Large-area perovskite solar cell module and preparation method thereof

Abstract

The invention discloses a large-area perovskite solar cell module. The large-area perovskite solar cell module is of a p-i-n structure, and a conductive oxide layer / inert metal layer is arranged between a hole blocking layer and an electrode; wherein the conductive oxide layer is one of IZO (indium tin oxide), ZTO (zinc oxide) or ITO (indium tin oxide); and the inert metal layer is Mo or Bi. The conductive oxide layer / inert metal layer serves as a buffer layer to isolate diffusion of the active metal electrode, direct contact between a perovskite cross section generated by laser and the metal electrode is effectively avoided, leakage current caused by direct contact between the tunneling composite layer and the cell is effectively reduced, the degradation speed of the cell is relieved, and the service life of the cell is prolonged. The stability of the perovskite solar cell module is improved, and the fill factor and PCE of the cell module are further improved. Meanwhile, in combination with the improvement of the preparation method, the series structure of the sub-cells between the large-area perovskite solar cell modules is ensured, so that the large-area perovskite solar cell modules can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and more specifically, to a large-area perovskite solar cell module and a preparation method thereof. Background Art

[0002] A solar cell is a device that directly converts light energy into electrical energy through the photovoltaic effect or a photochemical reaction. At present, the development of solar energy technology has roughly gone through three stages: The first-generation solar cells mainly refer to monocrystalline silicon and polycrystalline silicon solar cells, and their photoelectric conversion efficiencies in the laboratory have reached 25% and 20.4% respectively; the second-generation solar cells mainly include amorphous silicon thin-film cells and polycrystalline silicon thin-film cells. The third-generation solar cells mainly refer to some new concept cells with high conversion efficiencies, such as dye-sensitized cells, quantum dot cells, and perovskite solar cells, etc. As an artificial synthetic material, since 2009, the PCE of solar cells using perovskite as a light-absorbing material has rapidly increased from 3.8% to 26.1%, and it has gradually become a research hotspot of domestic and foreign research groups in the field of solar cell research.

[0003] However, the stability of solar cell materials directly determines the lifespan of the battery. Although perovskite solar cells have obvious advantages, perovskite is very sensitive to water, oxygen, and strong ultraviolet light. In addition, the commonly used electrode metals such as Ag and Cu in perovskite solar cells will induce the degradation of the photoactive layer when in contact with the perovskite layer. Currently, domestic and foreign research groups are mainly studying to improve the overall stability of the battery by selecting more stable materials to form the battery, optimizing the preparation process, improving the stability of the perovskite material itself, or through the screening of electron transport and hole transport materials, thin-film interface modification, device structure optimization, and encapsulation process improvement.

[0004] The preparation process of perovskite solar cell modules generally is to first perform laser scribing on FTO to etch P1, and then spin-coat a hole transport layer on the clean FTO, and deposit a perovskite layer as a light-absorbing layer on it through various preparation methods such as spin-coating, doctor-blading, slot-die coating, or screen printing, then spin-coat a 2D perovskite layer for passivation, and then prepare a charge transport layer by thermal evaporation, and form a dense hole blocking layer by atomic layer deposition (ALD), etch P2 by laser scribing, and finally vacuum-evaporate a layer of Ag or Cu to form an overall p-i-n structure. Finally, separate the metal anodes of each sub-cell through P3 to form a series structure, and finally perform edge cleaning treatment through P4 to form the battery.

[0005] Currently reported methods for improving stability mostly exist in small-area single-junction cells, and at the same time, only ALD is used alone to prevent the contact between the electrode active metal and the photoactive material. The research on the fill factor and battery stability of large-area perovskite solar cell modules needs to be improved. Summary of the Invention

[0006] The object of the present invention is to protect a large-area perovskite solar cell module. In the perovskite solar cell module, a conductive oxide layer / inert metal layer is added between the hole blocking layer and the electrode as a buffer layer, which not only improves the stability of the perovskite solar cell module, but also further enhances the fill factor and PCE of the cell module.

[0007] Another object of the present invention is to provide a method for preparing a large-area perovskite solar cell module.

[0008] The above object of the present invention is achieved by the following solutions:

[0009] A large-area perovskite solar cell module, the perovskite solar cell module has a p-i-n structure, and a conductive oxide layer / inert metal layer is provided between the hole blocking layer and the electrode;

[0010] The conductive oxide layer is one of IZO, ZTO or ITO; the inert metal layer is Mo or Bi.

[0011] In the perovskite solar cell module, by adding a conductive oxide layer / inert metal layer between the hole blocking layer and the electrode as a buffer layer, the diffusion of the active metal electrode is isolated. At the same time, it effectively avoids the direct contact between the perovskite cross-section and the metal electrode generated after laser P2 etching, effectively reduces the leakage current caused by the direct contact between the tunneling composite layer and the battery, alleviates the degradation rate of the battery itself, and finally significantly improves the stability of the large-area perovskite solar cell module; at the same time, after adding the conductive oxide layer / inert metal layer, the fill factor of the perovskite solar cell module will be further improved, thereby improving the photoelectric conversion performance and stability of the battery.

[0012] Preferably, the thickness of the conductive oxide layer is 25 - 100 nm; the thickness of the inert metal layer is 25 - 75 nm.

[0013] Preferably, the thickness of the conductive oxide layer is 25 - 50 nm; the thickness of the inert metal layer is 25 - 50 nm.

[0014] Preferably, the thickness of the inert metal layer is 25 - 50 nm.

[0015] Preferably, the conductive oxide layer and the inert metal layer have the same thickness.

[0016] Preferably, the conductive oxide layer / inert metal layer is one of IZO / Mo, ZTO / Bi, ITO / Mo or ITO / Bi.

[0017] Preferably, the thickness of IZO in IZO / Mo is 25 - 100 nm; the thickness of Mo is 25 - 75 nm.

[0018] Preferably, the thickness of IZO in IZO / Mo is 25 - 50 nm; the thickness of Mo is 25 - 50 nm.

[0019] Preferably, the thicknesses of IZO and Mo in IZO / Mo are the same.

[0020] Preferably, the thickness of ZTO in ZTO / Bi is 25 - 100 nm; the thickness of Bi is 25 - 75 nm.

[0021] Preferably, the thickness of ZTO in ZTO / Bi is 25 - 50 nm; the thickness of Bi is 25 - 50 nm.

[0022] Preferably, the thicknesses of ZTO and Bi in ZTO / Bi are the same.

[0023] Preferably, the thickness of ITO in ITO / Mo or ITO / Bi is 25 - 100 nm; the thickness of Mo or Bi is 25 - 75 nm.

[0024] Preferably, the thickness of ITO in ITO / Mo or ITO / Bi is 25 - 50 nm; the thickness of Mo or Bi is 25 - 50 nm.

[0025] Preferably, the thicknesses of ITO and the Mo or Bi of the inert metal layer in ITO / Mo or ITO / Bi are the same.

[0026] Preferably, the device structure of the perovskite solar cell module is, from bottom to top, FTO / hole transport layer / perovskite layer / charge transport layer / hole blocking layer / conductive oxide layer / inert metal layer / electrode; wherein the conductive oxide layer / inert metal layer is one of IZO / Mo, ZTO / Bi, ITO / Mo or ITO / Bi.

[0027] Preferably, in the perovskite solar cell module, the thickness of IZO in IZO / Mo is 25 - 100 nm; the thickness of Mo is 25 - 75 nm;

[0028] Preferably, in the perovskite solar cell module, the thickness of IZO in IZO / Mo is 25 - 50 nm; the thickness of Mo is 25 - 50 nm.

[0029] Preferably, in the perovskite solar cell module, the thicknesses of IZO and Mo in IZO / Mo are the same.

[0030] Preferably, in the perovskite solar cell module, the thickness of ZTO in ZTO / Bi is 25 - 100 nm; the thickness of Bi is 25 - 75 nm;

[0031] Preferably, in the perovskite solar cell module, the thickness of ZTO in ZTO / Bi is 25 - 50 nm; the thickness of Bi is 25 - 50 nm.

[0032] Preferably, in the perovskite solar cell module, the thicknesses of ZTO and Bi in ZTO / Bi are the same.

[0033] Preferably, in the perovskite solar cell module, the thickness of ITO in ITO / Mo or ITO / Bi is 25 - 100 nm; the thickness of Mo or Bi is 25 - 75 nm.

[0034] Preferably, in the perovskite solar cell module, the thickness of ITO in ITO / Mo or ITO / Bi is 25 - 50 nm; the thickness of Mo or Bi is 25 - 50 nm.

[0035] Preferably, in the perovskite solar cell module, the thickness of ITO in ITO / Mo or ITO / Bi is the same as the thickness of Mo or Bi in the inert metal layer.

[0036] Preferably, the electrode is an active metal.

[0037] Preferably, the electrode is Ag, Cu, Al or Mo.

[0038] Preferably, the perovskite layer is an organic - inorganic hybrid perovskite

[0039] Preferably, the hole - transporting layer is Me - 4PACz, 2PACz, Meo - 2PACz or PTAA, etc.

[0040] Preferably, the charge - transporting layer is C60 or PCBM, etc.

[0041] Preferably, the hole - blocking layer is SnOx or BCP, etc.

[0042] The present invention also protects a method for preparing a large - area perovskite solar cell module, comprising the following steps: After the FTO is cleaned, it is subjected to laser scribing P1, and then a hole - transporting layer, a perovskite layer, a charge - transporting layer and a hole - blocking layer are sequentially deposited on the FTO; laser scribing P2 is carried out; then a conductive metal oxide and an inert metal layer are sequentially deposited, and laser scribing P2ˋ is carried out; then a metal electrode is deposited, and laser scribing P3 is carried out; finally, laser scribing P4 is carried out for edge cleaning.

[0043] Preferably, the width of P2 is 80 μm - 150 μm.

[0044] More preferably, the width of P2 is 80 μm - 100 μm or 100 μm - 150 μm.

[0045] More preferably, the width of P2 is 80 μm - 100 μm, 100 μm - 120 μm, or 120 μm - 150 μm.

[0046] When the width of P2 is too wide, the performance of the device will decrease instead.

[0047] Preferably, the thickness of the hole transport layer is 1 - 5 nm.

[0048] Preferably, the hole transport layer can be deposited by spin coating.

[0049] Preferably, the perovskite layer can be deposited by common methods such as spin coating, blade coating, slot-die coating, or screen printing.

[0050] Preferably, after the perovskite layer is deposited, a passivation layer can be deposited thereon.

[0051] Preferably, the charge transport layer can be deposited by common methods, such as by thermal evaporation deposition.

[0052] Preferably, the hole blocking layer can be deposited by common methods, such as by atomic layer deposition (ALD).

[0053] Preferably, the conductive oxide layer and the inert metal layer can be deposited by common methods to form a dense layer, such as by magnetron sputtering deposition.

[0054] Preferably, both IZO and Mo are deposited by magnetron sputtering (Physical Vapor Deposition, PVD).

[0055] Preferably, ZTO is deposited by atomic layer deposition (Atomic Layer Deposition, ALD); Bi is deposited by a thermal evaporator.

[0056] Preferably, ITO is deposited by magnetron sputtering.

[0057] The specific preparation process of the large-area perovskite solar cell module of the present invention is as follows: First, P1 is etched by laser scribing on a clean FTO, and then a hole transport layer is spin-coated on the clean FTO; and a perovskite layer is deposited as a light absorption layer thereon by various common preparation methods such as spin coating, blade coating, slot-die coating, or screen printing. Then, a passivation layer is spin-coated, and then a charge transport layer and a dense hole blocking layer are prepared. P2 with a wider width is etched by laser scribing; then a conductive oxide layer and an inert metal layer are prepared on the blocking layer, and a narrower P2ˋ is etched in the original wider P2 by laser scribing. Finally, a layer of Ag or Cu is vacuum-evaporated to form a p-i-n structure, and the positive electrodes of each sub-cell are separated by P3 to form a series structure. Finally, the battery is formed by edge cleaning treatment with P4.

[0058] Among them, the conductive oxide layer and the inert metal layer, which are located above the hole blocking layer, have good continuity and density, can conformally grow on the patterned substrate to achieve complete coverage, and this layer has good carrier transport characteristics and conductivity, which can ensure the series structure of sub-cells between components.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] (1) By adding a conductive oxide layer / inert metal layer as a buffer layer between the hole blocking layer and the electrode of the large-area perovskite solar cell module, the present invention isolates the diffusion of the active metal electrode, and at the same time effectively avoids the direct contact between the perovskite cross-section generated by the laser and the metal electrode, effectively reducing the leakage current caused by the direct contact between the tunneling composite layer and the battery, alleviating the degradation rate of the battery itself, not only improving the stability of the perovskite solar cell module, but also further enhancing the fill factor and PCE of the battery module.

[0061] (2) After depositing the conductive oxide layer and the inert metal layer, a narrower P2ˋ is etched in the original wider P2. The general formula conductive oxide layer and the inert metal layer still have good carrier transport characteristics and conductivity, which can ensure the series structure of sub-cells between components. Therefore, large-area perovskite solar cell modules can be prepared. Description of the Drawings

[0062] Figure 1 It is a schematic diagram of the device structure for part of the preparation process of Device 1.

[0063] Figure 2 It is a schematic diagram of the device structure for part of the preparation process of a conventional perovskite solar cell.

[0064] Figure 3 It is a schematic diagram of the preparation flow chart of Device 1.

[0065] Figure 4 It is the performance test results of Device 1 and Device 3 under the same conditions.

[0066] Figure 5 It is the performance test results of Devices 4-6 under the same conditions.

[0067] Figure 6 It is the performance test results of Device 1, Devices 7-9 and Device C3 under the same conditions.

[0068] Figure 7 It is the performance test results of Device 1, Device 2 and Device C1 under the same conditions.

[0069] Figure 8 It is the performance test results of Device 2 and Device C4 under the same conditions.

[0070] Figure 9 Performance test results of device 1 and devices C1 - C4 under the same conditions.

[0071] Figure 10 Thermal stability test results of device 1 and devices C1 - C4 under the same conditions. Specific implementation manners

[0072] The present invention will be further elaborated in detail below in conjunction with specific embodiments. The embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. The test methods used in the following embodiments are all conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available reagents and materials unless otherwise specified.

[0073] Example 1 Large - area perovskite solar cell module

[0074] The preparation process of the large - area perovskite solar cell module is as follows:

[0075] S1. P1 scribing and hole - transporting layer preparation

[0076] The cleaned FTO conductive glass is scribed by a laser scribing device to separate each sub - cell, that is, the FTO between the sub - cells needs to be scribed away (P1 laser scribing frequency 70 kHz, pulse width 5 μs, scribing speed 100 mm / s). After that, the scribed FTO conductive glass is cleaned and irradiated by a UV machine for 25 min, and then 0.3 mg / mL of Me - 4Pacz is spin - coated in a glove box at a rotation speed of 3000 r / s, and finally annealed on a hot stage at 100 °C for 10 min.

[0077] S2. Perovskite layer preparation

[0078] Taking the spin - coating method as an example, the pre - prepared perovskite precursor solution is uniformly spin - coated on the FTO after S1 at a rotation speed of 6000 r / s and annealed on a hot stage at 100 °C for 30 min. Then, piperazine iodate is spin - coated on the 3D perovskite layer to form a passivation layer. After annealing at 100 °C for 10 min, the excess uncoordinated piperazine iodate is washed away with isopropanol and annealed at 100 °C for 5 min.

[0079] The passivation layer can also be omitted, and the influence on the device can be ignored.

[0080] S3. Charge - transporting layer preparation

[0081] The device coated in S2 is transferred to a vacuum thermal evaporation instrument. When the vacuum degree reaches 1*10 -3 Pa, by adjusting the evaporation power, the power is 38 W, and the thickness of the thermally evaporated C60 is controlled to be 30 nm.

[0082] S4. Hole Blocking Layer Preparation and P2 Scratching

[0083] Transfer the device with the charge transport layer prepared in S3 to the ALD chamber, and deposit a dense SnO x layer on the charge transport layer. The growth process is as follows: the temperature of the Sn source is 60 °C, the reaction temperature of the chamber is 80 °C, the Sn source is purged for 0.1 s - nitrogen is introduced for 10 s - water source is introduced for 0.15 s - nitrogen is introduced for 10 s to complete one cycle, and 1 nm of SnO is grown every 8 cycles. x After that, use a laser scribing device to scribe P2 at a distance of 60 microns from the edge of P1, ensuring that the P2 line does not scratch the FTO (the laser scribing frequency of P2 is 20 kHz, the pulse width is 42.6 μs, and the scribing speed is 100 mm / s).

[0084] S5. Conductive Oxide Layer (IZO) and Inert Metal Layer (Mo) Preparation and P2` Scratching

[0085] Place the device after scribing P2 in S4 in the magnetron sputtering chamber. After the vacuum reaches 2*10 -3 Pa, introduce argon with a flow rate of 20 and an argon-oxygen mixed gas with a flow rate of 3.6 (oxygen content 1%). Set the pressure control valve to 0.5 Pa, the sputtering power to 150 W, and the sputtering time to 7 min 40 s to deposit 50 nm of IZO. Then close the gas path of the argon-oxygen mixed gas. After simultaneously adjusting the sputtering power to 0 and closing it, turn on the DC sputtering source, set the power to 70%, the sputtering current to 200 mA, and the sputtering time to 8 min 2 s to deposit an inert metal Mo layer with an actual thickness of 50 nm. Then, scribe a narrower P2` in the middle of P2 on the prepared device (the laser scribing frequency of P2` is 20 kHz, the pulse width is 42.6 μs, and the scribing speed is 50 mm / s). At the same time, since the perovskite cross-section generated by P2 is protected by the newly added conductive oxide layer and inert metal layer, the self-degradation rate of the battery is reduced.

[0086] S6. Metal Electrode Preparation and P3 Scratching

[0087] Transfer the device with P2` scribed in S5 to a vacuum thermal evaporation instrument. Wait until the vacuum reaches 1*10 -3 Pa, and by adjusting the evaporation power to 58 W, control the actual thickness of the thermally evaporated Ag to be 150 nm. Then, use a laser scribing device to scribe P3 at a distance of 60 microns from the edge of P2, ensuring that the P3 line does not scratch the FTO (the laser scribing frequency of P3 is 18 kHz, the pulse width is 46 μs, and the scribing speed is 10 mm / s).

[0088] S7. Edge Cleaning and P4 Scratching

[0089] For the device with P3 scribed on S5, use a laser with higher energy to scribe P4 at both the left and right ends, and clear a 5-mm insulating boundary on each side to ensure that the metal electrodes of each sub-cell are completely separated. In this way, a perovskite solar cell module is fabricated, and the aperture area of the module is 21 cm 2 。

[0090] The fabricated large-area perovskite solar cell module is denoted as Device 1.

[0091] The fabrication process of Device 1 is different from that of existing conventional perovskite solar cells, and its device structure is also different. The schematic diagram of the device structure in part of the fabrication process is as Figure 1 shown, and the schematic diagram of the device structure in part of the fabrication process of existing conventional perovskite solar cells is as Figure 2 shown.

[0092] The complete fabrication flow chart of Device 1 is as Figure 3 shown.

[0093] Example 2: Large-area perovskite solar cell module

[0094] The fabrication process of Device 2 is the same as that of Device 1, except that the S5 step is different and is replaced with the following process:

[0095] S5. Preparation of the conductive oxide layer (ZTO) and the inert metal layer (Bi) and scribing of P2`

[0096] Transfer the device with the hole blocking layer prepared and P2 scribed to the ALD chamber again, and deposit the ZTO layer of the conductive oxide on the hole blocking layer; the growth process is as follows: the temperature of the Zn source is 75 °C, the temperature of the Sn source is 60 °C, the reaction temperature of the chamber is 80 °C, purge the Sn source for 0.1 s - purge with nitrogen for 10 s - purge the Zn source for 0.2 s - purge with nitrogen for 10 s - purge with water vapor for 0.015 s - purge with nitrogen for 10 s - purge the Zn source for 0.2 s - purge with nitrogen for 10 s to complete one cycle. Grow 1 nm of ZTO every 6 cycles. Then, put the device with ZTO prepared into a vacuum thermal evaporation instrument. When the vacuum reaches 1*10 -3 Pa, by adjusting the evaporation power to 32.1 W, control the actual thickness of the thermally evaporated Bi to be 50 nm. Then, use a laser scribing device to scribe P2ˋ in the middle of P2 (the laser scribing frequency of P2ˋ is 20 kHz, the pulse width is 42.6 μs, and the scribing speed is 50 mm / s), and ensure that the P2ˋ line does not scratch the FTO.

[0097] The large-area perovskite solar cell module fabricated in this way is denoted as Device 2, and the aperture area of the module is 21 cm 2 。

[0098] According to the preparation processes of Device 1 and Device 2, the conductive oxide therein can be replaced with ITO, and devices with better performance can also be prepared.

[0099] Verification of the necessity of the existence of Example 3 P2`

[0100] The preparation process of Device 3 is the same as that of Device 1, except that Step S5 is different. Specifically, the thickness of IZO is controlled to be 50 nm by adjusting the sputtering time, and after depositing the Mo layer, it is not necessary to scribe P2ˋ. Then, S6 and S7 are the same as those of Device 1.

[0101] Device 1 and Device 3 are tested in the same batch, and the measured results are as Figure 4 shown. It can be seen from Figure 4 that the existence of P2ˋ can increase the short-circuit current density of the battery and the fill factor of the device. The reason is that P2ˋ exposes the TCO electrode at the P2 connection, reducing the series resistance of the device.

[0102] Example 4 Influence of the scribing width of P2

[0103] The preparation processes of Device 4, Device 5, Device 6, Device 6-1, and Device 6-2 are the same as that of Device 1, except that Step S4 is different. Specifically, the scribing process of P2 is different. The energy of P2 scribing is adjusted by changing the focal length, and the change of the focal length affects the scribing width of P2. P2 of Device 4, Device 5, Device 6, Device 6-1, and Device 6-2 is scribed by multi-line superposition, and the corresponding widths of P2 are 60 μm, 80 μm, 100 μm, 120 μm, and 150 μm respectively.

[0104] Device 4-6, Device 6-1, and Device 6-2 are tested in the same batch, and the measured results are as Figure 5 shown. It can be seen from Figure 5 that the width of P2 has a certain influence on the performance of the device. The main function of P2 is to ensure the series connection of the front and rear sub-section batteries. According to the test results, when the width of P2 is in the range of 60 μm - 100 μm, as the width increases, the series resistance of the device becomes smaller, the fill factor of the device is higher, and the performance is better; but when the width of P2 increases in the range of 100 μm - 150 μm, the performance of the device does not change significantly. When P2 is too wide, the overall geometric fill factor of the device decreases, the dead area increases, the light-emitting area decreases, and the device efficiency will decrease.

[0105] Example 5 Influence of the thickness of the conductive oxide layer and the inert metal layer

[0106] The preparation processes of Device 7, Device 8, and Device 9 are the same as that of Device 1, except that Step S5 is different. Specifically, the deposited thicknesses of the conductive oxide IZO layer and the inert metal Mo layer are different, and the deposited thicknesses of the conductive oxide and the inert metal can be controlled by adjusting different sputtering times.

[0107] Among them, the thickness of the conductive oxide IZO layer in Device 7 is 100 nm.

[0108] Among them, the thickness of the conductive oxide IZO layer in Device 8 is 75 nm, and the thickness of the inert metal Mo layer is 25 nm.

[0109] Among them, the thickness of the conductive oxide IZO layer in Device 9 is 25 nm, and the thickness of the inert metal Mo layer is 75 nm.

[0110] Device 1, Devices 7 - 9, and Device C3 are tested in the same batch, and the measured results are as Figure 6 shown. It can be seen from Figure 6 that the introduction of both the conductive oxide layer and the inert metal can improve the performance of the device. In addition to the obvious improvement in stability, the open-circuit voltage and fill factor of the device are also improved well; among them, according to the results of Device 7 and Device C3, it shows that the conductive oxide layer has a greater effect on improving the open-circuit voltage of the device, while the inert metal layer has a greater effect on improving the fill factor of the device.

[0111] When the thickness of the conductive oxide is between 25 nm and 100 nm, and the thickness of the inert metal layer is between 25 nm and 75 nm, the devices all show good performance, and among them, the performance of Device 1 is the best. It can be seen that when the thicknesses of the conductive oxide layer and the inert metal layer are the same, the performance of the device is the best.

[0112] Comparative Example 1 Preparation of Conventional Perovskite Solar Cell Modules

[0113] The preparation process of Device C1 is the same as that of Device 1, except that there is no Step S5. After completing Step S4, Steps S6 and S7 are directly carried out, that is, Device C1 is prepared.

[0114] Device 1, Device 2, and Device C1 are tested in the same batch, and the measured results are as Figure 7 shown. It can be seen from Figure 7 that the introduction of the intermediate layer of the conductive oxide layer and the inert metal layer will greatly improve the performance of the device. There is no clear limitation on the conductive oxide layer and the inert metal layer. The conductive oxide layers such as IZO / ZTO / ITO and the inert metal layers such as Mo / Bi used in this article can all greatly improve the performance of the device.

[0115] Comparative Example 2

[0116] The preparation process of Device C2 is the same as that of Device 1, except for Step S6, in which the metal electrode is Mo, and Device C2 is obtained.

[0117] Comparative Example 3

[0118] The preparation process of Device C3 is the same as that of Device 1, except for Step S5, in which only an inert metal Mo layer is deposited and no conductive oxide layer IZO is deposited, and Device C3 is obtained.

[0119] Comparative Example 4

[0120] The preparation process of Device C4 is the same as that of Device 2, except for Steps S5 and S6. In Step S5, only a Bi layer is deposited and no conductive oxide layer ZTO is deposited. In S6, the metal electrode is Mo, and Device C4 is obtained.

[0121] Device 2 and Device C4 were tested in the same batch, and the measured results are as Figure 8 shown. It can be seen from Figure 8 that the Ag electrode has better conductivity than the Mo electrode, and the presence of the Ag electrode will improve the fill factor and voltage of the device.

[0122] Performance Test: Device Stability Test

[0123] 1. MgF 2 Encapsulation

[0124] The above-mentioned device was covered with a special mask to cover the electrodes at both ends, and then transferred to a vacuum thermal evaporation instrument. When the vacuum reached 1*10 -3 Pa, by adjusting the evaporation power to 55W, the actual thickness of the thermally evaporated MgF 2 was controlled to be 100 nm.

[0125] 2. Stability Test

[0126] The encapsulated device was transferred to an 85°C hot stage, and the J-V performance of the device was tested under simulated sunlight of AM1.5 every 60 h, and the J-V curve of the battery was recorded using a Keithley current source meter.

[0127] The measured results are as follows:

[0128] Device 1 and Devices C1-C4 were tested in the same batch, and the measured results are as Figure 9 shown. It can be seen from Figure 9 that compared with Devices C1-C4, the performance of Device 1 has been significantly improved, indicating that the introduction of the conductive oxide layer and the inert metal layer can improve the performance of the device; at the same time, the comparison between Device 1 and Device C2 also shows that using an inert metal as the electrode layer will result in a large reduction in the efficiency of the device, mainly affecting the short-circuit current density and the fill factor of the device.

[0129] Device 1 and devices C1 - C4 were tested in the same batch, and the measured results are as Figure 10 shown. It can be seen from Figure 10 that devices 1, C2, C3, and C4 all showed good thermal stability and maintained an initial efficiency of over 97% after 1000 - hour aging at 85 degrees Celsius. However, device C1 showed a phenomenon of rapid aging, indicating that the introduction of the intermediate layer can significantly improve the stability of the device. At the same time, the efficiency of device 1 is the highest, that is, it can maintain long - term stability while having a high efficiency, and its energy production value is more excellent compared with other devices.

[0130] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description and ideas. It is not necessary and impossible to list all implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A large-area perovskite solar cell module, characterized in that: The perovskite solar cell module is a pin structure, with a conductive oxide layer / inert metal layer between the hole blocking layer and the electrode; The conductive oxide layer is one of IZO, ZTO or ITO; and the inert metal layer is Mo or Bi.

2. The large-area perovskite solar cell module according to claim 1, characterized in that: The thickness of the conductive oxide layer is 25-100 nm; the thickness of the inert metal layer is 25-75 nm; Preferably, the thickness of the conductive oxide layer is 25-50 nm; the thickness of the inert metal layer is 25-75 nm; Preferably, the thickness of the inert metal layer is 25-50 nm; Preferably, the conductive oxide layer and the inert metal layer have the same thickness.

3. The large-area perovskite solar cell module according to claim 2, characterized in that: The conductive oxide layer / inert metal layer is one of IZO / Mo, ZTO / Bi, ITO / Mo or ITO / Bi.

4. The large-area perovskite solar cell module according to claim 3, characterized in that: The thickness of IZO in the IZO / Mo is 25-100 nm; the thickness of Mo is 25-75 nm; Preferably, the thickness of IZO in the IZO / Mo is 25-50 nm; the thickness of Mo is 25-50 nm; Preferably, the thickness of IZO and Mo in the IZO / Mo is the same.

5. The large-area perovskite solar cell module according to claim 3, characterized in that: The thickness of ZTO in the ZTO / Bi is 25-100 nm; the thickness of Bi is 25-75 nm; Preferably, the thickness of ZTO in the ZTO / Bi is 25-50 nm; the thickness of Bi is 25-50 nm; Preferably, the thickness of ZTO and Bi in the ZTO / Bi is the same.

6. The large-area perovskite solar cell module according to claim 3, characterized in that: The thickness of ITO in the ITO / Mo or ITO / Bi is 25-100 nm; the thickness of Mo or Bi is 25-75 nm; Preferably, the thickness of ITO in the ITO / Mo or ITO / Bi is 25-50 nm; the thickness of Mo or Bi is 25-50 nm; Preferably, in the ITO / Mo or ITO / Bi, the thickness of ITO and the Mo or Bi of the inert metal layer are the same.

7. The large-area perovskite solar cell module according to claim 3, characterized in that: The device structure of the perovskite solar cell assembly is, from bottom to top, FTO / hole transport layer / perovskite layer / charge transport layer / hole blocking layer / conductive oxide layer / inert metal layer / electrode; wherein the conductive oxide layer / inert metal layer is one of IZO / Mo, ZTO / Bi, ITO / Mo or ITO / Bi.

8. The large-area perovskite solar cell module according to claim 7, characterized in that: The thickness of IZO in the IZO / Mo is 25-100 nm; the thickness of Mo is 25-75 nm; Preferably, the thickness of IZO in the IZO / Mo is 25-50 nm; the thickness of Mo is 25-50 nm; Preferably, the thickness of IZO and Mo in the IZO / Mo is the same; The thickness of ZTO in the ZTO / Bi is 25-100 nm; the thickness of Bi is 25-75 nm; Preferably, the thickness of ZTO in the ZTO / Bi is 25-50 nm; the thickness of Bi is 25-50 nm; Preferably, the thickness of ZTO and Bi in the ZTO / Bi is the same The thickness of ITO in the ITO / Mo or ITO / Bi is 25-100 nm; the thickness of Mo or Bi is 25-75 nm; Preferably, the thickness of ITO in the ITO / Mo or ITO / Bi is 25-50 nm; the thickness of Mo or Bi is 25-50 nm; Preferably, in the ITO / Mo or ITO / Bi, the thickness of ITO and the Mo or Bi of the inert metal layer are the same.

9. The large-area perovskite solar cell module according to claim 7, characterized in that: The electrode is an active metal; preferably, the electrode is Ag, Cu, Al or Mo.

10. The method for preparing a large-area perovskite solar cell module according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: washing the FTO and then laser scribing P1, and then sequentially depositing a hole transport layer, a perovskite layer, a charge transport layer and a hole blocking layer on the FTO; laser scribing P2; then sequentially depositing a conductive metal oxide and an inert metal layer, and laser scribing P2ˋ; then depositing a metal electrode, and laser scribing P3; and finally laser scribing P4 to clean the edges.

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