A method for preparing a semi-transparent perovskite solar cell

Abstract

The present invention discloses a method for preparing a semi-transparent perovskite solar cell, including a semi-transparent perovskite solar cell with an n-i-p type structure or a p-i-n type structure. The beneficial effects of the present invention are as follows: the preparation method of the transparent conductive oxide film used is reactive plasma deposition, which can avoid damage to the substrate during the deposition process and eliminate the need to add a buffer layer to the perovskite cell; the raw material used to prepare the transparent conductive oxide film is a purchased bulk target material, and no other process gas is required except the argon gas required for the ion gun, and the preparation method is simple; the semi-transparent perovskite solar cell using reactive plasma deposition of a transparent conductive oxide film as the top transparent conductive layer does not require annealing of the top transparent electrode, is suitable for perovskites that are not resistant to high temperatures, has a relatively simple preparation process, can achieve a wide-bandgap perovskite cell conversion efficiency of >20%, has high efficiency and low cost potential, and is suitable for large-area cells.

Description

Technical Field

[0001] The present invention relates to a method for preparing a solar cell, in particular to a method for preparing a semi-transparent perovskite solar cell, and belongs to the technical field of photovoltaic applications. Background Art

[0002] Semi-transparent perovskite solar cells (ST-PSCs) can be formed by replacing the opaque metal electrode of conventional perovskite cells with a transparent conductive electrode (referred to as the top transparent electrode, to distinguish it from the transparent electrode on the glass substrate). The adjustable bandgap of the absorber layer and the semi-transparency of the cell make ST-PSCs suitable for high-efficiency perovskite / crystalline silicon (or CIGS, etc.) tandem cells and building-integrated photovoltaic power generation. The realization of high-efficiency ST-PSCs is difficult. The perovskite layer's poor tolerance to temperature and ion bombardment places high demands on the preparation process of the transparent conductive electrode on top of the perovskite layer (referred to as the top transparent electrode). It can be said that the material properties and preparation process of the transparent conductive layer on top of the perovskite layer are one of the key factors affecting the performance of ST-PSCs or tandem cells.

[0003] Transparent conductive oxide (TCO) films are the most commonly used transparent conductive materials. Common TCOs include indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), indium hydroxide-doped (IO:H), and indium zinc oxide (IZO). Methods for preparing these materials primarily include thermal evaporation, atomic layer deposition, and magnetron sputtering. Currently, magnetron sputtering is commonly used to prepare the top transparent electrode of semi-transparent perovskite solar cells. To reduce damage to the substrate caused by the sputtering process, a buffer layer is typically deposited before the top transparent electrode is formed. Furthermore, to obtain TCO films with excellent photoelectric properties, high-temperature annealing at temperatures exceeding 200°C is often required after film deposition or before device application. This annealing temperature can cause perovskite degradation. Consequently, several novel top transparent electrode preparation methods have been investigated and reported in recent years. However, these methods often suffer from complex preparation processes or are not suitable for large-scale production.

[0004] Reactive plasma deposition (RPD), also known as hollow cathode discharge ion plating (HCD), has attracted considerable attention in recent years for its advantages in producing high-quality oxide films at relatively low substrate temperatures, including high ionization rates, rapid growth rates, and minimal plasma bombardment damage. However, there are currently no reports on the application of RPD technology to the top transparent electrode of semi-transparent perovskite cells. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a semi-transparent perovskite solar cell in order to solve at least one of the above technical problems.

[0006] The present invention achieves the above-mentioned object through the following technical solutions: a method for preparing a semi-transparent perovskite solar cell, comprising a semi-transparent perovskite solar cell with a nip-type structure or a pin-type structure, wherein the solar cell structure comprises, from top to bottom, an Ag grid line, a top transparent conductive layer, a first transmission layer, a perovskite layer, a second transmission layer, and an ITO glass layer;

[0007] The first transport layer of the nip-type solar cell is a hole transport layer, and the second transport layer is an electron transport layer; the first transport layer of the pin-type solar cell is an electron transport layer, and the second transport layer is a hole transport layer; the Ag grid line located on the top layer is the anode of the solar cell, and the Ag grid line located on the bottom layer of the ITO glass layer is the cathode of the solar cell;

[0008] The preparation method of the semi-transparent perovskite solar cell comprises the following steps:

[0009] Step 1: ultrasonically clean the ITO glass layer substrate using an ITO glass cleaning agent, deionized water, acetone, and ethanol in sequence;

[0010] Step 2: Treat the ITO glass substrate prepared in step 1 with UV-ozone for 10-30 minutes.

[0011] Step 3: Prepare a second carrier transport layer on the ITO glass layer substrate processed in step 2.

[0012] Step 4: Spin-coat a perovskite solution on the carrier transport layer prepared in step 3 to form a perovskite film to prepare a perovskite layer.

[0013] Step 5: Spin-coat the first carrier transport layer on the perovskite layer prepared in step 4.

[0014] Step 6. Place the oxide target and the sample prepared in step 5 into the reactive plasma deposition equipment to prepare a top transparent conductive layer composed of a transparent conductive oxide thin film. Evacuate the chamber until the vacuum reaches 10-4Pa, introduce argon into the chamber, turn on the main power supply when the air pressure in the chamber is 0.4-0.7Pa, adjust the argon flow rate after ignition until the chamber pressure stabilizes at 0.1-0.4Pa, adjust the working current to 30-60A, open the baffle, and start the film deposition. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle covers the sample, the main power supply and argon are turned off, and the deposition of the transparent conductive oxide thin film is completed.

[0015] Step 7: Ag grid lines are prepared on the surface of the transparent conductive oxide film prepared in step 6 by using thermal evaporation technology as an anode, and Ag grid lines are prepared on the surface of the ITO glass layer by using thermal evaporation technology as a cathode.

[0016] As a further solution of the present invention, the hole transport layer adopts spiro-OMeTAD solution, and the electron transport layer adopts diluted tin dioxide aqueous colloidal dispersion.

[0017] As a further solution of the present invention: in step 1, the ITO glass layer is ultrasonically cleaned for 10-40 minutes.

[0018] As a further solution of the present invention: in step 4, the prepared perovskite layer is annealed for 10-60 minutes.

[0019] As a further solution of the present invention: in step 6, the preparation of the top transparent conductive layer specifically includes:

[0020] Evacuate the chamber until the vacuum reaches 10-4Pa, then introduce argon into the chamber. When the pressure inside the chamber reaches 0.4-0.7Pa, turn on the main power supply.

[0021] After ignition, adjust the argon flow rate until the chamber pressure is stable at 0.1-0.4Pa, and adjust the operating current to 30-60A;

[0022] Open the baffle and the film deposition begins. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle is used to cover the sample, the main power supply and argon gas are turned off, and the transparent conductive oxide film deposition is completed.

[0023] As a further solution of the present invention: in step six, the raw material used to prepare the transparent conductive oxide film is a purchased bulk target material, and no other gas needs to be added except the argon gas required by the ion gun.

[0024] The beneficial effects of the present invention are:

[0025] (1) The transparent conductive oxide film used in the method of the present invention is prepared by reactive plasma deposition, which can avoid damage to the substrate during the deposition process and does not require the addition of a buffer layer on the perovskite cell;

[0026] (2) The raw materials used in the method of the present invention for preparing the transparent conductive oxide thin film are purchased bulk target materials, and no other process gases are required except for the argon gas required for the ion gun, so the preparation method is simple;

[0027] (3) The method of the present invention uses a semi-transparent perovskite solar cell with a transparent conductive oxide film deposited by reactive plasma as the top transparent conductive layer. The top transparent electrode does not need to be annealed, and is suitable for perovskites that are not resistant to high temperatures. The preparation process is relatively simple, and a wide-bandgap perovskite cell conversion efficiency of >20% can be achieved. It has the potential for high efficiency and low cost, and is suitable for large-area cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the structure of a NIP-type semi-transparent perovskite solar cell with a transparent conductive oxide film prepared by reactive plasma deposition as the top transparent electrode;

[0029] Figure 2 Schematic diagram of the structure of a PIN-type semi-transparent perovskite solar cell with a transparent conductive oxide film prepared by reactive plasma deposition as the top transparent electrode;

[0030] Figure 3 This is the light IV curve of the NIP-type semi-transparent perovskite solar cell with the transparent conductive oxide film prepared by reactive plasma deposition as the top transparent electrode in Example 1;

[0031] Figure 4 This is the light IV curve of a PIN-type semi-transparent perovskite solar cell using the transparent conductive oxide film prepared by reactive plasma deposition as the top transparent electrode in Example 1.

[0032] In the figure: 1. Ag gate line, 2. Top transparent conductive layer, 3. First transmission layer, 4. Perovskite layer, 5. Second transmission layer, 6. ITO glass layer. DETAILED DESCRIPTION

[0033] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0034] Example 1

[0035] like Figures 1 to 4 As shown, a method for preparing a semi-transparent perovskite solar cell includes a semi-transparent perovskite solar cell with a nip-type structure or a pin-type structure, wherein the solar cell structure is, from top to bottom, an Ag grid line 1, a top transparent conductive layer 2, a first transmission layer 3, a perovskite layer 4, a second transmission layer 5, and an ITO glass layer 6;

[0036] The first transport layer 3 of the nip-type solar cell is a hole transport layer, and the second transport layer 5 is an electron transport layer; the first transport layer 3 of the pin-type solar cell is an electron transport layer, and the second transport layer 5 is a hole transport layer; the Ag grid line 1 located on the top layer is the anode of the solar cell, and the Ag grid line 1 located on the bottom layer of the ITO glass layer 6 is the cathode of the solar cell. The pin-type solar cell structure is, from top to bottom, the Ag grid line 1, the top transparent conductive layer 2, the electron transport layer 3, the perovskite layer 4, the hole transport layer 5, and the ITO glass layer 6;

[0037] The preparation method of the semi-transparent perovskite solar cell comprises the following steps:

[0038] Step 1: ultrasonically clean the ITO glass layer 6 substrate using an ITO glass cleaning agent, deionized water, acetone, and ethanol in sequence;

[0039] Step 2: Treat the ITO glass layer 6 substrate prepared in step 1 with UV-ozone for 10-30 minutes.

[0040] Step 3: Prepare the second carrier transport layer 5 on the ITO glass layer 6 substrate processed in step 2.

[0041] Step 4: Spin-coat the perovskite solution on the carrier transport layer prepared in step 3 to form a perovskite film to prepare a perovskite layer 4.

[0042] Step 5: Prepare the first carrier transport layer 3 by spin coating on the perovskite layer 4 prepared in step 4.

[0043] Step 6: Place the oxide target and the sample prepared in step 5 into a reactive plasma deposition device to prepare a top transparent conductive layer 2 composed of a transparent conductive oxide thin film.

[0044] Step 7: Ag grid lines 1 are prepared as anodes on the surface of the transparent conductive oxide film prepared in step 6 by using thermal evaporation technology, and Ag grid lines 1 are prepared as cathodes on the surface of the ITO glass layer 6 by using thermal evaporation technology.

[0045] Example 2

[0046] In addition to all the technical features of the first embodiment, this embodiment also includes:

[0047] The hole transport layer adopts spiro-OMeTAD solution, and the electron transport layer adopts diluted tin dioxide aqueous colloidal dispersion.

[0048] In step 1, the ITO glass layer 6 is ultrasonically cleaned for 10-40 minutes.

[0049] In step 4, the prepared perovskite layer 4 is annealed for 10-60 minutes.

[0050] In step six, the preparation of the top transparent conductive layer 2 specifically includes:

[0051] Evacuate the chamber until the vacuum reaches 10-4Pa, then introduce argon into the chamber. When the pressure inside the chamber reaches 0.4-0.7Pa, turn on the main power supply.

[0052] After ignition, adjust the argon flow rate until the chamber pressure is stable at 0.1-0.4Pa, and adjust the operating current to 30-60A;

[0053] Open the baffle and the film deposition begins. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle is used to cover the sample, the main power supply and argon gas are turned off, and the transparent conductive oxide film deposition is completed.

[0054] In step six, the raw material used to prepare the transparent conductive oxide film is a purchased bulk target material, and no other gas needs to be added except the argon gas required by the ion gun.

[0055] Example 3

[0056] A method for preparing a semi-transparent perovskite solar cell, using ITO glass as a substrate, and preparing a NIP-type semi-transparent perovskite solar cell thereon, comprising the following steps:

[0057] (1) Ultrasonic cleaning of the ITO glass substrate was performed using an ITO glass cleaning agent, deionized water, acetone, and ethanol in sequence for 20 minutes;

[0058] (2) treating the ITO glass substrate prepared in step (1) with UV-ozone;

[0059] (3) spin coating the diluted tin dioxide hydrocolloid dispersion on the ITO glass substrate treated in step (2) to prepare an electron transport layer, and annealing;

[0060] (4) treating the tin dioxide electron transport layer prepared in step (3) with UV-ozone, spin-coating a perovskite solution on the layer to prepare a perovskite film with a band gap of approximately 1.68 eV, and annealing at 100° C. for 20 minutes;

[0061] (5) spin coating the spiro-OMeTAD solution on the perovskite layer prepared in step (4) to prepare a hole transport layer;

[0062] (6) placing the cerium-doped indium oxide target and the sample prepared in step (5) into a reactive plasma deposition device, evacuating the chamber until the vacuum reaches 10-4 Pa, introducing argon gas into the chamber, turning on the main power supply when the pressure in the chamber is about 0.5 Pa, adjusting the argon gas flow rate after ignition until the chamber pressure stabilizes at about 0.17 Pa, opening the baffle, and starting the film deposition. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle is used to cover the sample, and the main power supply and argon gas are turned off. The transparent conductive oxide film deposition is completed;

[0063] (7) A silver electrode is prepared on the surface of the transparent conductive oxide film prepared in step (6) by thermal evaporation technology to complete the preparation of the battery. The light IV curve of the semi-transparent perovskite solar cell obtained in this embodiment is shown in the attached figure. Figure 3 , among which the open circuit voltage (VOC) is 1.20V, the short circuit current (JSC) is 20.76mA / cm2, the fill factor (FF) is 76.10%, and the conversion efficiency (Eff) is 18.96%.

[0064] Example 4

[0065] A method for preparing a semi-transparent perovskite solar cell, wherein ITO glass is selected as a substrate and a PIN-type semi-transparent perovskite solar cell is prepared thereon, comprising the following steps:

[0066] (1) Ultrasonic cleaning of the ITO glass substrate was performed using an ITO glass cleaning agent, deionized water, acetone, and ethanol in sequence for 20 minutes;

[0067] (2) treating the ITO glass substrate prepared in step (1) with UV-ozone;

[0068] (3) spin coating the PTAA solution on the ITO glass substrate treated in step (2) to prepare a hole transport layer, and annealing;

[0069] (4) spin coating a perovskite solution on the PTAA hole transport layer prepared in step (3) to prepare a perovskite film with a band gap of approximately 1.68 eV, and annealing;

[0070] (5) spin coating a PCBM solution on the perovskite layer prepared in step (4) to prepare an electron transport layer;

[0071] (6) placing the cerium-doped indium oxide target and the sample prepared in step (5) into a reactive plasma deposition device, evacuating the chamber until the vacuum reaches 10-4 Pa, introducing argon gas into the chamber, turning on the main power supply when the pressure in the chamber is about 0.5 Pa, adjusting the argon gas flow rate after ignition until the chamber pressure stabilizes at about 0.17 Pa, opening the baffle, and starting the film deposition. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle is used to cover the sample, and the main power supply and argon gas are turned off. The transparent conductive oxide film deposition is completed;

[0072] (7) A silver electrode is prepared on the surface of the transparent conductive oxide film prepared in step (6) by thermal evaporation technology to complete the preparation of the battery. The light IV curve of the semi-transparent perovskite solar cell obtained in this embodiment is shown in the attached figure. Figure 4 , among which, the open circuit voltage (VOC) is 841.4mV, the short circuit current (JSC) is 20.18mA / cm2, the fill factor (FF) is 57.61%, and the conversion efficiency (Eff) is 9.78%

[0073] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0074] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a semi-transparent perovskite solar cell, characterized in that: A semi-transparent perovskite solar cell with a nip-type structure or a pin-type structure, wherein the solar cell structure comprises, from top to bottom, an Ag grid line (1), a top transparent conductive layer (2), a first transmission layer (3), a perovskite layer (4), a second transmission layer (5), and an ITO glass layer (6); The first transmission layer (3) of the nip-type structure solar cell is a hole transmission layer, and the second transmission layer (5) is an electron transmission layer; the first transmission layer (3) of the pin-type structure solar cell is an electron transmission layer, and the second transmission layer (5) is a hole transmission layer; the Ag grid line (1) located on the uppermost layer is the anode of the solar cell, and the Ag grid line (1) located on the lowermost layer of the ITO glass layer (6) is the cathode of the solar cell; The preparation method of the semi-transparent perovskite solar cell comprises the following steps: Step 1, ultrasonically cleaning the ITO glass layer (6) substrate using an ITO glass cleaning agent, deionized water, acetone, and ethanol in sequence; Step 2: treating the ITO glass layer (6) substrate prepared in step 1 with UV-ozone for 10-30 minutes; Step 3: preparing a second carrier transport layer (5) on the ITO glass layer (6) substrate processed in step 2; Step 4: Spin-coating a perovskite solution on the carrier transport layer prepared in step 3 to form a perovskite film to prepare a perovskite layer (4); Step 5: Spin-coating a first carrier transport layer (3) on the perovskite layer (4) prepared in step 4; Step 6: Place the oxide target and the sample prepared in step 5 into a reactive plasma deposition device to prepare a top transparent conductive layer (2) composed of a transparent conductive oxide thin film. Evacuate the chamber until the vacuum reaches 10-4Pa, introduce argon gas into the chamber, turn on the main power supply when the pressure in the chamber is 0.4-0.7Pa, adjust the argon gas flow rate to stabilize the chamber pressure at 0.1-0.4Pa after ignition, adjust the operating current to 30-60A, open the baffle, start the film deposition, and control the film thickness by controlling the time. After the deposition is completed, cover the sample with the baffle, turn off the main power supply and argon gas, and the transparent conductive oxide thin film deposition is completed. Step 7: Prepare Ag grid lines (1) as anodes on the surface of the transparent conductive oxide film prepared in step 6 by using thermal evaporation technology, and prepare Ag grid lines (1) as cathodes on the surface of the ITO glass layer (6) by using thermal evaporation technology.

2. The method for preparing a semi-transparent perovskite solar cell according to claim 1, characterized in that: The hole transport layer uses a spiro-OMeTAD solution, and the electron transport layer uses a diluted tin dioxide aqueous colloidal dispersion.

3. The method for preparing a semi-transparent perovskite solar cell according to claim 1, wherein: In the step 1, the ultrasonic cleaning time for the ITO glass layer (6) is 10-40 minutes.

4. The method for preparing a semi-transparent perovskite solar cell according to claim 1, wherein: In the step 4, the prepared perovskite layer (4) is annealed for 10-60 minutes.

5. The method for preparing a semi-transparent perovskite solar cell according to claim 1, wherein: In step 6, the preparation of the top transparent conductive layer (2) specifically includes: Evacuate the chamber until the vacuum reaches 10-4Pa, then introduce argon into the chamber. When the pressure inside the chamber reaches 0.4-0.7Pa, turn on the main power supply. After ignition, adjust the argon flow rate until the chamber pressure is stable at 0.1-0.4Pa, and adjust the operating current to 30-60A; Open the baffle and the film deposition begins. The film thickness is controlled by controlling the time. After the deposition is completed, the baffle is used to cover the sample, the main power supply and argon gas are turned off, and the transparent conductive oxide film deposition is completed.

6. The method for preparing a semi-transparent perovskite solar cell according to claim 1, wherein: In step six, the raw material used to prepare the transparent conductive oxide film is a purchased bulk target material, and no other gas needs to be added except the argon gas required by the ion gun.

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