the first stage is a slow stage, the preferred spin coating speed is 1000 ⁇ 4000rpm/min, and the spin coating time is 1 ⁇ 3 seconds; the second stage is a high speed stage, preferably The spin-coating speed is 4000-5000 rpm/min, and the spin-coating time is 30-50 seconds.
  • the anti-solvent is chlorobenzene
  • the volume of the solvent is 100-200 ⁇ l
  • the anti-solvent is added dropwise 20 seconds before the spin coating stops.
  • the anti-solvent is added within 2 seconds.
  • the perovskite solar cell with optical microcavity structure provided by the present invention is more excellent in photoelectric conversion performance, especially output current.
  • the patterned FTO glass is cleaned by the method described above, and then treated with UVO for 15 minutes for later use;
  • step (3) Spin-coat the perovskite precursor solution described in step (4) on the NiO x hole-transport layer obtained in step (3): the whole spin-coating process is divided into three steps, first with 4000rpm/min spin-coating 3 second; then spin-coat at 5000rpm/min for 30 seconds; finally add 200 ⁇ l of chlorobenzene (anti-solvent) dropwise when 5000rpm/min high-speed spin-coat for 11 seconds. The requirement is that all anti-solvents are added dropwise within 2 seconds.
  • the thickness of the light-absorbing layer is controlled at about 500nm;
  • step (5) The sheet obtained in step (5) is annealed at 130° C. for 20 minutes in an oven and taken out after being cooled;
  • step (6) The sheet obtained in step (6) is moved into a vacuum evaporation chamber, and after vacuuming until the vacuum degree is lower than 4*10 -4 Pa, the thermal evaporation deposition method is started to prepare the electron transport layer; the evaporation rate of C 60 is less than 0.05 angstrom/s, film thickness 20nm; BCP evaporation rate less than 0.1 angstrom/s, film thickness 9nm;
  • the sheet prepared in step (7) is also prepared by the thermal evaporation deposition method to prepare silver electrodes, the vacuum degree is controlled to be lower than 4*10 -4 Pa, the initial evaporation rate is 0.8nm/s, and the online film thickness testing equipment is passed Monitor the real-time film thickness. When the film thickness is greater than 10nm, adjust the evaporation rate to 1.5nm/s. After the film thickness is greater than 20nm, adjust the evaporation rate to 4nm/s. The final thickness of the silver electrode is 100nm, and the perovskite solar cell device is prepared. .
  • Example 1 Preparation of perovskite solar cells based on microcavity structure
  • the substrate after magnetron sputtering NiO x and annealing was moved into the vacuum evaporation chamber, and after vacuuming until the vacuum degree was lower than 4*10 -4 Pa, a discontinuous silver film layer was evaporated, and the evaporation rate was 0.02nm/second, the silver film thickness is controlled to 5nm; the subsequent perovskite active layer, electron transport layer and silver metal electrode layer are the same as those described in Comparative Example 1.
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 5nm, and the other steps remained unchanged.
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.1 nm/sec, the film thickness was 5 nm, and the other steps remained unchanged.
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.2nm/second, the film thickness was 5nm, and other steps remained unchanged.
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.5nm/second, the film thickness was 5nm, and the other steps remained unchanged.
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 2nm, and the other steps remained unchanged.
  • Example 8 Preparation of perovskite solar cells based on microcavity structure
  • Example 1 The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 8nm, and the other steps remained unchanged.
  • the perovskite solar cell prepared by the above-mentioned embodiment is tested under a standard sunlight intensity (AM1.5G, 100mW/cm 2 ) using a solar simulator (xenon lamp as a light source), and the solar simulation
  • the detectors were calibrated at the National Renewable Energy Laboratory using silicon diodes (with KG9 visible filters). The corresponding test results are shown in Table 1 and Figure 6.
  • the perovskite solar cell based on the microcavity structure of the present invention can adjust the output current value of the battery by regulating the thickness and evaporation rate of the discontinuous silver film, and then can realize the same Traditional structure perovskite solar cells have comparable or higher photoelectric conversion efficiency.

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Abstract

Provided in the present invention is a perovskite solar cell comprising an optical micro-cavity structure. The perovskite solar cell comprises a substrate, a discontinuous metal silver thin-film layer, a hole transport layer, a perovskite active layer, an electron transport layer and a compact metal silver thin-film layer, which are sequentially stacked together. Compared with a perovskite solar cell with a traditional structure, the perovskite solar cell with an optical micro-cavity structure provided in the present invention has better performance in the aspect of photoelectric conversion performance, especially in the aspect of output current.

Description

一种包含光学微腔结构的钙钛矿太阳能电池A perovskite solar cell comprising an optical microcavity structure
本申请要求于2021年12月15日提交中国专利局、申请号为202111535306.3、发明名称为“一种包含光学微腔结构的钙钛矿太阳能电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 15, 2021, with the application number 202111535306.3 and the title of the invention "A Perovskite Solar Cell Containing an Optical Microcavity Structure", the entire content of which is passed References are incorporated in this application.
技术领域technical field
本发明涉及电池技术领域，尤其涉及一种包含光学微腔结构的钙钛矿太阳能电池。The invention relates to the technical field of batteries, in particular to a perovskite solar battery including an optical microcavity structure.
背景技术Background technique
光学微腔是一种能够把光场限制在微米甚至纳米量级区域中的光学谐振腔。它利用在介电常数不连续的材料界面处的反射、散射或衍射，将光能量限制在很小的区域内来回振荡，从而增加光子寿命。在钙钛矿太阳能电池中，光学微腔结构可以通过界面处的反射和散射增加入射光的光程，极大地提高电池结构中的光活性层对入射光的吸收，进而提高电池的光电转换效率(PCE)。An optical microcavity is an optical resonant cavity that can confine the light field in the micron or even nanometer range. It uses reflection, scattering or diffraction at material interfaces with discontinuous dielectric constants to confine light energy to oscillate back and forth in a small area, thereby increasing photon lifetime. In perovskite solar cells, the optical microcavity structure can increase the optical path of incident light through reflection and scattering at the interface, which greatly improves the absorption of incident light by the photoactive layer in the cell structure, thereby improving the photoelectric conversion efficiency of the cell. (PCE).
真空沉积薄膜工艺通常包含三个过程：1)蒸发材料由凝聚相转变成气相，形成蒸发粒子；2)蒸发粒子在蒸发源与基片之间的运动；3)蒸发粒子到达基片后凝结、成核、长大、成膜。高真空条件下基片上薄膜的沉积顺序具有明确的阶段性(如薄膜生长各阶段示意图1所示)：1)首先形成无序分布的三维核，核的形成的无序和各向同性的，然后基片表面的蒸发粒子迅速到达饱和密度，三维核慢慢长大形成三维岛状的微观结构，岛的形状由界面能和沉积条件决定，整个生长过程受扩散控制；2)随着蒸发粒子的进一步沉积，岛的尺寸逐渐增大，岛与岛互相靠近并合并成大岛，岛的密度以沉积条件决定的速率单调减少；3)岛的分布达到某一临界状态时，岛与岛迅速合并形成联通网络结构(网络包含大量的空隧道)；4)最终的阶段是蒸发粒子填充各岛之间的网络及隧道并生成连续致密的薄膜层。The vacuum deposition thin film process usually includes three processes: 1) the evaporation material changes from the condensed phase to the gas phase to form evaporated particles; 2) the movement of the evaporated particles between the evaporation source and the substrate; 3) the condensation of the evaporated particles after reaching the substrate, Nucleation, growth, and film formation. The deposition sequence of the film on the substrate under high vacuum conditions has a clear stage (as shown in the schematic diagram 1 of each stage of film growth): 1) firstly form a three-dimensional nucleus with disordered distribution, the formation of the nucleus is disordered and isotropic, Then the evaporated particles on the surface of the substrate quickly reach the saturation density, and the three-dimensional nucleus grows slowly to form a three-dimensional island-like microstructure. The shape of the island is determined by the interface energy and deposition conditions, and the entire growth process is controlled by diffusion; With further deposition, the size of the islands gradually increases, and the islands approach each other and merge into large islands, and the density of the islands decreases monotonously at a rate determined by the deposition conditions; 3) when the distribution of the islands reaches a certain critical state, the islands and islands rapidly Merge to form a Unicom network structure (the network contains a large number of empty tunnels); 4) The final stage is to evaporate particles to fill the network and tunnels between the islands and generate a continuous dense film layer.
如何在钙钛矿太阳能电池中引入光学微腔以提高其电池性能，具有重要意义。How to introduce optical microcavities in perovskite solar cells to improve their cell performance is of great significance.
发明内容Contents of the invention
本发明解决的技术问题在于提供了一种包含光学微腔结构的钙钛矿太阳能电池，其可增加对入射光的收集效率，且不影响电池的其他性能，最终提高电池的光电转换效率。The technical problem solved by the present invention is to provide a perovskite solar cell including an optical microcavity structure, which can increase the collection efficiency of incident light without affecting other performances of the cell, and finally improve the photoelectric conversion efficiency of the cell.
有鉴于此，本申请提供了一种包括光学微腔结构的钙钛矿太阳能电池，包括依次叠加设置的基片、不连续金属银薄膜层、空穴传输层、钙钛矿活性层、电子传输层和致密金属银薄膜层。In view of this, the application provides a perovskite solar cell comprising an optical microcavity structure, including a substrate, a discontinuous metallic silver thin film layer, a hole transport layer, a perovskite active layer, an electron transport layer and dense metallic silver thin film layer.
优选的，所述不连续金属银薄膜层的厚度为2～10nm，所述致密金属银薄膜层的厚度为50～200nm。Preferably, the thickness of the discontinuous metallic silver thin film layer is 2-10 nm, and the thickness of the dense metallic silver thin film layer is 50-200 nm.
优选的，所述基片选自硬质基底或柔性基底；所述空穴传输层选自NiO x、PEDOT:PSS或聚[双(4-苯基)(2,4,6-三甲基苯基)胺]；所述电子传输层选自TiO 2、SnO 2、PCBM、C 60和BCP中的一种或多种。 Preferably, the substrate is selected from a hard substrate or a flexible substrate; the hole transport layer is selected from NiO x , PEDOT:PSS or poly[bis(4-phenyl)(2,4,6-trimethyl phenyl)amine]; the electron transport layer is selected from one or more of TiO 2 , SnO 2 , PCBM, C 60 and BCP.
优选的，所述钙钛矿太阳能电池的制备方法包括以下步骤：A)基片清洗；B)空穴传输层制备；C)不连续金属银薄膜层制备；D)钙钛矿活性层制备；E)电子传输层制备；F)致密金属银薄膜层的制备。Preferably, the preparation method of the perovskite solar cell comprises the following steps: A) substrate cleaning; B) preparation of a hole transport layer; C) preparation of a discontinuous metal silver film layer; D) preparation of a perovskite active layer; E) Preparation of electron transport layer; F) Preparation of dense metallic silver thin film layer.
优选的，所述不连续金属银薄膜层制备采用真空蒸镀法制备，所述真空蒸镀法的真空度小于4*10 -4帕斯卡，镀膜速度0.05nm/s～0.5nm/s，薄膜厚度2～10nm。 Preferably, the discontinuous metal silver film layer is prepared by vacuum evaporation method, the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascal, the coating speed is 0.05nm/s～0.5nm/s, and the film thickness is 2 ~ 10nm.
优选的，所述镀膜速度为0.02nm/s～0.08nm/s。Preferably, the coating speed is 0.02nm/s˜0.08nm/s.
优选的，所述致密金属银薄膜层制备采用真空蒸镀法制备，所述真空蒸镀法的真空度小于4*10 -4帕斯卡，镀膜速度0.5nm/s～5nm/s，薄膜厚度50～200nm。 Preferably, the dense metal silver film layer is prepared by vacuum evaporation method, the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascal, the coating speed is 0.5nm/s～5nm/s, and the film thickness is 50～ 200nm.
本申请提供了一种包含光学微腔结构的钙钛矿太阳能电池，其中引入了不连续的银薄膜层和致密的银薄膜层作为光学微腔，在此种结构下，入射的太阳光经钙钛矿活性层吸收后透射的光照射到致密的银薄膜后绝大部分光经反射后再次进入钙钛矿太阳能电池内部被钙钛矿活性层吸收，二次透射过活性层的光到达不连续的银薄膜后，发生漫反射，这样前述二次透射过活性层的光经漫反射后第三次进入钙钛矿太阳能电池内部被活性层吸收，然后多次重复上述过程；不连续的银薄膜层不影响光的入射，而致密的银薄膜层则可以反射绝大部 分的入射光。因此，微腔结构的应用可以大幅度增加钙钛矿太阳能电池对入射太阳光的吸收效率，进而提高电池的光电转换效率。The application provides a perovskite solar cell comprising an optical microcavity structure, wherein a discontinuous silver thin film layer and a dense silver thin film layer are introduced as an optical microcavity, under this structure, the incident sunlight passes through calcium After being absorbed by the titanium active layer, the transmitted light is irradiated on the dense silver film, and most of the light is reflected and enters the interior of the perovskite solar cell again to be absorbed by the perovskite active layer. After the thin silver film, diffuse reflection occurs, so that the light transmitted through the active layer for the second time enters the interior of the perovskite solar cell for the third time and is absorbed by the active layer after diffuse reflection, and then repeats the above process many times; the discontinuous silver thin film The layer does not affect the incidence of light, while the dense silver film layer can reflect most of the incident light. Therefore, the application of the microcavity structure can greatly increase the absorption efficiency of perovskite solar cells for incident sunlight, thereby improving the photoelectric conversion efficiency of the cells.
附图说明Description of drawings
图1为本发明背景技术中真空沉积薄膜的生长各阶段示意图；Fig. 1 is the schematic diagram of each stage of the growth of vacuum deposited film in the background technology of the present invention;
图2为本发明不连续的银薄膜层的微观照片；Fig. 2 is the microphotograph of discontinuous silver film layer of the present invention;
图3为本发明致密的银薄膜层的微观照片；Fig. 3 is the microphotograph of dense silver film layer of the present invention;
图4为本发明钙钛矿太阳能电池的基本结构示意图；Fig. 4 is the basic structure schematic diagram of perovskite solar cell of the present invention;
图5为本发明钙钛矿太阳能电池的微腔结构工作原理示意图；5 is a schematic diagram of the working principle of the microcavity structure of the perovskite solar cell of the present invention;
图6为本发明实施例和对比例电流-电压特性曲线。Fig. 6 is the current-voltage characteristic curve of the embodiment of the present invention and the comparative example.
具体实施方式Detailed ways
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention.
本发明在钙钛矿太阳能电池内部增设可提高钙钛矿太阳能电池光收集效率的光学微腔，该结构与经典的钙钛矿太阳能电池(包括p-i-n和n-i-p结构)有机的结合起来，增加了对入射光的收集效率，同时不影响电池的其他特性，提升了电池的光电转换效率。具体的，本申请实施例公开了一种包含光学微腔结构的钙钛矿太阳能电池，包括依次叠加设置的基片、不连续金属银薄膜层、空穴传输层、钙钛矿活性层、电子传输层和致密金属银薄膜层。The present invention adds an optical microcavity inside the perovskite solar cell that can improve the light collection efficiency of the perovskite solar cell. This structure is organically combined with the classic perovskite solar cell (including p-i-n and n-i-p structures), increasing the The collection efficiency of incident light does not affect other characteristics of the battery, which improves the photoelectric conversion efficiency of the battery. Specifically, the embodiment of the present application discloses a perovskite solar cell containing an optical microcavity structure, including a substrate, a discontinuous silver metal film layer, a hole transport layer, a perovskite active layer, an electronic Transport layer and dense metallic silver film layer.
本申请所述钙钛矿太阳能电池的基本结构示意图如图4所示，其中p-i-n性钙钛矿太阳能电池的基本结构为：1-基片(含透明电极层)；2-微腔结构层；3-空穴传输层；4-钙钛矿活性层；5-电子传输层；6-微腔结构层；n-i-p型钙钛矿太阳能电池基本结构为：1-基片(含透明电极层)；2-微腔结构层；3-电子传输层；4-钙钛矿活性层；5-空穴传输层；6-微腔结构层。The schematic diagram of the basic structure of the perovskite solar cell described in this application is shown in Figure 4, wherein the basic structure of the p-i-n perovskite solar cell is: 1-substrate (containing a transparent electrode layer); 2-microcavity structure layer; 3-hole transport layer; 4-perovskite active layer; 5-electron transport layer; 6-microcavity structure layer; n-i-p type perovskite solar cell basic structure is: 1-substrate (including transparent electrode layer); 2-microcavity structure layer; 3-electron transport layer; 4-perovskite active layer; 5-hole transport layer; 6-microcavity structure layer.
在本申请提供的钙钛矿太阳能电池的基础上，本申请中的不连续金属银薄膜层和致密金属银薄膜层作为了光学微腔，其工作原理具体如图5所示，图5中1-基片；2-不连续银薄膜层；3-载流子传输层(空穴和电子传输层)以及钙 钛矿活性层；4-连续或致密银薄膜层；5-金属电极；6-反射光；7-反射光；8-入射光。On the basis of the perovskite solar cell provided by the present application, the discontinuous metallic silver thin film layer and the dense metallic silver thin film layer in the present application are used as an optical microcavity, and its working principle is specifically shown in Figure 5, and 1 in Figure 5 -substrate; 2-discontinuous silver film layer; 3-carrier transport layer (hole and electron transport layer) and perovskite active layer; 4-continuous or dense silver film layer; 5-metal electrode; 6- Reflected light; 7-reflected light; 8-incident light.
本申请所述钙钛矿太阳能电池的所述基片(含透明电极)通常为商用高透FTO玻璃和ITO玻璃等硬质基底，或覆盖ITO的柔性基底材料(PET、PEN、PI、PC膜等)。The described substrate (containing transparent electrode) of the perovskite solar cell described in the application is usually hard substrates such as commercial high-transmission FTO glass and ITO glass, or the flexible substrate material (PET, PEN, PI, PC film that covers ITO) wait).
所述空穴传输层材料通常为NiO x、PEDOT:PSS、聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)等。其中，NiO x层通常采用磁控溅射方法制备得到，NiO x层的厚度在20～30nm，优选25nm。 The material of the hole transport layer is usually NiO x , PEDOT:PSS, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) and the like. Wherein, the NiO x layer is usually prepared by a magnetron sputtering method, and the thickness of the NiO x layer is 20-30 nm, preferably 25 nm.
所述银薄膜层(不连续层和致密层)通过真空蒸镀制备得到，薄膜的厚度和微观结构通过调控蒸镀速率和蒸镀时间制备得到，其中致密层同时可用作金属电极。透明电极侧的银薄膜厚度为2～10nm，此处银薄膜层的微观结构为不连续的岛状，如图2所示，所述不连续的银薄膜层的透光性能良好，对光线的反射为漫反射；金属电极侧的银薄膜厚度为50～200nm，此处银薄膜层为致密的连续膜层，如图3所示；所述致密的银薄膜层透光性较差，存在镜面反射，导电性能优良。The silver film layer (discontinuous layer and dense layer) is prepared by vacuum evaporation, and the thickness and microstructure of the film are prepared by adjusting the evaporation rate and evaporation time, wherein the dense layer can be used as a metal electrode at the same time. The silver thin film thickness of transparent electrode side is 2～10nm, and the microscopic structure of silver thin film layer here is discontinuous island shape, as shown in Figure 2, the translucency performance of described discontinuous silver thin film layer is good, to light The reflection is diffuse reflection; the thickness of the silver film on the metal electrode side is 50-200nm, where the silver film layer is a dense continuous film layer, as shown in Figure 3; the light transmission of the dense silver film layer is poor, and there are mirror surfaces. Excellent reflective and conductive properties.
本申请中所述不连续的金属银薄膜层和致密的金属银电极层共同构成了微腔结构，致密金属银薄膜层同时可作为导电电极层。The discontinuous metallic silver thin film layer and the dense metallic silver electrode layer described in this application together constitute a microcavity structure, and the dense metallic silver thin film layer can also serve as a conductive electrode layer.
所述钙钛矿活性层的材料为ABX 3型化合物，其中A选自K +、Rb +、Cs +、CH 3NH 3 +或CH(NH 2) 2 +，B为Pb 2+，X为Cl -、Br -、I -或SCN -，钙钛矿活性层的厚度为100～1000nm。所述钙钛矿活性层材料通过前驱体溶液采用溶液加工成膜工艺制备得到。 The material of the perovskite active layer is an ABX type 3 compound, wherein A is selected from K + , Rb + , Cs + , CH 3 NH 3 + or CH(NH 2 ) 2 + , B is Pb 2+ , and X is Cl - , Br - , I - or SCN - , the thickness of the perovskite active layer is 100-1000nm. The perovskite active layer material is prepared by a solution processing film forming process from a precursor solution.
所述电子传输层选自TiO 2、SnO 2、PCBM、C 60和BCP中的一种或多种；优选的，电子传输层为PCBM或C 60和BCP的组合薄膜。其中，PCBM薄膜采用溶液成膜工艺沉积于钙钛矿活性层薄膜上方，薄膜厚度10～50nm；C 60薄膜采用真空热蒸镀工艺沉积于钙钛矿活性层薄膜层上方，薄膜厚度5～25nm；BCP薄膜同样采用真空热蒸镀工艺沉积于PCBM或C 60薄膜层上方，厚度5～10nm。所述PCBM薄膜选用匀胶旋涂法制备，旋涂速度为3000～5000rpm/min。所述C 60和BCP的蒸镀速率为0.01～0.2埃每秒。 The electron transport layer is selected from one or more of TiO 2 , SnO 2 , PCBM, C 60 and BCP; preferably, the electron transport layer is a composite film of PCBM or C 60 and BCP. Among them, the PCBM film is deposited on the perovskite active layer film by the solution film forming process, and the film thickness is 10-50nm; the C 60 film is deposited on the perovskite active layer film layer by the vacuum thermal evaporation process, and the film thickness is 5-25nm ; The BCP film is also deposited on the PCBM or C 60 film layer by vacuum thermal evaporation process, with a thickness of 5-10nm. The PCBM thin film is prepared by a spin-coating method, and the spin-coating speed is 3000-5000 rpm/min. The vapor deposition rate of the C 60 and BCP is 0.01-0.2 angstroms per second.
所述金属电极选自金、铜、银、铝和导电碳材料电极中的一种或多种。The metal electrodes are selected from one or more of gold, copper, silver, aluminum and conductive carbon material electrodes.
本发明所述的钙钛矿太阳能电池的制备方法按照本领域技术人员熟知的方法制备，可分为依次进行的以下几个步骤：(1)基片清洗；(2)空穴传输层制备；(3)不连续金属银薄膜层制备；(4)钙钛矿活性层前驱体溶液制备；(5)钙钛矿活性层制备：(6)电子传输层制备；(7)致密金属银薄膜层即金属电极层制备。The preparation method of the perovskite solar cell according to the present invention is prepared according to methods well known to those skilled in the art, and can be divided into the following steps carried out in sequence: (1) cleaning of the substrate; (2) preparation of the hole transport layer; (3) Preparation of discontinuous metallic silver thin film layer; (4) Preparation of perovskite active layer precursor solution; (5) Preparation of perovskite active layer: (6) Preparation of electron transport layer; (7) Dense metallic silver thin film layer That is, the metal electrode layer is prepared.
所述基片清洗指覆盖透明导电电极的衬底材料和玻璃、PET和PC、PI等柔性基底依次以表面活性剂、去离子水、丙酮、异丙醇超声清洗两次，每次10～15分钟，之后烘干或以氮气吹干，紫外臭氧(UVO)或等离子体进行表面处理10～20分钟后备用。The substrate cleaning refers to the substrate material covered with transparent conductive electrodes and flexible substrates such as glass, PET, PC, and PI, which are ultrasonically cleaned twice with surfactant, deionized water, acetone, and isopropanol in sequence, each time for 10 to 15 minutes. Minutes, then dried or blown dry with nitrogen, surface treated with ultraviolet ozone (UVO) or plasma for 10 to 20 minutes before use.
所述不连续的银薄膜制备工艺如下：真空度小于4*10 -4帕斯卡，镀膜速度0.02nm/s～0.5nm/s，薄膜厚度2～10nm，得到的薄膜微观结构为不连续的岛状结晶；其中，优选的镀膜速度为0.02nm/s～0.08nm/s。 The preparation process of the discontinuous silver thin film is as follows: the degree of vacuum is less than 4*10 -4 Pascals, the coating speed is 0.02nm/s-0.5nm/s, the film thickness is 2-10nm, and the microstructure of the obtained film is discontinuous island-like Crystallization; wherein, the preferred coating speed is 0.02nm/s-0.08nm/s.
所述连续、致密的银薄膜制备工艺如下：真空度小于4*10 -4帕斯卡，镀膜速度0.5nm/s～5nm/s，薄膜厚度50～200nm，得到完全覆盖载流子传输层的致密和连续的银薄膜层。 The preparation process of the continuous and dense silver thin film is as follows: the degree of vacuum is less than 4*10 -4 Pascal, the coating speed is 0.5nm/s-5nm/s, and the film thickness is 50-200nm, to obtain a dense and dense silver film that completely covers the carrier transport layer. Continuous silver film layer.
所述钙钛矿活性层制备包括前驱液制备和薄膜沉积两个部分：前驱液制备选用甲基碘化铵(MAI)和碘化铅(PbI 2)以1：1的摩尔比溶于混合溶剂中；薄膜沉积选用匀胶旋涂法、线棒涂布法、刮刀涂布法、狭缝挤出式涂布法、丝网印刷、凹版印刷、凸版印刷等常规溶液成膜方法中的任意一种。所述混合溶剂为DMF和DMSO混合溶剂，溶液浓度为0.5～5mol/ml，DMF和DMSO两种溶剂体积比为(0.2～5):1。 The preparation of the perovskite active layer includes two parts: precursor solution preparation and thin film deposition: the precursor solution is prepared by dissolving methyl ammonium iodide (MAI) and lead iodide (PbI 2 ) in a mixed solvent at a molar ratio of 1:1 Medium; thin film deposition chooses any one of conventional solution film-forming methods such as spin coating method, wire bar coating method, doctor blade coating method, slit extrusion coating method, screen printing, gravure printing, letterpress printing, etc. kind. The mixed solvent is a mixed solvent of DMF and DMSO, the concentration of the solution is 0.5-5 mol/ml, and the volume ratio of the two solvents of DMF and DMSO is (0.2-5):1.
优选的，钙钛矿活性层制备选用匀胶涂布法制备，高效率的钙钛矿吸光层采用反溶剂法制备，可分为三个步骤：(Ⅰ)前驱液滴加到所述空穴传输层表面；(Ⅱ)开始旋涂制备薄膜，旋涂过程中滴加反溶剂，得到高效率钙钛矿活性层；(Ⅲ)退火。Preferably, the preparation of the perovskite active layer is prepared by uniform coating method, and the high-efficiency perovskite light-absorbing layer is prepared by anti-solvent method, which can be divided into three steps: (I) the precursor liquid is added dropwise to the hole The surface of the transport layer; (II) start to spin-coat to prepare a thin film, and anti-solvent is added dropwise during the spin-coating process to obtain a high-efficiency perovskite active layer; (III) annealing.
所述钙钛矿活性层的溶液加工成膜工艺，优选匀胶旋涂、刮刀涂布以及狭缝挤出涂布薄膜制备工艺。所述匀胶旋涂法选用台式匀胶机旋转涂膜，优选涂膜速度1000～6000rpm/min(转/分钟)。所述刮刀涂布法选用平板式涂布机涂膜，涂布速度0.02～1m/min(米/分钟)，涂布宽度0.2～5厘米。所述狭缝涂布工艺， 溶液供给速度5～500微升/分钟，涂布速度0.2～2m/min，涂布时基片温度25～100℃，涂布宽度0.2～5厘米，狭缝宽度10～50微米。The solution processing film-forming process of the perovskite active layer is preferably a film preparation process of uniform glue spin coating, doctor blade coating and slit extrusion coating. The spin-coating method adopts a table-top coating machine to spin the film, and the preferred film coating speed is 1000-6000 rpm/min (rev/min). The blade coating method adopts a flat coater to coat the film, the coating speed is 0.02-1 m/min (meter/min), and the coating width is 0.2-5 cm. In the slit coating process, the solution supply speed is 5-500 microliters/minute, the coating speed is 0.2-2m/min, the substrate temperature is 25-100°C during coating, the coating width is 0.2-5 cm, and the slit width 10-50 microns.
优选的，旋涂制备活性层分为两个阶段，第一阶段为慢速阶段，优选的旋涂速度为1000～4000rpm/min，旋涂时间1～3秒；第二阶段为高速阶段，优选的旋涂速度为4000～5000rpm/min，旋涂时间为30～50秒。Preferably, the preparation of the active layer by spin coating is divided into two stages, the first stage is a slow stage, the preferred spin coating speed is 1000 ~ 4000rpm/min, and the spin coating time is 1 ~ 3 seconds; the second stage is a high speed stage, preferably The spin-coating speed is 4000-5000 rpm/min, and the spin-coating time is 30-50 seconds.
优选的，所述反溶剂选用氯苯，溶剂体积为100～200μl，在旋涂停止前20秒开始滴加所述反溶剂。优选的，所述反溶剂在2秒内加完。Preferably, the anti-solvent is chlorobenzene, the volume of the solvent is 100-200 μl, and the anti-solvent is added dropwise 20 seconds before the spin coating stops. Preferably, the anti-solvent is added within 2 seconds.
本发明提供的具备光学微腔结构的钙钛矿太阳能电池与传统结构的钙钛矿太阳能电池相比，在光电转换性能方面尤其是输出电流方面表现更为优异。Compared with perovskite solar cells with traditional structure, the perovskite solar cell with optical microcavity structure provided by the present invention is more excellent in photoelectric conversion performance, especially output current.
为了进一步理解本发明，下面结合实施例对本发明提供的钙钛矿太阳能电池进行详细说明，本发明的保护范围不受以下实施例的限制。In order to further understand the present invention, the perovskite solar cell provided by the present invention will be described in detail below in conjunction with examples, and the scope of protection of the present invention is not limited by the following examples.
对比例1：以致密的银薄膜为金属电极的钙钛矿太阳能电池制备Comparative Example 1: Preparation of perovskite solar cells with dense silver films as metal electrodes
(1)带图案的FTO玻璃以前文所述方法清洗，之后UVO处理15分钟后备用；(1) The patterned FTO glass is cleaned by the method described above, and then treated with UVO for 15 minutes for later use;
(2)处理后的FTO玻璃通过磁控溅射工艺制备25nm厚的NiO x空穴传输层； (2) The FTO glass after treatment prepares 25nm thick NiO x hole transport layer by magnetron sputtering process;
(3)覆盖NiO x空穴传输层的FTO玻璃放入高温烘箱，300℃条件下退火30分钟，冷却后取出备用； (3) Put the FTO glass covered with the NiO x hole transport layer into a high-temperature oven, anneal at 300°C for 30 minutes, and take it out after cooling for later use;
(4)取1290.8mg PbI 2和445.2mg MAI溶于DMF和DMSO的混合溶剂(DMF和DMSO的体积比为4:1),常温搅拌过夜得到钙钛矿前驱体溶液，溶液中溶质总浓度为1.4mol/ml； (4) Get 1290.8mg PbI 2 and 445.2mg MAI and dissolve in the mixed solvent of DMF and DMSO (the volume ratio of DMF and DMSO is 4:1), stir overnight at room temperature to obtain the perovskite precursor solution, the total concentration of solute in the solution is 1.4mol/ml;
(5)在步骤(3)得到的NiO x空穴传输层上旋涂步骤(4)所述钙钛矿前驱体溶液：整个旋涂过程分为三个步骤，首先以4000rpm/min旋涂3秒；然后以5000rpm/min旋涂30秒；最后在5000rpm/min高速旋涂11秒时滴加200μl的氯苯(反溶剂)，要求是所有反溶剂在2秒内滴加完成，钙钛矿吸光层的厚度控制在500nm左右； (5) Spin-coat the perovskite precursor solution described in step (4) on the NiO x hole-transport layer obtained in step (3): the whole spin-coating process is divided into three steps, first with 4000rpm/min spin-coating 3 second; then spin-coat at 5000rpm/min for 30 seconds; finally add 200 μl of chlorobenzene (anti-solvent) dropwise when 5000rpm/min high-speed spin-coat for 11 seconds. The requirement is that all anti-solvents are added dropwise within 2 seconds. The thickness of the light-absorbing layer is controlled at about 500nm;
(6)步骤(5)得到的片子烘箱中130℃退火20分钟待冷却后取出；(6) The sheet obtained in step (5) is annealed at 130° C. for 20 minutes in an oven and taken out after being cooled;
(7)步骤(6)制得的片子移入真空蒸镀腔室，抽真空至真空度低于4*10 -4Pa后开始进行热蒸镀沉积法制备电子传输层；C 60蒸镀速率小于0.05埃/秒，薄膜厚度20nm；BCP蒸镀速率小于0.1埃/秒，薄膜厚度9nm； (7) The sheet obtained in step (6) is moved into a vacuum evaporation chamber, and after vacuuming until the vacuum degree is lower than 4*10 -4 Pa, the thermal evaporation deposition method is started to prepare the electron transport layer; the evaporation rate of C 60 is less than 0.05 angstrom/s, film thickness 20nm; BCP evaporation rate less than 0.1 angstrom/s, film thickness 9nm;
(8)步骤(7)制得的片子同样采用热蒸镀沉积法制备银电极，控制真空度低于4*10 -4Pa，初始蒸镀速率0.8nm/秒，同时通过在线膜厚测试设备监测实时膜厚，膜厚大于10nm后，调整蒸镀速率为1.5nm/秒，膜厚大于20nm后，调整蒸镀速率为4nm/秒，银电极最终厚度100nm，制备得到钙钛矿太阳能电池器件。 (8) The sheet prepared in step (7) is also prepared by the thermal evaporation deposition method to prepare silver electrodes, the vacuum degree is controlled to be lower than 4*10 -4 Pa, the initial evaporation rate is 0.8nm/s, and the online film thickness testing equipment is passed Monitor the real-time film thickness. When the film thickness is greater than 10nm, adjust the evaporation rate to 1.5nm/s. After the film thickness is greater than 20nm, adjust the evaporation rate to 4nm/s. The final thickness of the silver electrode is 100nm, and the perovskite solar cell device is prepared. .
实施例1：基于具有微腔结构的钙钛矿太阳能电池制备Example 1: Preparation of perovskite solar cells based on microcavity structure
对比例1中磁控溅射NiO x并退火后的基片移入真空蒸镀腔室，抽真空至真空度低于4*10 -4Pa后开始蒸镀不连续的银薄膜层，蒸镀速率0.02nm/秒，控制银薄膜厚度5nm；后续钙钛矿活性层、电子传输层和银金属电极层同对比例1所述。 In comparative example 1, the substrate after magnetron sputtering NiO x and annealing was moved into the vacuum evaporation chamber, and after vacuuming until the vacuum degree was lower than 4*10 -4 Pa, a discontinuous silver film layer was evaporated, and the evaporation rate was 0.02nm/second, the silver film thickness is controlled to 5nm; the subsequent perovskite active layer, electron transport layer and silver metal electrode layer are the same as those described in Comparative Example 1.
实施例2：基于具有微腔结构的钙钛矿太阳能电池制备Example 2: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.05nm/秒，薄膜厚度5nm，其他步骤不变。Change the evaporation rate of the discontinuous silver thin film layer in Example 1 to 0.05nm/sec, the film thickness to 5nm, and keep other steps unchanged.
实施例3：基于具有微腔结构的钙钛矿太阳能电池制备Example 3: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.08nm/秒，薄膜厚度5nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 5nm, and the other steps remained unchanged.
实施例4：基于具有微腔结构的钙钛矿太阳能电池制备Example 4: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.1nm/秒，薄膜厚度5nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.1 nm/sec, the film thickness was 5 nm, and the other steps remained unchanged.
实施例5：基于具有微腔结构的钙钛矿太阳能电池制备Example 5: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.2nm/秒，薄膜厚度5nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.2nm/second, the film thickness was 5nm, and other steps remained unchanged.
实施例6：基于具有微腔结构的钙钛矿太阳能电池制备Example 6: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.5nm/秒，薄膜厚度5nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.5nm/second, the film thickness was 5nm, and the other steps remained unchanged.
实施例7：基于具有微腔结构的钙钛矿太阳能电池制备Example 7: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.08nm/秒，薄膜厚度2nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 2nm, and the other steps remained unchanged.
实施例8：基于具有微腔结构的钙钛矿太阳能电池制备Example 8: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.08nm/秒，薄膜厚度8nm，其他步骤不变。The evaporation rate of the discontinuous silver thin film layer in Example 1 was changed to 0.08nm/second, the film thickness was 8nm, and the other steps remained unchanged.
实施例9：基于具有微腔结构的钙钛矿太阳能电池制备Example 9: Preparation of perovskite solar cells based on microcavity structure
更改实施例1中的不连续银薄膜层蒸镀速率为0.08nm/秒，薄膜厚度10nm，其他步骤不变。Change the evaporation rate of the discontinuous silver thin film layer in Example 1 to 0.08nm/sec, the film thickness to 10nm, and keep other steps unchanged.
电池性能测试：上述实施例制备得到的钙钛矿太阳能电池使用太阳光模拟器(氙灯作为光源)在一个标准太阳光强度(AM1.5G，100mW/cm2)下进行测试，所述的太阳光模拟器在美国国家可再生能源实验室中使用硅二极管(具备KG9可见滤光器)进行校正。相应的测试结果如表1和图6所示。Battery performance test: the perovskite solar cell prepared by the above-mentioned embodiment is tested under a standard sunlight intensity (AM1.5G, 100mW/cm 2 ) using a solar simulator (xenon lamp as a light source), and the solar simulation The detectors were calibrated at the National Renewable Energy Laboratory using silicon diodes (with KG9 visible filters). The corresponding test results are shown in Table 1 and Figure 6.
表1 依据不同实施例制备得到的钙钛矿太阳能电池性能参数表Table 1 Performance parameter list of perovskite solar cells prepared according to different examples
Figure PCTCN2022100716-appb-000001
Figure PCTCN2022100716-appb-000001
从电池性能测试数据可以看到，基于本发明所述微腔结构的钙钛矿太阳能电池，可以通过调控不连续的银薄膜的厚度和蒸镀速率来调节电池的输出电流值，进而可以实现与传统结构钙钛矿太阳能电池相当或是更高的光电转换效率。As can be seen from the battery performance test data, the perovskite solar cell based on the microcavity structure of the present invention can adjust the output current value of the battery by regulating the thickness and evaporation rate of the discontinuous silver film, and then can realize the same Traditional structure perovskite solar cells have comparable or higher photoelectric conversion efficiency.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

  1. 一种包括光学微腔结构的钙钛矿太阳能电池，包括依次叠加设置的基片、不连续金属银薄膜层、空穴传输层、钙钛矿活性层、电子传输层和致密金属银薄膜层。A perovskite solar cell including an optical microcavity structure comprises a substrate, a discontinuous metal silver film layer, a hole transport layer, a perovskite active layer, an electron transport layer and a dense metal silver film layer arranged in sequence.
  2. 根据权利要求1所述的钙钛矿太阳能电池，其特征在于，所述不连续金属银薄膜层的厚度为2～10nm，所述致密金属银薄膜层的厚度为50～200nm。The perovskite solar cell according to claim 1, wherein the thickness of the discontinuous metallic silver thin film layer is 2-10 nm, and the thickness of the dense metallic silver thin film layer is 50-200 nm.
  3. 根据权利要求1所述的钙钛矿太阳能电池，其特征在于，所述基片选自硬质基底或柔性基底；所述空穴传输层选自NiO x、PEDOT:PSS或聚[双(4-苯基)(2,4,6-三甲基苯基)胺]；所述电子传输层选自TiO 2、SnO 2、PCBM、C 60和BCP中的一种或多种。 The perovskite solar cell according to claim 1, wherein the substrate is selected from a hard substrate or a flexible substrate; the hole transport layer is selected from NiO x , PEDOT:PSS or poly[bis(4 -phenyl)(2,4,6-trimethylphenyl)amine]; the electron transport layer is selected from one or more of TiO 2 , SnO 2 , PCBM, C 60 and BCP.
  4. 根据权利要求1所述的钙钛矿太阳能电池，其特征在于，所述钙钛矿太阳能电池的制备方法包括以下步骤：A)基片清洗；B)空穴传输层制备；C)不连续金属银薄膜层制备；D)钙钛矿活性层制备；E)电子传输层制备；F)致密金属银薄膜层的制备。The perovskite solar cell according to claim 1, wherein the preparation method of the perovskite solar cell comprises the following steps: A) substrate cleaning; B) hole transport layer preparation; C) discontinuous metal Preparation of silver thin film layer; D) preparation of perovskite active layer; E) preparation of electron transport layer; F) preparation of dense metallic silver thin film layer.
  5. 根据权利要求4所述的钙钛矿太阳能电池，其特征在于，所述不连续金属银薄膜层制备采用真空蒸镀法制备，所述真空蒸镀法的真空度小于4*10 -4帕斯卡，镀膜速度0.05nm/s～0.5nm/s，薄膜厚度2～10nm。 The perovskite solar cell according to claim 4, wherein the discontinuous metal silver film layer is prepared by a vacuum evaporation method, and the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascal, The coating speed is 0.05nm/s～0.5nm/s, and the film thickness is 2～10nm.
  6. 根据权利要求5所述的钙钛矿太阳能电池，其特征在于，所述镀膜速度为0.02nm/s～0.08nm/s。The perovskite solar cell according to claim 5, wherein the coating speed is 0.02nm/s˜0.08nm/s.
  7. 根据权利要求5所述的钙钛矿太阳能电池，其特征在于，所述致密金属银薄膜层制备采用真空蒸镀法制备，所述真空蒸镀法的真空度小于4*10 -4帕斯卡，镀膜速度0.5nm/s～5nm/s，薄膜厚度50～200nm。 The perovskite solar cell according to claim 5, wherein the dense metal silver film layer is prepared by a vacuum evaporation method, and the vacuum degree of the vacuum evaporation method is less than 4*10 -4 Pascals, and the coating The speed is 0.5nm/s~5nm/s, and the film thickness is 50~200nm.
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