Liquid cell, device, preparation method, perovskite film and perovskite solar cell

Abstract

The present invention discloses a liquid pool, equipment, preparation method, perovskite film and perovskite solar cell, which are applied to the production of perovskite film and creatively integrate printing technology, chemical deposition and two-step heating annealing process. The inorganic component film is prepared by printing process, and after drying, it is immersed in organic component solution for chemical deposition. The thickness of the inorganic component film is controlled by adjusting the concentration of inorganic component solution and printing parameters. The reaction speed of perovskite and the deposition thickness of organic component are controlled by adjusting the concentration of organic component solution, immersion length and film running speed. The perovskite film is grown by heating annealing. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves the production efficiency. The controllability of chemical deposition also improves the uniformity of perovskite film.

Description

Technical Field

[0001] The present invention relates to the field of research, development and production of perovskite thin films and perovskite solar cells, and in particular to a liquid pool, equipment, preparation method, perovskite thin film and perovskite solar cell used for preparing perovskite thin films. Background Art

[0002] Energy shortage and environmental pollution are still the two major crises that restrict the development of today's society. The development and utilization of clean and sustainable solar energy is one of the effective means to solve these two crises. The production process of traditional silicon-based solar cells is very complicated, and it faces the problems of high energy consumption and environmental pollution, which is contrary to the original intention of developing solar cells. In addition, the efficiency of silicon-based solar cells has reached its limit, and the cost space is also very limited. In the past decade, the explosive development of perovskite solar cells has allowed us to see the rise of a new generation of solar cells.

[0003] In recent years, with the continuous breakthroughs in the conversion efficiency of perovskite solar cells, the call for industrialization has become increasingly louder. The improvement in the performance of small-area perovskite solar cells in the laboratory is mainly due to the improvement in the quality of perovskite films. Therefore, in the process of developing the industrialization of perovskite solar cells, how to control the quality of perovskite films has become a top priority.

[0004] The laboratory has a lot of successful experience in preparing small-area perovskite films. For example, a two-step method has been developed. First, a lead salt film is deposited, and then an amine salt film is deposited. Combined with the annealing process, it can effectively control the perovskite crystallization and the surface morphology of the film. Based on the deposition of two layers of film, a combination of multiple deposition methods is provided, such as the two-step physical vacuum vapor deposition method developed by Southeast University, and the two-step slit coating method developed by Jinan University. At present, the best preparation method for perovskite solar cells is still the solution method. Vacuum vapor deposition not only has low production efficiency, but also low efficiency of the prepared battery. Although the two-step slit coating greatly improves production efficiency, the rapid deposition process makes it difficult to control the quality of perovskite film formation. Summary of the invention

[0005] In order to solve the above technical problems and better control the quality of perovskite film formation, the present invention proposes a design concept that combines printing and chemical deposition, which can ensure production efficiency and effectively control the reaction rate of inorganic components and organic components to obtain the high-quality perovskite film.

[0006] The solution-processable property of perovskite solar cells allows them to be prepared theoretically through printing technology suitable for production. In fact, there have been many studies on the preparation of perovskite solar cells using printing technology, which are mainly based on one-step preparation methods. However, in large-area printing, it is difficult to use anti-solvents to regulate perovskite crystallization in the one-step method, making it difficult to control the quality of the film. Therefore, in previous studies, we reported a new process for producing perovskite films using a two-step method, which involves immersion chemical deposition of amine salts. This process can effectively regulate the reaction rate of lead salts and amine salts, thereby regulating the crystallization of perovskites. We found that immersion chemical deposition can regulate the reaction rate of lead salts and organic components (such as amine salts) to a certain extent by regulating the concentration of organic components (such as amine salts). The present invention proposes a new design idea for this immersion chemical deposition process, which can produce a liquid pool with a gradient distribution of amine salt concentration, so that the reaction rate can be more effectively regulated to achieve the purpose of regulating perovskite crystallization.

[0007] The technical solution of the present invention is as follows:

[0008] A liquid cell for preparing a perovskite film, comprising:

[0009] The liquid pool body has a container with length, width and height that can hold the liquid;

[0010] A drainage hole penetrating the liquid pool body is provided at the front end of the liquid pool body;

[0011] A liquid injection device is arranged at the rear end of the liquid pool body, or liquid is injected through the liquid injection hole.

[0012] In practical applications, the injection flow rate and the discharge flow rate can be adjusted or controlled in real time as needed.

[0013] Preferably, a flow controller is also provided for adjusting or controlling the injection flow and / or discharge flow in real time as required.

[0014] Preferably, the organic matter concentration of the liquid in the container decreases from the rear end to the front end of the liquid pool.

[0015] The present invention also provides a device for preparing a perovskite film, which comprises:

[0016] An inorganic component printing device, used for printing the inorganic component onto a flexible substrate to form an inorganic component film;

[0017] A heating and curing device, used for heating and curing the printed inorganic component film;

[0018] A chemical deposition device, comprising the above-mentioned liquid pool and an organic solvent contained in a container for containing liquid in the liquid pool, wherein the inorganic component film after being heated and solidified is introduced into the chemical deposition device for chemical deposition reaction;

[0019] A heating annealing device is used to introduce the chemically deposited film into the heating annealing device for heating annealing, so that the organic solvent can be fully volatilized and the perovskite grains can grow as large as possible, and finally a perovskite film is produced.

[0020] Preferably, the liquid pool comprises:

[0021] The liquid pool body has a container with length, width and height that can hold the liquid;

[0022] A drainage hole penetrating the liquid pool body is provided at the front end of the liquid pool body;

[0023] A liquid injection device is arranged at the rear end of the liquid pool body, or liquid is injected through the liquid injection hole.

[0024] Preferably, a flow controller is also provided for adjusting or controlling the injection flow and / or discharge flow in real time as required.

[0025] Preferably, the organic matter concentration of the liquid in the container decreases from the rear end to the front end of the liquid pool.

[0026] Preferably, it also includes a conveying device, which includes a plurality of rollers, and the rollers guide the flexible substrate to pass through the liquid pools of the inorganic component printing device, the heating and curing device, and the chemical deposition device one by one, and then enter the heating annealing device after coming out of the liquid pool, and finally be rolled up by the subsequent winding device.

[0027] The above design has advantages:

[0028] 1. After the inorganic components are printed on the flexible substrate to form an inorganic film (such as a lead salt film), it then enters and is immersed in a liquid pool, moving from the front end to the rear end of the liquid pool. During this process, the organic components in the solution (such as amine salts) react with the inorganic components on the inorganic film (such as lead salts). The front end of the liquid pool reacts quickly, while the rear end reacts slowly.

[0029] 2. In a liquid pool without injection and drainage, the amine salt at the front end of the liquid pool reacts quickly and is lost, while the rear end reacts slowly and has a high content. Therefore, the present invention sets a drainage hole at the front end of the liquid pool, and the amine salt concentration in the solution discharged from the front end is low, resulting in less waste.

[0030] 3. Liquid injection at the back end. Continuous liquid injection at the back end ensures that the concentration of amine salt in the entire liquid pool has a gradient decreasing trend from the back end to the front end. By adjusting the appropriate liquid injection speed and the film running speed of the lead salt, the gradient will continue to exist. It ensures the stability of the reaction environment and the stability of production quality. The flow rate of liquid injection and liquid discharge can be adjusted or controlled in real time as needed to ensure the above purpose.

[0031] 4. The low concentration of amine salt at the front end can effectively slow down the reaction rate of lead salt at the front end, while the high concentration of amine salt at the back end can appropriately increase the reaction rate at the back end, thereby achieving the purpose of regulating the reaction rate of lead salt and amine salt.

[0032] In the existing technology, the two-step method for preparing perovskite films, specifically the deposition technology of amine salts, is suitable for large-scale production and can be simply divided into two types: one is printing amine salt films, and the other is chemical dipping. The challenge of the former lies in the coverage and thickness uniformity of the film, and the latter has repeated immersion that causes the solution concentration to continue to decrease, which makes the conditions difficult to control, and the perovskite crystallization is difficult to control.

[0033] In order to make the immersion process meet the requirements of production, we designed a liquid pool with controllable amine salt concentration, so that the injection and discharge are balanced, and the reaction consumption of amine salt is balanced with the injection. This can not only effectively save materials and improve the utilization efficiency of materials, but also effectively regulate the entire reaction rate of lead salt and amine salt, so as to achieve the purpose of regulating the crystallization of perovskite.

[0034] The present invention also provides a device for preparing a perovskite film, which is used in a two-step preparation process, and is arranged in order:

[0035] An inorganic component printing device, used for printing the inorganic component onto a flexible substrate to form an inorganic component film;

[0036] The heating and drying device uses hot air heating, infrared heating, or hot plate heating to heat and dry the inorganic component film.

[0037] The chemical deposition device comprises the liquid pool and the organic solvent contained in the liquid container of the liquid pool. The inorganic component film is introduced into the chemical deposition device to carry out chemical deposition reaction.

[0038] Preferably, a flow controller is also provided for adjusting or controlling the injection flow and / or discharge flow in real time as required.

[0039] Preferably, the organic matter concentration of the liquid in the container decreases from the rear end to the front end of the liquid pool.

[0040] Preferably, the roller guides the flexible substrate through the inorganic component printing device, and then enters the liquid pool of the chemical deposition device, and then enters the subsequent processing device after coming out of the liquid pool.

[0041] Operation process: The configured amine salt solution is continuously injected from the main inlet at the rear end of the liquid pool through the injection flow control system. When the solution height in the liquid pool reaches a certain height, the roll-to-roll coating equipment is started to immerse the lead salt film in the amine salt solution, and evenly pass through the liquid pool from the front end of the liquid pool and leave from the rear end of the liquid pool. By scientifically regulating the concentration of the amine salt solution, the amine salt injection flow, the length of the liquid pool and the transmission speed of the lead salt film, the lead salt film slowly reacts with the amine salt in the liquid pool and generates a perovskite film with uniform thickness, complete reaction, good crystallization and flat morphology.

[0042] Preferably, the liquid pool comprises:

[0043] The liquid pool body has a container with length, width and height that can hold the liquid;

[0044] A drainage hole penetrating the liquid pool body is provided at the front end of the liquid pool body;

[0045] A liquid injection device is arranged at the rear end of the liquid pool body, or liquid is injected through the liquid injection hole.

[0046] A method for preparing a perovskite film includes a perovskite film deposition process, wherein the perovskite film deposition process includes the following steps:

[0047] S1, printing an inorganic component on a flexible substrate to form an inorganic component thin film;

[0048] S2, heating and curing the inorganic component film;

[0049] S3, immersing the inorganic component film in an organic component solution for chemical deposition; the organic matter concentration of the liquid in the liquid pool decreases from the rear end to the front end of the liquid pool;

[0050] S4, heating and annealing the chemically deposited film to form a perovskite film.

[0051] The present invention can be used to produce perovskite films based on a roll-to-roll production line, creatively integrating printing technology, chemical deposition and two-step heating annealing processes. The inorganic component film is prepared by the printing process, and after drying, it is immersed in an organic component solution for chemical deposition. The thickness of the inorganic component film is controlled by adjusting the concentration of the inorganic component solution and the printing parameters. The reaction speed of the perovskite and the deposition thickness of the organic component are controlled by adjusting the concentration of the organic component solution, the immersion length and the film running speed. The perovskite film is grown by heating annealing. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves the production efficiency. The controllability of chemical deposition also improves the uniformity of the perovskite film.

[0052] Furthermore, the perovskite film deposition process is based on a roll-to-roll production line to produce the perovskite film.

[0053] Furthermore, the inorganic component in S1 is AX 2 Solution or AX 2 -CsX, wherein the A element includes one or a combination of lead (Pb) or tin (Sn), the X element includes one or two or a combination of more than two of iodine (I), bromine (Br), chlorine (Cl), and acetic acid (Ac), and the inorganic component is dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF), or a mixture of the two.

[0054] Furthermore, the heating method in S2 is hot air heating, infrared heating, or hot plate heating, and the inorganic component film is first heated and dried.

[0055] Furthermore, the organic component S3 is a BX solution, wherein the B position includes methylamine (CH 3 NH 3 ) and formamidine (CH(NH 2 ) 2 ), the X element includes one, two or three of I, Br and Cl, and the organic component is dissolved in isopropyl alcohol (IPA) solution; a chemical deposition method is used to realize the immersion process of the inorganic component film in the organic component solution, and the reaction rate of the inorganic component and the organic component and the deposition thickness are regulated by adjusting the concentration of the organic component in the solution and the roll-to-roll film running speed.

[0056] Furthermore, the heating annealing method in S4 includes hot air heating, infrared heating or hot plate heating, so that the solvent evaporates completely, the deposited inorganic components react with the organic components to generate perovskite, and the perovskite seed crystals are promoted to grow.

[0057] Furthermore, the printing process of the inorganic component in S1 includes slit coating and concave coating, and the thickness of the printed inorganic component is 200-1500nm.

[0058] The present invention also provides a method for preparing a perovskite film, including a perovskite film deposition process, wherein the perovskite film deposition process includes the following steps:

[0059] S1, printing an inorganic component on a flexible substrate to form an inorganic component thin film;

[0060] S2, immersing the inorganic component film into the organic component solution in the liquid pool for chemical deposition; the organic matter concentration of the liquid in the liquid pool decreases from the rear end to the front end of the liquid pool.

[0061] Among them, the inorganic component in S1 is AX 2 Solution or AX 2-CsX, wherein the A element includes one or a combination of lead (Pb) or tin (Sn), the X element includes one or two or a combination of more than two of iodine (I), bromine (Br), chlorine (Cl), and acetic acid (Ac), and the inorganic component is dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF), or a mixture of the two.

[0062] The organic component S3 is a BX solution, wherein the B position includes methylamine (CH 3 NH 3 ) and methylamine (CH(NH 2 ) 2 ), the X element includes one, two or three of I, Br and Cl, and the organic component is dissolved in isopropyl alcohol (IPA) solution; a chemical deposition method is used to realize the immersion process of the inorganic component film in the organic component solution, and the reaction rate of the inorganic component and the organic component and the deposition thickness are regulated by adjusting the concentration of the organic component in the solution and the roll-to-roll film running speed.

[0063] The present invention also provides a perovskite film, which is prepared by a device comprising any of the above-mentioned liquid pools, or is prepared according to any of the above-mentioned methods for preparing the perovskite film.

[0064] The present invention also provides a perovskite solar cell, which is prepared by a perovskite film prepared by a device comprising any of the above-mentioned liquid pools, or a perovskite film prepared according to any of the above-mentioned perovskite film preparation methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art are briefly introduced below.

[0066] Figure 1 and Figure 2 It is a schematic diagram of the production method and equipment of the present invention. DETAILED DESCRIPTION

[0067] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0068] like Figure 1 and Figure 2 As shown in the partial device of reference numeral 3, a liquid cell for preparing a perovskite film comprises:

[0069] The liquid pool body 3 has a container with length, width and height that can hold liquid;

[0070] A liquid discharge hole 33 penetrating the liquid pool body is provided at the front end of the liquid pool body 3;

[0071] A liquid injection device is installed at the rear end of the liquid pool body 3, or liquid is injected through the liquid injection hole 32.

[0072] In practical applications, the injection flow rate and the discharge flow rate can be adjusted or controlled in real time as needed.

[0073] The front end and rear end of the liquid pool body are determined according to the moving direction of the material to be processed. The side of the liquid pool body that the material to be processed first enters is defined as the front end, and the side of the liquid pool body away from the front end is defined as the rear end. Specifically, in the example shown in the accompanying drawings, the flexible substrate 6 (film) to be processed moves from left to right in the accompanying drawings. Therefore, the front end of the liquid pool body 3 is on the left, and the rear end of the liquid pool body 3 is on the right. We introduce the flexible substrate 6 (film) that has undergone the inorganic printing process into the liquid pool, and do not let it be immersed in the liquid statically as in the prior art, but move the film along the length direction of the liquid pool, from a certain part of the film being immersed in the liquid pool to finally leaving the liquid pool. The time it is immersed in the solution is determined by the length of the liquid pool and the speed at which the film moves. Therefore, it is convenient to achieve a balance between product quality and production efficiency by adjusting the length of the liquid pool and the speed at which the film moves. Furthermore, the inorganic component film is prepared by printing process. The high or low solution concentration, fast or slow injection speed, large or small distance between the coating head and the substrate, and slow or fast printing speed can increase or decrease the thickness of the printed film. Therefore, the thickness of the perovskite film obtained by the complete reaction of organic components and inorganic components can be conveniently adjusted. The quality of the product can be controlled and stabilized under the premise of meeting the production efficiency. Compared with the existing technology, it is a great improvement.

[0074] In practical applications, in order to further optimize the control of solution concentration, a flow controller is also provided to adjust or control the injection flow and / or discharge flow in real time as required.

[0075] In practical applications, the concentration of organic matter in the liquid in the container can be controlled to decrease from the rear end to the front end of the liquid pool by controlling the discharge flow rate and the injection flow rate. The advantages brought are described below.

[0076] As attached Figure 1 and 2 As shown, the present invention also provides a device for preparing a perovskite film, which is arranged in sequence:

[0077] The inorganic component printing device 1 is used to print the inorganic component onto the flexible substrate 6 to form an inorganic component film. In practical applications, the existing slit coating equipment can be used, and the inorganic component solution is used as the coating ink. The ink is continuously injected into the coating head at a uniform speed using an injection pump, and the inorganic component material is coated on the flexible substrate 6 (film). An inorganic component layer is formed on the flexible substrate 6 to obtain an inorganic component film.

[0078] A heating and curing device 2 is used to heat and cure the printed inorganic component film;

[0079] A chemical deposition device, comprising the above-mentioned liquid pool and an organic solvent 31 contained in a liquid container of the liquid pool, wherein the inorganic component film after being heated and solidified is introduced into the chemical deposition device for chemical deposition reaction;

[0080] The heating annealing device 5 is used to introduce the chemically deposited thin film into the heating annealing device for heating annealing, so that the organic solvent can be fully volatilized and the perovskite grains can grow as large as possible, thereby finally forming a perovskite thin film.

[0081] Likewise, the chemical deposition device may use the aforementioned liquid pool, wherein the liquid pool comprises:

[0082] The liquid pool body 3 has a container with length, width and height that can hold liquid;

[0083] A liquid discharge hole 33 penetrating the liquid pool body is provided at the front end of the liquid pool body 3;

[0084] A liquid injection device is installed at the rear end of the liquid pool body 3, or liquid is injected through the liquid injection hole 32.

[0085] In some examples, a flow controller is also provided for adjusting or controlling the injection flow and / or drainage flow as required. In practical applications, a flow control device is formed by means of an electrically controlled valve, a flow sensor, a liquid level sensor, etc. There are many of them in the prior art and they will not be described in detail. However, in this application, the concentration of the organic solution in the liquid pool can be controlled, and the concentration gradient of the organic solution can be controlled by regulating the drainage flow and the injection flow. For example, reducing the drainage speed and increasing the injection speed in a certain period of time can increase the solution concentration and change the concentration gradient. In some embodiments, multiple injection holes can also be provided, and the concentrations of the organic solutions injected into different injection holes are different, so the solution concentration can be adjusted in real time.

[0086] In some embodiments, it is particularly emphasized that the concentration of organic matter in the liquid in the container decreases from the rear end to the front end of the liquid pool.

[0087] In a specific application, a conveying device is also included, which includes a plurality of rollers. The rollers guide the flexible substrate to pass through the liquid pools of the inorganic component printing device, the heating and curing device, and the chemical deposition device one by one, and then enter the heating annealing device after coming out of the liquid pool, and finally be rolled up by the subsequent winding device. Figure 1 and Figure 2 The roller 4 shown in the figure is a part of the roller in the conveying device, which introduces the flexible substrate 6 coated with an inorganic component (which becomes an inorganic component film at this time) from the front end of the liquid pool into the solution in the liquid pool, and then guides the liquid pool out of the rear end of the liquid pool after the chemical deposition reaction, and moves to the subsequent heating and annealing device 5.

[0088] The above design has advantages:

[0089] 1. After the inorganic components are printed on the flexible substrate to form an inorganic film (such as a lead salt film), it then enters and is immersed in a liquid pool, moving from the front end to the rear end of the liquid pool. During this process, the organic components in the solution (such as amine salts) react with the inorganic components on the inorganic film (such as lead salts). The front end of the liquid pool reacts quickly, while the rear end reacts slowly.

[0090] 2. In a liquid pool without injection and drainage, the amine salt at the front end of the liquid pool reacts quickly and is lost, while the rear end reacts slowly and has a high content. Therefore, the present invention sets a drainage hole at the front end of the liquid pool, and the amine salt concentration in the solution discharged from the front end is low, resulting in less waste.

[0091] 3. Liquid injection at the back end. Continuous liquid injection at the back end ensures that the concentration of amine salt in the entire liquid pool has a gradient decreasing trend from the back end to the front end. By adjusting the appropriate liquid injection speed and the film running speed of the lead salt, the gradient will continue to exist. It ensures the stability of the reaction environment and the stability of production quality. The flow rate of liquid injection and liquid discharge can be adjusted or controlled in real time as needed to ensure the above purpose.

[0092] 4. The low concentration of amine salt at the front end can effectively slow down the reaction rate of lead salt at the front end, while the high concentration of amine salt at the back end can appropriately increase the reaction rate at the back end, thereby achieving the purpose of regulating the reaction rate of lead salt and amine salt.

[0093] In the existing technology, the two-step method for preparing perovskite films, specifically the deposition technology of amine salts, is suitable for large-scale production and can be simply divided into two types: one is printing amine salt films, and the other is chemical dipping. The challenge of the former lies in the coverage and thickness uniformity of the film, and the latter has repeated immersion that causes the solution concentration to continue to decrease, which makes the conditions difficult to control, and the perovskite crystallization is difficult to control.

[0094] In order to make the immersion process meet the requirements of production, we designed a liquid pool with controllable amine salt concentration, so that the injection and discharge are balanced, and the reaction consumption of amine salt is balanced with the injection. This can not only effectively save materials and improve the utilization efficiency of materials, but also effectively regulate the entire reaction rate of lead salt and amine salt, so as to achieve the purpose of regulating the crystallization of perovskite.

[0095] The present invention provides a roll-to-roll production method for perovskite thin films that combines coating and chemical deposition technology. The method integrates the printing process of inorganic components, the chemical deposition process of organic components, and a two-step heating annealing process. The printing process of inorganic components can select coating methods such as slit coating and concave coating, and the thickness of the printed inorganic components is within the range of 200-1500nm; the first drying unit (heating and curing device) can select heating methods such as hot air, infrared, and hot plate to make the solvent evaporate quickly and the inorganic components solidify into a thin film; chemical deposition controls the concentration of the organic component solution and the roll-to-roll film running speed, regulates the reaction speed of the inorganic component and the organic component and the deposition thickness of the organic component, so that the inorganic component film reacts completely; the second drying unit (heating and annealing device) can select heating methods such as hot air, infrared, and hot plate to make the wet film solvent evaporate completely, promote the reaction to generate perovskite, and help the growth of perovskite seed crystals.

[0096] Operation process: The flexible substrate first passes through the coating unit (inorganic component printing device), and the inorganic component film of appropriate thickness is printed by adjusting the coating parameters such as the concentration of the inorganic component solution and the film running speed; as the substrate moves, the inorganic component film reaches the first drying unit (heating and curing device), and the solvent in the inorganic component wet film is accelerated to evaporate completely by hot air, infrared or hot plate, and solidified and condensed on the flexible substrate; then, the cured inorganic component film passes through the liquid pool, and the liquid pool (container containing organic solution) is filled with organic component solution. By adjusting the concentration of the organic component solution, the immersion length and the film running speed, the reaction rate of the organic component and the inorganic component is regulated; then the film enters the second drying unit (heating annealing device), and the length of the second drying unit or the film running speed is adjusted to control the perovskite annealing time, so that the solvent is fully volatilized and the perovskite grains grow as much as possible. The above four stages are carried out continuously and synchronously, thereby improving production efficiency. The appropriate concentration of the organic component solution helps to control the reaction rate between the inorganic component and the organic component, thereby controlling the crystallization rate of the perovskite, which is beneficial to improving the surface morphology of the perovskite film.

[0097] In practical applications, when the inorganic component film is prepared by the printing process, the high or low value of the solution concentration, the fast or slow injection speed, the large or small distance between the coating head and the substrate, and the slow or fast printing speed can all increase or decrease the thickness of the printed film. Prepare an inorganic component solution with a concentration of 0.5-1.5 mol / L, the injection speed is 20-200ul / min, adjust the distance between the coating head and the substrate within the range of 30-150um, the printing speed is 1-30mm / s, and anneal at 50-100℃ for 1-10min, then an inorganic component film with a thickness of 200-800nm ​​can be obtained. The inorganic film is immersed in an organic component solution for chemical deposition. The high concentration of the organic component solution and the long immersion time (long immersion length and slow film running speed can obtain sufficient immersion time) can increase the deposition thickness of the organic component. The concentration of the organic component solution is maintained at 0.05-0.5 mol / L, the immersion time is 1-10 min (immersion length is 10-200 cm, film running speed is 1-30 mm / s), and after heating and annealing at 80-150 ° C for 10-30 min, the organic component and the inorganic component are completely reacted to obtain a perovskite film with a thickness of 300-1200 nm. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves production efficiency. The controllability of chemical deposition also improves the uniformity of the perovskite film.

[0098] In practical applications, based on the premise of cost saving, the solution depth in the liquid pool is as small as possible and can be set to 2 cm. The width of the liquid pool is larger than that of PbI 2 The film width is 5cm, and the length needs to match the film running speed (PbI 2 The printing speed is generally 1-30mm / s), the solution concentration in the liquid pool (0.05-0.5mol / L) and the required immersion time (1-10min), the liquid pool length is generally between 0.5-2m, the discharge and injection are balanced, the flow rate is controlled at 10-100ml / min, and the solution concentration at the front end of the liquid pool is kept about half of the concentration at the back end. The solution depth and the width of the liquid pool will increase the waste of materials. Increasing the depth and width will increase the total amount of solution in the liquid pool, which will help maintain the stability of the solution concentration and control the uniformity of film formation.

[0099] According to the above-mentioned equipment for preparing perovskite film, we can cooperate with a method for preparing perovskite film, including a perovskite film deposition process, and the perovskite film deposition process includes the following steps:

[0100] S1, printing an inorganic component on a flexible substrate to form an inorganic component thin film;

[0101] S2, heating and curing the inorganic component film;

[0102] S3, immersing the inorganic component film in an organic component solution for chemical deposition; the organic matter concentration of the liquid in the liquid pool decreases from the rear end to the front end of the liquid pool;

[0103] S4, heating and annealing the chemically deposited film to form a perovskite film.

[0104] The present invention can be used to produce perovskite films based on a roll-to-roll production line, creatively integrating printing technology, chemical deposition and two-step heating annealing processes. The inorganic component film is prepared by the printing process, and after drying, it is immersed in an organic component solution for chemical deposition. The thickness of the inorganic component film is controlled by adjusting the concentration of the inorganic component solution and the printing parameters. The reaction speed of the perovskite and the deposition thickness of the organic component are controlled by adjusting the concentration of the organic component solution, the immersion length and the film running speed. The perovskite film is grown by heating annealing. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves the production efficiency. The controllability of chemical deposition also improves the uniformity of the perovskite film.

[0105] In practical applications, in conjunction with a roll-to-roll production line, the perovskite film deposition process can improve the efficiency of producing perovskite films based on a roll-to-roll production line.

[0106] In practical applications, the inorganic component in S1 is AX 2 Solution or AX 2 -CsX, wherein the A element includes one or a combination of lead (Pb) or tin (Sn), the X element includes one or a combination of two or more of iodine (I), bromine (Br), chlorine (Cl), acetic acid (Ac), and the inorganic component is dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF), or a mixture of the two. In practical applications, the molar ratio of A to Cs can be greater than 1:1, the concentration of the inorganic component solution is 0.5-1.5 mol / L, and the coating speed is 1-30 mm / s.

[0107] For example, the AX 2 PbI 2 , soluble in a mixture of DMF and DMSO in a volume ratio of 95:5, with a concentration of 1 mol / L and a coating speed of 10 mm / s.

[0108] Furthermore, the heating method in S2 is hot air heating, infrared heating, or hot plate heating, and the inorganic component film is first heated and dried.

[0109] Furthermore, the organic component S3 is a BX solution, wherein the B position includes methylamine (CH 3 NH 3 ) and methylamine (CH(NH 2 ) 2), the X element includes one, two or three of I, Br and Cl, the organic component is dissolved in isopropyl alcohol (IPA) solution, and the solution concentration is 0.05-0.5 mol / L; the chemical deposition method is adopted, the film moving speed is 1-30 mm / s, the liquid pool length is between 0.5-2 m, and the immersion time is controlled to be 1-10 min. The inorganic component film is immersed in the organic component solution, and the reaction speed and deposition thickness of the inorganic component and the organic component are regulated by regulating the concentration of the organic component in the solution and the roll-to-roll film running speed. For example, the organic component BX is CH 3 NH 3 I, concentration is 0.2mol / L.

[0110] Furthermore, the heating annealing method in S4 includes hot air heating, infrared heating or hot plate heating, so that the solvent evaporates completely, the deposited inorganic components react with the organic components to generate perovskite, and the perovskite seed crystals are promoted to grow.

[0111] Furthermore, the printing process of the inorganic component in S1 includes slit coating and concave coating, and the thickness of the printed inorganic component is 200-800nm.

[0112] The present invention also provides a perovskite film, which is prepared by a device comprising any of the above-mentioned liquid pools, or is prepared according to any of the above-mentioned methods for preparing the perovskite film.

[0113] The present invention also provides a perovskite solar cell, which is prepared by a perovskite film prepared by a device comprising any of the above-mentioned liquid pools, or a perovskite film prepared according to any of the above-mentioned perovskite film preparation methods.

[0114] The present invention can produce perovskite films based on a roll-to-roll production line, creatively integrating printing technology, chemical deposition and two-step heating annealing processes. The inorganic component film is prepared by the printing process, and after drying, it is immersed in an organic component solution for chemical deposition. The thickness of the inorganic component film is controlled by adjusting the concentration of the inorganic component solution and the printing parameters. The reaction speed of the perovskite and the deposition thickness of the organic component are controlled by adjusting the concentration of the organic component solution, the immersion length and the film running speed. The perovskite film is grown by heating annealing. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves the production efficiency. The controllability of chemical deposition also improves the uniformity of the perovskite film.

[0115] In actual implementation, the inorganic component film is prepared by printing process. The high or low value of the solution concentration, the fast or slow injection speed, the large or small distance between the coating head and the substrate, and the slow or fast printing speed can increase or decrease the thickness of the printed film. The inorganic component solution with a concentration of 0.5-1.5 mol / L is prepared, the injection speed is 20-200ul / min, the distance between the coating head and the substrate is adjusted to be in the range of 30-150um, the printing speed is 1-30mm / s, and the inorganic component film with a thickness of 200-800nm ​​can be obtained by heating and annealing at 50-100℃ for 1-10min. Then the inorganic film is immersed in the organic component solution for chemical deposition. The high concentration of the organic component solution and the long immersion time (long immersion length and slow film running speed can obtain sufficient immersion time) can increase the deposition thickness of the organic component. The concentration of the organic component solution is maintained at 0.05-0.5 mol / L, the immersion time is 1-10 min (immersion length is 10-200 cm, film running speed is 1-30 mm / s), and after heating and annealing at 80-150 ° C for 10-30 min, the organic component and the inorganic component are completely reacted to obtain a perovskite film with a thickness of 300-1500 nm. The process system integrates four processes into one production line, and the four processes are operated synchronously, which greatly improves production efficiency. The controllability of chemical deposition also improves the uniformity of the perovskite film.

[0116] Furthermore, the perovskite film deposition process can produce perovskite films based on a roll-to-roll production line. The roll-to-roll production method can realize full automation of unloading, processing and receiving. The so-called roll-to-roll means that the substrate raw material is in a roll shape, and the unloading is realized by rotating the rotating shaft, and the final product is also wound into a roll shape by rotating the winding shaft. If necessary, the feeding and unloading can also be done without roll-to-roll. For example, the equipment is directly connected to the production line of the substrate and directly uses rollers to introduce it for production.

[0117] Operation process: The configured amine salt solution (or other available organic component solution) is continuously injected from the main inlet at the rear end of the liquid pool through the injection flow control system. When the solution height in the liquid pool reaches a certain height, the roll-to-roll coating equipment is started to immerse the lead salt film in the amine salt solution, and evenly pass through the liquid pool from the front end of the liquid pool and leave from the rear end of the liquid pool. By scientifically regulating the concentration of the amine salt solution, the amine salt injection flow, the length of the liquid pool and the transmission speed of the lead salt film, the lead salt film slowly reacts with the amine salt in the liquid pool, and generates a perovskite film with uniform thickness, complete reaction, good crystallization and flat morphology.

[0118] The present invention also provides a perovskite solar cell, which is prepared by a perovskite film prepared by any of the above-mentioned liquid pools or devices for preparing perovskite films, or any of the above-mentioned methods for preparing perovskite films.

[0119] The above is only a preferred embodiment of a liquid cell, an apparatus and a preparation method for preparing a perovskite film disclosed in the present invention. It should be pointed out that a person skilled in the art can make several modifications and improvements without departing from the creative concept of the present invention, which all fall within the scope of protection of the present invention.

Claims

1. A liquid cell for preparing a perovskite film, It is characterized in that include: The liquid pool body has a container with length, width and height that can hold the liquid; A drainage hole penetrating the liquid pool body is provided at the front end of the liquid pool body; A liquid injection device is installed at the rear end of the liquid pool body, or liquid is injected through the liquid injection hole; The organic matter concentration of the liquid in the container decreases from the rear end to the front end of the liquid pool.

2. The liquid cell for preparing a perovskite thin film according to claim 1, It is characterized in that A flow controller is also provided for adjusting or controlling the injection flow and / or discharge flow in real time as required.

3. A device for preparing a perovskite film, It is characterized in that In order: An inorganic component printing device, used for printing the inorganic component onto a flexible substrate to form an inorganic component film; A heating and curing device, used for heating and curing the printed inorganic component film; A chemical deposition device, comprising the liquid pool of claim 1 or 2, and an organic solvent contained in a container for containing liquid in the liquid pool, wherein the inorganic component film after being heated and solidified is introduced into the chemical deposition device for chemical deposition reaction; A heating annealing device is used to introduce the chemically deposited film into the heating annealing device for heating annealing, so that the organic solvent can be fully volatilized and the perovskite grains can grow as large as possible, and finally a perovskite film is produced.

4. A method for preparing a perovskite film, It is characterized in that The perovskite thin film deposition process includes the following steps: S1, printing an inorganic component on a flexible substrate to form an inorganic component thin film; S2, heating and curing the inorganic component film; S3, immersing the inorganic component film into an organic component solution in a liquid pool for chemical deposition; the organic matter concentration of the liquid in the liquid pool decreases from the rear end to the front end of the liquid pool; S4, heating and annealing the chemically deposited film to form a perovskite film.

5. The method for preparing a perovskite thin film according to claim 4, It is characterized in that The inorganic component in S1 is AX 2 Solution or AX 2 -CsX, wherein the A element includes one or a combination of lead (Pb) or tin (Sn), the X element includes one or two or a combination of more than two of iodine (I), bromine (Br), chlorine (Cl), and acetic acid (Ac), and the inorganic component is dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF), or a mixture of the two.

6. The method for preparing a perovskite thin film according to claim 4, It is characterized in that The organic component of S3 is a BX solution, in which the B position includes methylamine (CH 3 NH 3 ) and formamidine (CH(NH 2 ) 2 ), the X element includes one, two or three of I, Br and Cl, and the organic component is dissolved in isopropyl alcohol (IPA) solution; a chemical deposition method is used to realize the immersion process of the inorganic component film in the organic component solution, and the reaction rate of the inorganic component and the organic component and the deposition thickness are regulated by adjusting the concentration of the organic component in the solution and the roll-to-roll film running speed.

7. A method for preparing a perovskite film, It is characterized in that The perovskite thin film deposition process includes the following steps: S1, printing an inorganic component on a flexible substrate to form an inorganic component thin film; S2, immersing the inorganic component film into the organic component solution in the liquid pool for chemical deposition; the organic matter concentration of the liquid in the liquid pool decreases from the rear end to the front end of the liquid pool.

8. The method for preparing a perovskite thin film according to claim 7, It is characterized in that The inorganic component in S1 is AX 2 Solution or AX 2 -CsX, wherein the A element includes one or a combination of lead (Pb) or tin (Sn), the X element includes one or two or a combination of more than two of iodine (I), bromine (Br), chlorine (Cl), and acetic acid (Ac), and the inorganic component is dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF), or a mixture of the two.

9. The method for preparing a perovskite thin film according to claim 7, It is characterized in that The organic component of S3 is a BX solution, in which the B position includes methylamine (CH 3 NH 3 ) and formamidine (CH(NH 2 ) 2 ), the X element includes one, two or three of I, Br and Cl, and the organic component is dissolved in isopropyl alcohol (IPA) solution; a chemical deposition method is used to realize the immersion process of the inorganic component film in the organic component solution, and the reaction rate of the inorganic component and the organic component and the deposition thickness are regulated by adjusting the concentration of the organic component in the solution and the roll-to-roll film running speed.

10. A perovskite film prepared by a device comprising the liquid pool according to claim 1 or 2, or prepared by the method for preparing a perovskite film according to any one of claims 4 to 9.

11. A perovskite solar cell, prepared by a perovskite film prepared by a device comprising the liquid pool according to claim 1 or 2, or prepared by a perovskite film prepared by the method for preparing a perovskite film according to any one of claims 4 to 9.

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