Preparation method of TCO / NiOX composite film based on flexible substrate

Abstract

The invention relates to the technical field of solar cells, and particularly discloses a preparation method of a TCO / NiOX composite film based on a flexible substrate. The preparation method of the TCO / NiOX composite film based on the flexible substrate comprises the following steps: (1) placing a flexible base material on an ITO cathode of winding equipment for ITO deposition to obtain a transparent conductive film layer, then placing the flexible base material on a NiOX cathode for NiOX deposition to obtain a hole transport layer, and preparing a composite layer; and (2) sequentially performing P1 laser scribing, cleaning, perovskite coating, sintering, electron transport layer preparation, buffer layer preparation, P2 laser scribing, metal electrode preparation, P3 laser scribing, P4 laser scribing and packaging on the composite layer to prepare the TCO / NiOX composite film based on the flexible substrate. According to the TCO / NiOX composite film based on the flexible substrate prepared by adopting the flexible winding equipment, the cost is greatly saved while the efficiency is ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of solar cells, and in particular to TCO / NiO based on flexible substrates. X Preparation method of composite film. Background Art

[0002] As global demand for renewable energy increases, the importance of solar energy as a clean energy source is becoming increasingly prominent. While traditional crystalline silicon solar cells are technologically mature, they suffer from high manufacturing costs, high energy consumption, and heavy weight, limiting their adoption in certain applications.

[0003] Perovskite solar cells, due to their high photoelectric conversion efficiency, low cost, and simple fabrication process, have become a research hotspot for the next generation of photovoltaic technology. Flexible perovskite solar cells, in particular, are lightweight, thin, and bendable, making them suitable for applications in wearable devices and building-integrated photovoltaics (BIPV), offering promising market prospects.

[0004] At present, the conventional process for preparing transparent conductive layer and hole transport layer of single-junction inverse perovskite solar cell module is: transparent conductive film layer (TCO) → cleaning → P1 laser → cleaning → physical vapor deposition PVD NiO X →TCO glass / NiO X However, TCO glass is heavy, limiting its use in flexible and portable applications. Furthermore, TCO glass is expensive to produce and is not suitable for roll-to-roll production, leading to increased production costs and complexity.

[0005] Therefore, it is necessary to provide TCO / NiO based on flexible substrates X The preparation method of the composite film can be applied to flexible batteries to broaden the application scenarios, reduce the preparation steps and improve production efficiency, thereby greatly reducing the cost of perovskite solar cells. Summary of the Invention

[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a TCO / NiO based on a flexible substrate. X The preparation method of the composite film can be applied to flexible batteries to broaden the application scenarios, reduce the preparation steps and improve production efficiency, thereby greatly reducing the cost of perovskite solar cells.

[0007] The first aspect of the present invention provides a TCO / NiO based on a flexible substrate X Preparation method of composite film.

[0008] Specifically, TCO / NiO based on flexible substrate X The method for preparing a composite film comprises the following steps:

[0009] (1) Place the flexible substrate on the ITO cathode of the winding device to deposit ITO to obtain a transparent conductive film layer, and then place the NiO X NiO cathode X Depositing a hole transport layer to obtain a composite layer;

[0010] (2) The composite layer is then subjected to P1 laser scribing, cleaning, perovskite coating, sintering, preparation of electron transport layer, preparation of buffer layer, P2 laser scribing, preparation of metal electrode, P3 laser scribing, P4 laser scribing, and packaging to obtain TCO / NiO based on flexible substrate. X Composite film.

[0011] Preferably, the thickness of the hole transport layer is 8 to 12 nm.

[0012] More preferably, the hole transport layer has a thickness of 10 to 12 nm.

[0013] More preferably, the hole transport layer has a thickness of 10 to 11 nm.

[0014] Preferably, in step (1), the flexible substrate includes at least one of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

[0015] Preferably, in step (1), the ITO deposition step includes: using an ITO planar target as a target material, vacuuming the chamber, introducing oxygen into the chamber, maintaining the total gas flow rate at 300 to 1000 sccm, maintaining the chamber pressure at 0.3 to 0.6 Pa, and setting the power to 1 to 6 kW before starting the coating.

[0016] Preferably, the ratio of oxygen introduced into the chamber is 1-10%.

[0017] Preferably, in step (1), the NiO X The deposition steps include: using a NiO planar target as a target material, vacuuming the chamber, introducing oxygen into the chamber, maintaining a total gas flow rate of 300 to 1000 sccm, maintaining a chamber pressure of 0.3 to 0.6 Pa, setting the power to 1 to 6 kW, and then starting the coating.

[0018] Preferably, the pressure of the vacuum treatment is 4 to 6×10 -4 Pa.

[0019] More preferably, the pressure of the vacuum treatment is 5×10 -4 Pa.

[0020] Preferably, in step (2), the sintering temperature is 145-155°C.

[0021] Further preferably, in step (2), the sintering temperature is 150-155°C.

[0022] More preferably, in step (2), the sintering temperature is 150°C.

[0023] Preferably, in step (2), the step of preparing the electron transport layer includes placing it in an evaporation device to plate C60.

[0024] More preferably, the thickness of the C60 is 15 to 25 nm.

[0025] More preferably, the thickness of the C60 is 20 nm.

[0026] Preferably, in step (2), the step of preparing the buffer layer includes placing the film in a vacuum coating device and a reactive plasma deposition device to coat IWO.

[0027] More preferably, the thickness of the IWO is 20-30 nm.

[0028] More preferably, the thickness of the IWO is 25 nm.

[0029] Preferably, in step (2), the P1 laser scribing step includes: scribing the hole transport layer and the transparent conductive film layer (TCO layer) to form independent strip-shaped conductive electrodes.

[0030] Preferably, in step (2), the perovskite coating step includes: first pre-coating to remove waste liquid from the knife edge to ensure the coating quality, then sending the device into the coating machine, and after the coating is completed, sending the device into the vacuum equipment through the automated equipment to increase the vacuum degree, accelerate the volatilization of the solvent, and improve the crystallization quality.

[0031] Preferably, in step (2), the P2 laser scribing step includes: scribing NiO X / PVK / C60 / IWO.

[0032] Preferably, in step (2), the step of preparing the metal electrode includes: sending the device into a magnetron sputtering device to plate Cu.

[0033] More preferably, the thickness of the Cu is 95-105 nm.

[0034] More preferably, the thickness of the Cu is 100 nm.

[0035] Preferably, the P3 laser scribing step includes: scribing NiO X / PVK / C60 / IWO metal electrodes form independent sub-batteries.

[0036] Preferably, the P4 laser scribing step includes: scribing TCO / NiO X / PVK / C60 / IWO metal electrodes, clean edges.

[0037] The second aspect of the present invention provides a TCO / NiO based on a flexible substrate X Composite film.

[0038] Specifically, the TCO / NiO based on flexible substrate X The composite film is prepared by the preparation method provided by the first aspect.

[0039] The third aspect of the present invention provides a TCO / NiO based on a flexible substrate X Application of composite films in solar cells, building-integrated photovoltaics, power supply for wearable devices, and portable energy systems.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] The present invention adopts the flexible winding equipment to prepare the TCO / NiO based on the flexible substrate X The composite film can save costs to a great extent while ensuring a certain efficiency. The introduction of PET substrate has greatly reduced the cost of perovskite solar cells, and the application scenarios of flexible batteries are more extensive. The continuous coating process of TCO and hole transport layer has changed the NiO X The coating and P1 scribing sequence not only eliminates a cleaning process, but also reduces the steps of winding and unwinding, greatly improving production efficiency. DETAILED DESCRIPTION

[0042] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0043] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0044] Example 1

[0045] TCO / NiO based on flexible substrate X Preparation method of composite film.

[0046] The following steps are involved:

[0047] (1) The PET film was fed into the chamber for plasma cleaning, and then the plasma-cleaned PET film was placed on the ITO cathode of the winding device for ITO deposition. An ITO flat target with a ratio of (99:1) was used as the target material, and the chamber pressure was pumped to 5×10 - 4 After 1.5 kW, 5% oxygen was introduced into the chamber, the total gas flow was maintained at 500 sccm, and the chamber pressure was maintained at 0.35 Pa. The power was set to 1.5 kW and the coating was started to obtain the TCO layer.

[0048] Then put NiO X NiO cathode X Deposition, using a NiO planar target with a ratio of (95:5) as the target material, the chamber pressure was pumped to 5×10 -4 After Pa, 5% oxygen was introduced into the chamber, the total gas flow was maintained at 500 sccm, the chamber pressure was maintained at 0.35 Pa, and the power was set to 1.5KW before the film coating was started to obtain 10nm NiO X layer, to obtain a composite layer;

[0049] (2) Then perform P1 laser scribing on the composite layer in turn to cut the NiO X The device is then sent to an automated cleaning device to remove the particle impurities caused by laser scribing. The device is then plasma cleaned to increase wettability and facilitate perovskite solution coating. Perovskite coating is then performed, with two pre-coatings to eliminate waste liquid from the blade to ensure coating quality. The device is then sent to a coating machine. After coating, the device is sent to a vacuum device through automated equipment to increase the vacuum degree, accelerate solvent evaporation, and improve crystallization quality. The device is then placed on a heating table, the temperature is raised to 150°C, annealed and crystallized, and sintering is completed. The device is sent to an evaporation device to coat 20nm C60 to obtain an electron transport layer. The device is sent to a vacuum coating device, and a reactive plasma deposition device is used to coat 25nm IWO to obtain a buffer layer. P2 laser scribing is then performed to cut the NiO X / PVK / C60 / IWO; the device was sent to the magnetron sputtering equipment and plated with 100nm Cu to make the metal electrode; then P3 laser scribing was performed to cut the NiO X / PVK / C60 / IWO metal electrodes to form independent sub-cells; perform P4 laser scribing to cut off TCO / NiO X / PVK / C60 / IWO metal electrodes, edge cleaning, encapsulation, and the production of TCO / NiO based on flexible substrates X Composite film.

[0050] Comparative Example 1

[0051] TCO / NiO based on glass substrate XPreparation method of composite film.

[0052] The following steps are involved:

[0053] 1. PVD deposition of ITO: PVD coating equipment was used for deposition, with an ITO rotating target with a ratio of (99:1) as the target material, and the chamber pressure was pumped to 5×10 -4 After Pa, 6 sccm of oxygen and 294 sccm of argon were introduced into the chamber, and the total gas flow was maintained at 300 sccm. The chamber pressure was maintained at 0.35 Pa, and the power was set to 1.5 kW before the coating was started. The carrier speed was set to 6.5 mm / s, and the rotating target speed was 6 r / min to obtain the TCO layer.

[0054] 2. Cleaning: Send the TCO glass to the automated cleaning equipment, use a brush to remove dust, perform ultrasonic cleaning, rinse with pure water to remove the cleaning agent, dry with an air knife, and perform plasma cleaning to improve wettability;

[0055] 3. P1 laser scribing: Scribing the TCO layer to form independent strip-shaped conductive electrodes;

[0056] 4. Cleaning: The device is sent to an automated cleaning device to remove particulate impurities caused by laser scribing. The device is then plasma cleaned to increase wettability and facilitate perovskite solution coating.

[0057] 5. Preparation of NiO layer: The cleaned TCO glass substrate was sent to the magnetron sputtering coating equipment, and the NiO rotating target was used as the target material. The chamber pressure was pumped to 5×10 -4 After Pa, oxygen 20sccm and argon 380sccm were introduced into the chamber, and the total gas flow was maintained at 400sccm. The chamber pressure was maintained at 0.35Pa, and the power was set to 1.5KW before the coating was started. The carrier speed was set to 10mm / s, and the rotating target speed was 6r / min. 10nm NiO was plated. X ;

[0058] 6. Perovskite coating: Pre-coat twice to eliminate waste liquid from the knife edge to ensure coating quality, then send the device into the coating machine. After coating is completed, send the device into the vacuum equipment through automated equipment to increase the vacuum degree, accelerate solvent volatilization, and improve crystallization quality;

[0059] 7. Sintering: Place the device on a heating table, raise the temperature to 150°C, and anneal for crystallization;

[0060] 8. Prepare the electron transport layer: send the device into the evaporation equipment and coat it with 20nm C60;

[0061] 9. Prepare the buffer layer: send the device into the vacuum coating equipment, and then coat 25nm IWO with reactive plasma deposition equipment;

[0062] 10.P2 laser scribing: cutting NiO X / PVK / C60 / IWO;

[0063] 11. Prepare metal electrodes: Place the device into a magnetron sputtering device and plate 100nm of Cu;

[0064] 12.P3 laser scribing: cutting NiO X / PVK / C60 / IWO metal electrodes to form independent sub-cells;

[0065] 13.P4 laser scribing: cutting TCO / NiO X / PVK / C60 / IWO metal electrode, edge cleaning;

[0066] 14. Packaging to obtain TCO / NiO based on glass substrate X Composite film.

[0067] Performance testing:

[0068] The ITO layer and NiO layer prepared in Example 1 and Comparative Example 1 were tested respectively, and the test data were the test results of two different positions on the same layer;

[0069] The film thickness was measured using an ellipsometer, the transmittance was measured using a UV-visible spectrometer, and the open circuit voltage Voc, short circuit current density Jsc, fill factor FF, and conversion efficiency Eff were measured using an IV tester.

[0070] The following describes the test method for square resistance: Sample preparation: Secure the sample on the test platform to ensure a flat surface. Calibrate the four-probe tester using a standard sample (known square resistance value). Gently touch the four probes to the sample surface to ensure good contact between the probes and the sample. Apply a constant current (usually 1 to 10 mA) and measure the voltage drop between the probes. Calculate square resistance using the formula: Rs = (π / ln²)·(V / I)·k, where Rs is square resistance, V is voltage drop, I is current, and k is a correction factor. Measure each sample at least five times, and take the average value as the final result.

[0071] Table 1 Comparison results of ITO layers of Example 1 and Comparative Example 1

[0072]

[0073] Table 2 Comparison results of NiO layer between Example 1 and Comparative Example 1

[0074]

[0075] Table 3 Comparison results of composite films of Example 1 and Comparative Example 1

[0076]

[0077] As shown in Table 3, the TCO / NiO based on the flexible substrate prepared by the flexible winding equipment in Example 1 of the present invention is X The composite film can save costs to a great extent while ensuring a certain efficiency. The introduction of PET substrate has greatly reduced the cost of perovskite solar cells, and the application scenarios of flexible batteries are more extensive. The continuous coating process of TCO and hole transport layer has changed the NiO X The coating and P1 scribing sequence not only eliminates a cleaning process, but also reduces the steps of winding and unwinding, greatly improving production efficiency.

[0078] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions derived from modifications, equivalent substitutions, improvements, etc. made by those skilled in the art based on the concepts of the present invention through logical analysis, reasoning, or limited experimentation on the basis of the prior art shall be within the scope of protection defined by the claims.

Claims

1. TCO / NiO based on flexible substrate X The method for preparing a composite film is characterized in that: The following steps are involved: (1) Place the flexible substrate on the ITO cathode of the winding device to deposit ITO to obtain a transparent conductive film layer, and then place the NiO X NiO cathode X Depositing a hole transport layer to obtain a composite layer; (2) The composite layer is then subjected to P1 laser scribing, cleaning, perovskite coating, sintering, preparation of electron transport layer, preparation of buffer layer, P2 laser scribing, preparation of metal electrode, P3 laser scribing, P4 laser scribing, and packaging to obtain TCO / NiO based on flexible substrate. X Composite film.

2. The preparation method according to claim 1, characterized in that In step (1), the flexible substrate includes at least one of polyethylene terephthalate and polyethylene naphthalate.

3. The preparation method according to claim 1, characterized in that In step (1), the ITO deposition step includes: using an ITO planar target as a target material, vacuuming the chamber, introducing oxygen into the chamber, maintaining the total gas flow at 300 to 1000 sccm, maintaining the chamber pressure at 0.3 to 0.6 Pa, and setting the power to 1 to 6 kW before starting the coating.

4. The preparation method according to claim 3, characterized in that The proportion of oxygen introduced into the chamber is 1-10%.

5. The preparation method according to claim 1, characterized in that In step (1), the NiO X The deposition steps include: using a NiO planar target as a target material, vacuuming the chamber, introducing oxygen into the chamber, maintaining a total gas flow rate of 300 to 1000 sccm, maintaining a chamber pressure of 0.3 to 0.6 Pa, setting the power to 1 to 6 kW, and then starting the coating.

6. The preparation method according to claim 1, characterized in that In step (2), the sintering temperature is 145-155°C.

7. The preparation method according to claim 1, characterized in that In step (2), the step of preparing the electron transport layer includes placing it in an evaporation device to plate C60.

8. The preparation method according to claim 1, characterized in that In step (2), the step of preparing the buffer layer includes placing it in a vacuum coating device and a reactive plasma deposition device to plate IWO.

9. A TCO / NiO based on a flexible substrate X The composite film is characterized in that The TCO / NiO based on flexible substrate X The composite film is prepared by the preparation method according to any one of claims 1 to 8.

10. The TCO / NiO based on a flexible substrate as claimed in claim 9 X Application of composite films in solar cells, building-integrated photovoltaics, power supply for wearable devices, and portable energy systems.

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