CN110098333B - Preparation method of perovskite absorption layer and processing method of perovskite solar cell - Google Patents
Preparation method of perovskite absorption layer and processing method of perovskite solar cell Download PDFInfo
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- CN110098333B CN110098333B CN201910380503.9A CN201910380503A CN110098333B CN 110098333 B CN110098333 B CN 110098333B CN 201910380503 A CN201910380503 A CN 201910380503A CN 110098333 B CN110098333 B CN 110098333B
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Abstract
The invention provides a preparation method of a perovskite absorption layer and a processing method of a perovskite solar cell. The preparation method of the perovskite absorption layer comprises the following steps: forming process gas containing a gaseous organic source or process gas containing an inorganic source in a gas generation cavity, and controlling the temperature of the process gas to reach a preset process temperature; introducing process gas into the reaction cavity from the gas generation cavity, so that the pressure in the reaction cavity reaches a preset reaction pressure and the temperature reaches a preset reaction temperature; and placing the substrate carrying the inorganic film into a reaction chamber, and reacting the inorganic film with a gaseous organic source or an inorganic source to form the perovskite absorption layer on the substrate. According to the preparation method of the perovskite absorption layer, the gaseous organic source or the inorganic source is formed in the independent closed cavity and the gas-solid reaction is carried out, so that the influence caused by uneven concentration of the gaseous organic source or the inorganic source in the initial reaction stage is reduced, and the quality of the perovskite absorption layer is improved.
Description
Technical Field
The invention relates to a solar cell technology, in particular to a preparation method of a perovskite absorption layer and a processing method of a perovskite solar cell.
Background
Perovskite solar cells (perovskite solar cells) are solar cells using a perovskite-type organic metal halide semiconductor as a light absorbing material. In recent years, the maximum photoelectric conversion efficiency of the perovskite solar cell is improved from 3.8% to 23.2%. The photoelectric conversion efficiency not only exceeds other thin-film solar cells which are developed earlier, but also approaches or even exceeds the industrialized solar cell technology such as polycrystalline silicon solar cells which are developed for years, and the method has huge industrial development prospects.
Perovskite solar cells generally comprise two electrodes: the transparent conductive glass comprises transparent conductive glass, a metal electrode, a hole transport layer and an electron transport layer (compact layer) which are arranged between the two electrodes, and a perovskite absorption layer which is arranged between the hole transport layer and the electron transport layer. The perovskite absorption layer mainly has the functions of absorbing sunlight and generating electron-hole pairs, and the quality of a thin film of the perovskite absorption layer greatly affects the overall photoelectric conversion efficiency of the perovskite solar cell.
The perovskite absorption layer is prepared by a liquid phase method or a gas phase method at the present stage, wherein various organic solvents are inevitably used in the process of preparing the perovskite absorption layer by the liquid phase method, and the adverse effects are generated on the human health and the environmental safety, so that the liquid phase method is difficult to prepareTo obtain large-scale application; the perovskite absorption layer prepared by the gas phase method can avoid the problems. In the existing technology for preparing the perovskite absorption layer by a gas phase method, a gas-solid chemical reaction is mostly carried out on a gaseous organic source or an inorganic source and a solid inorganic thin film to obtain the perovskite absorption layer. Patent application 201810257299.7 describes a method for forming a perovskite absorption layer by in-situ gas-solid reaction, which comprises placing an organic source and a lead halide film in a same sealed chamber, heating the organic source to gasify the organic source and react with the lead halide film to form a final perovskite absorption layer. The method has the problems that the concentration of a gas-phase reactant is not easy to regulate and control, excessive deposition is easy to cause, and a cleaning step needs to be added, so that working procedures are increased, and raw materials are wasted. In the application 201610066196.3, when preparing an organic-inorganic perovskite thin film, a lead oxide thin film is first prepared on a conductive substrate, and then fumigated with hydrogen halide (HCl, HBr, or HI) vapor, followed by methylamine vapor, ethylamine vapor, or formamidine vapor, to prepare a perovskite absorption layer. The method has more complicated steps and also has the problem that the concentration of the gas-phase reactant is difficult to regulate and control. Patent application 201580044633.5 discloses the separation of organic powder AX and supported BX2The substrate of the film is placed at the front end and the rear end of a chamber, organic source powder vapor is carried to the surface of the substrate by inert carrier gas under low pressure and is contacted with BX2The film is chemically reacted to form a perovskite film. The preparation process also has the defect that the perovskite absorption layer is uneven in component due to uneven distribution of gas-phase reactants in the cavity, so that the performance of the perovskite solar cell is influenced.
Disclosure of Invention
In view of the above-mentioned drawbacks, the present invention provides a method for manufacturing a perovskite absorption layer, in which a process gas containing a gas-phase reactant is formed in two independent and connected closed chambers, and a reaction between the gas-phase reactant and an inorganic thin film is performed, thereby reducing the influence of the non-uniform concentration of the gas-phase reactant at the initial stage of the reaction and improving the quality of the perovskite absorption layer.
The invention provides a system for realizing the preparation method.
The invention also provides a processing method of the perovskite solar cell, which comprises the step of preparing the perovskite absorption layer according to the preparation method, so that the perovskite solar cell with good performance can be obtained.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a perovskite absorption layer, comprising the steps of:
forming process gas containing a gaseous organic source or process gas containing an inorganic source in a gas generation cavity, and controlling the temperature of the process gas to reach a preset process temperature;
introducing the process gas reaching the preset process temperature into the reaction cavity from the gas generation cavity, and enabling the pressure in the reaction cavity to reach the preset reaction pressure and the temperature to reach the preset reaction temperature;
and placing the substrate loaded with the inorganic film into a reaction chamber, and reacting the inorganic film with a gaseous organic source or an inorganic source at a preset reaction temperature and a preset reaction pressure to form a perovskite absorption layer on the substrate.
According to the technical scheme provided by the invention, the process gas of a gaseous organic source or the process gas containing an inorganic source is formed in the gas generation cavity, then the process gas enters the reaction cavity, after the temperature and the pressure in the reaction cavity reach the preset reaction conditions, the substrate loaded with the inorganic film is placed in the reaction cavity, so that the gaseous organic source or the inorganic source reacts with the inorganic film under the preset reaction conditions, and the problem of uneven components of the perovskite absorption layer caused by uneven distribution of gas-phase reactants in the closed cavity in the early reaction stage in the process of preparing the perovskite absorption layer in the single closed cavity at the present stage is avoided.
In the whole gas-solid reaction process, the generation rate of the gaseous organic source or inorganic source can be controlled through the conditions such as temperature in the gas generation cavity, so that the gas-solid reaction is controlled more accurately, the gas-solid reaction is more stable and smooth, and finally the obtained whole perovskite absorption layer has a very uniform structure.
In the present invention, the organic source, the inorganic source and the solid thin film can be used as raw materials for the perovskite absorption layer in the current perovskite solar cell. Roughly classified into the following three cases:
1) the organic source is amine compound and/or amidine compound, and the inorganic film has CBX3The composition of (1). Common amine compounds such as methylamine and ethylamine, common amidine compounds such as formamidine; in the composition of the inorganic thin film, B represents one or more divalent metals, such as lead, tin, copper, zinc, palladium, cadmium and mercury; c represents one or more of a monovalent metal and a monovalent cation containing a hydrogen atom, such as a hydrogen ion (H)+) Ammonium ion (NH)4 +) Etc.; x represents a halide ion (e.g. I)-、Br-) One or more of thiocyanato, cyanide and cyanooxysulfate.
For example, the organic source is CH3NH2The composition of the inorganic film is HPbI3The two react in a gas-solid reaction to generate CH3NH3PbI3。
2) The organic source has a composition of AX and the inorganic thin film has BX2The two react to form ABX3Wherein A represents an amino (amino) group or an amidino group; b represents one or more divalent metals, and X represents one or more of halide ions, thiocyanato, cyanide and oxocyanide.
For example, the organic source is CH3NH3I, the composition of the inorganic film is PbI2The two react to form CH3NH3PbI3。
3) The inorganic source has the composition of DX, D represents one or more alkali metals such as cesium, rubidium and potassium; the inorganic film has BX2Wherein represents one or more divalent metals, and X represents one or more of halide ions, thiocyanato, cyanide and oxocyanide.
In addition to the above, the inorganic films may be DX and BX2Composite films of (2), e.g. cesium iodide CsI and lead iodide PbI2The composite film of (1).
It will be understood that in actual production, if two or more gaseous organic sources are required to participate in the reaction, or if a gaseous organic source and an inorganic source are required to participate in the reaction, a plurality of parallel gas generating chambers may be provided, each gas generating chamber is internally provided with a required process gas, and then the process gas is introduced into the reaction chamber to react with the inorganic thin film.
In the specific implementation process of the present invention, the process gas containing the gaseous organic source or the process gas containing the inorganic source is formed in the gas generation chamber, and may be determined according to the properties of the organic source and the inorganic source, and specifically may include the following cases:
case 1: injecting an organic source in a gaseous state into the gas generation chamber; namely, the organic source is gaseous at normal temperature, and can be injected into the gas generation cavity by adopting modes such as decompression release of a high-pressure tank and the like. The rate of formation of the gaseous organic source is controlled by controlling factors such as the release pressure and flow rate.
Case 2: placing the organic source in a solid or liquid state in a gas generation cavity, and heating to form a gaseous organic source; if the organic source is in a solid or liquid state at normal temperature, the organic source can be changed into a gaseous state by heating. By controlling the temperature within the gas generation chamber, the rate at which the solid or liquid organic source is converted to the gaseous organic source can be controlled.
Case 3: and (3) placing the solution dissolved with the organic source in a gas generation cavity, and heating to separate out the organic source to form the gaseous organic source. By controlling the temperature within the gas generation chamber, the rate of precipitation of the organic source can be controlled.
Case 4: and placing the solution dissolved with the inorganic source in the gas generation cavity, and enabling the carrier gas to pass through the solution dissolved with the inorganic source to form the gas flow with the inorganic source. Specifically, a carrier gas may be passed through the solution in which the inorganic source is dissolved, so that the carrier gas carries the inorganic source and the solute, that is, the process gas containing the inorganic source. The rate of formation of the inorganic source can be controlled by controlling the flow rate of the carrier gas and the surface area of the solution in contact with the carrier gas.
In case 4, if the flow rate of the carrier gas is very large, the process gas formed in the gas generation chamber is substantially similar to a spray, where the process gas is composed of the carrier gas and the inorganic source and small droplets of solute entrained in the carrier gas. For convenience of description, the present invention still refers to the reaction of the inorganic source with the solid film as a "gas-solid reaction".
In the specific implementation process of the present invention, aiming at the situations 1to 3, the organic source in the process gas is in a gaseous state, and in the gas-solid reaction process, the temperature in the gas generation chamber is usually controlled to reach the preset process temperature, the partial pressure of the process gas is stably maintained at the saturated vapor pressure, and the process gas, especially the organic source, is ensured to enter the reaction chamber at a constant rate.
It will be appreciated that by controlling the heating temperature, the rate of formation of the gaseous organic source can be controlled, thereby facilitating control of the subsequent gas-solid reaction process. In particular, when the organic source is in a liquid or solid state at room temperature, the temperature of the process gas in the gas generation chamber can be controlled to a predetermined process temperature, and the partial pressure thereof can be controlled to a saturated vapor pressure.
In some embodiments of the invention, the process gas may simply be a gaseous organic source; in other embodiments of the present invention, a carrier gas is introduced into the gas generation chamber, and the carrier gas and the gaseous organic source or the carrier gas and the inorganic source (and the solute) together form the process gas. In addition, the carrier gas is introduced into the gas generation cavity, and the flow of the carrier gas is controlled, so that the composition of the process gas is favorably and accurately controlled, the speed of the process gas, particularly the speed of a gaseous organic source or an inorganic source entering the reaction cavity is favorably controlled, and the speed of the gas-solid reaction is more accurately controlled.
Specifically, the flow of the carrier gas can be controlled to be 0-10000 sccm. In the practice of the present invention, for small scale laboratory experiments, if the reactant is an organic source, the carrier gas may not be used (i.e., the flow rate of the carrier gas is 0) or the flow rate of the carrier gas may be controlled to be small. For large-scale industrial production, carrier gas is required to be introduced into both a gaseous organic source and an inorganic source, and the flow rate of the carrier gas is generally controlled to be 10-10000 sccm.
The carrier gas may be one or more of those commonly used in the art, such as nitrogen and inert gases like helium, neon, argon, etc.
It can be understood that, in order to avoid the temperature fluctuation of the process gas caused by the carrier gas entering the gas generation cavity, the carrier gas can be heated in advance to make the temperature of the carrier gas reach the preset process temperature. For example, a heating device can be arranged on a pipeline between the carrier gas source and the gas generation cavity, so that the temperature of the carrier gas is increased in the transportation process to reach the preset process temperature.
When the process gas in the gas generating cavity reaches the preset process temperature and is stable, the process gas can be introduced into the reaction cavity, so that the pressure in the reaction cavity reaches the preset reaction pressure, and the temperature reaches the preset reaction temperature. As previously mentioned, the temperature within the gas-generating chamber is determined by the nature of the organic or inorganic source. In the specific implementation process of the invention, the temperature in the gas generation cavity is usually controlled to be 50-300 ℃.
The temperature and the pressure in the reaction cavity are determined according to actual gas-solid reaction conditions, wherein the preset reaction temperature can be 50-300 ℃. In the practice of the present invention, the temperature in the gas generation chamber is generally different from the temperature in the reaction chamber, i.e., the predetermined process temperature is different from the predetermined reaction temperature. In order to avoid temperature fluctuation caused when the process gas from the gas generation chamber enters the reaction chamber, a gas heating device is generally required to be arranged between the gas generation chamber and the reaction chamber, for example, a heating coil is arranged around a pipeline between the gas generation chamber and the reaction chamber, so that the process gas reaches a preset reaction temperature in the transportation process in the pipeline.
The preset reaction pressure can be high pressure or low pressure, namely, the gas-solid reaction can be carried out under high pressure or vacuum environment, wherein the high pressure is 0.1013MPa to 1MPa, namely, one standard atmosphere is 1 MPa; the low pressure is generally not less than 0.1Pa and less than a standard atmospheric pressure.
When the temperature and the pressure in the reaction chamber reach the preset reaction temperature and the preset reaction pressure respectively, the substrate carrying the inorganic thin film can be placed in the reaction chamber to perform a gas-solid reaction, wherein the time of the gas-solid reaction can be reasonably set according to actual requirements on the perovskite absorption layer, the thickness of the inorganic thin film, the composition of the gaseous organic source and other factors, and generally can be 1-120 min.
In the gas-solid reaction process, in order to maintain the preset reaction temperature constant, a temperature control device can be arranged in the reaction cavity. If the gas-solid reaction is finished under low pressure, a vacuum device is required to continuously vacuumize, so that the pressure in the reaction cavity is kept stable; if the gas-solid reaction is completed under high pressure, the pressure can be properly released to ensure that the pressure in the reaction cavity is kept stable in order to avoid overhigh pressure.
In addition, a flow dividing device can be arranged in the reaction cavity, so that the process gas from the gas generation cavity can be uniformly distributed in the reaction cavity.
Further, when the pressure in the reaction chamber reaches a preset reaction pressure and the temperature reaches a preset reaction temperature, the process gas can be stabilized in the reaction chamber for 0.1-60 min, and then the substrate loaded with the inorganic thin film is placed in the reaction chamber.
The term "stable" is an actual industrial term, which means that the process gas in the reaction chamber is maintained for a period of time at a preset reaction pressure and a preset reaction temperature, so as to ensure that the process gas in the reaction chamber is uniformly distributed in the whole reaction chamber, and the components are relatively uniform, thereby further ensuring that the perovskite absorption layer formed at the initial stage of the gas-solid reaction is more uniform.
Optionally, after the reaction is completed, annealing treatment may be performed according to actual requirements, and it is generally determined whether the annealing treatment needs to be performed according to performance test results of the perovskite solar cell before and after annealing. The annealing temperature can be 50-300 ℃, and the annealing temperature is lower than the preset reaction temperature.
The second aspect of the invention provides a system for realizing the preparation method of the first aspect, which comprises a vacuum device, a first closed cavity and a second closed cavity which are connected in series and are communicated, wherein the first closed cavity is a gas generation cavity and the second closed cavity is a reaction cavity along the trend of process gas, the gas generation cavity is provided with a temperature control device, the reaction cavity is provided with a temperature control device, a pressure control device and a gas shunting device, and the vacuum device is communicated with the first closed cavity or the second closed cavity.
The third aspect of the invention provides a processing method of a perovskite solar cell, which comprises the following steps:
sequentially forming one of an electron transport layer and a hole transport layer and an inorganic thin film on a substrate;
according to the production method described in the first aspect, a perovskite absorption layer is formed on a substrate;
and finally, sequentially forming the other of the electron transport layer and the hole transport layer and an electrode on the perovskite absorption layer.
Specifically, the substrate used for processing the perovskite solar cell may be a transparent conductive substrate commonly used in the current perovskite solar cell, such as transparent FTO glass, transparent AZO glass, transparent ITO glass, a PET flexible transparent conductive film, or a PI flexible transparent conductive film.
The electron transport layer, the hole transport layer, the inorganic thin film and the electrode can be prepared by adopting conventional means in the field, for example, the inorganic thin film can be prepared by a spin coating method, a vacuum method and other process methods, wherein the thickness of the inorganic thin film can be 0.05-1 μm.
According to the preparation method of the perovskite absorption layer, the organic source/inorganic source and the inorganic film are respectively arranged in the independent closed cavities, so that the formation of the gaseous organic source/inorganic source and the gas-solid reaction are respectively completed in different closed cavities, and therefore before the gas-solid reaction, the state of the process gas in the reaction cavity reaches the stable preset reaction temperature and the stable preset reaction pressure, and the problem of uneven distribution of the perovskite absorption layer caused by uneven concentration of gas-phase reactants when the perovskite absorption layer is heated in the same closed cavity is solved; in addition, the gas-solid reaction process is accurately controlled by controlling the formation rate, the reaction time, the reaction pressure, the reaction temperature and the like of the gaseous organic source/inorganic source, so that the gas-solid reaction is carried out at a stable rate, the whole perovskite absorption layer has more uniform components, the perovskite absorption layer can better exert the photoelectric conversion function, and the performance of the perovskite solar cell is improved.
The system for implementing the preparation method provided by the invention has a simple structure, and can be improved on the basis of the existing perovskite absorption layer preparation system.
The processing method of the perovskite solar cell comprises the preparation method of the perovskite absorption layer, so that the performance of the perovskite solar cell is improved.
Drawings
FIG. 1 is a schematic diagram of a system for producing a perovskite absorber layer provided in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a system for producing a perovskite absorber layer provided in another embodiment of the present invention.
Description of reference numerals:
10-vacuum device; 20-a gas generation chamber; 21-an air intake line;
22-a gas flow meter; 23-a valve; 24-a heating coil;
25-a gas agitation device; 26-gas pipeline; 30-a reaction chamber;
31-a gas diversion device; 32-an exhaust line; 33-a pressure relief valve;
34-an air intake line; 35-a valve; 40-a carrier gas source;
50-a tail gas treatment device; 61-preload chamber; 62-unloading the cavity;
63-an air intake line; 64-an exhaust line; 65-valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Fig. 1 and fig. 2 are schematic structural diagrams of systems for preparing a perovskite absorption layer, respectively, provided in an embodiment of the present invention. As shown in fig. 1 and fig. 2, the present embodiment provides a system for preparing a perovskite absorption layer, which includes a vacuum device 10, and a first closed cavity and a second closed cavity connected in series and in conduction, along the trend of a process gas, the first closed cavity is a gas generation cavity 20, the second closed cavity is a reaction cavity 30, wherein the gas generation cavity 20 is provided with a temperature control device (not shown), the reaction cavity 30 is provided with a temperature control device (not shown), a pressure control device (not shown) and a gas diversion device 31, and the vacuum device 10 is communicated with the first closed cavity and/or the second closed cavity.
Specifically, the first sealed cavity and the second sealed cavity, which are respectively used as the gas generating cavity 20 and the reaction cavity 30, may be sealed cavities commonly used for processing a perovskite absorption layer at present, specifically, flat plate cavities, or tubular cavities. The size of the closed cavity can be suitable for industrialized large-area battery production and also suitable for laboratory small-area battery scientific research.
As shown in FIG. 1, the number of the gas generating chambers 20 may be one; alternatively, as shown in fig. 2, the number of the gas generating chambers 20 may be two or more, and the number of the gas generating chambers 20 may be set appropriately according to the kind of the gaseous organic source or inorganic source. When the number of the gas generating chambers 20 is plural, the plural gas generating chambers 20 are arranged in parallel, and each gas generating chamber 20 is respectively communicated with the reaction chamber 30.
The temperature control device is used to control the temperature within the gas generation chamber 20 and the reaction chamber 30. In this embodiment, the temperature control device is not particularly limited, and may be a heating device cooperating with the first sealed cavity and the second sealed cavity.
Referring further to fig. 1 and 2, the system may further include a carrier gas source 40, and specifically, the gas generation chamber 20 may be communicated with the carrier gas source 40 through the gas inlet line 21, so that the carrier gas in the carrier gas source 40 can enter the gas generation chamber 20 through the gas inlet line 21.
Further, the gas inlet pipe 21 may further include a gas flow meter 22 and a valve 23, wherein the gas flow meter 22 is configured to measure the flow rate of the carrier gas, and the valve 23 is configured to control the flow rate of the carrier gas.
Further, the gas inlet pipe 21 may be wound with a heating coil 24 to heat the carrier gas flowing in the gas inlet pipe 21, so that the carrier gas reaches a predetermined process temperature before entering the gas generation chamber 20.
Further, a gas stirring device 25 may be further disposed in the gas generation chamber 20 to stir the process gas in the gas generation chamber, so that the carrier gas and the organic or inorganic source of the gas are rapidly mixed, and the process gas is rapidly and uniformly distributed in the entire gas generation chamber 20.
Specifically, the gas generating chamber 20 and the reaction chamber 30 can be communicated through a gas pipeline 26. Further, a valve 23 is also arranged on the gas transmission pipeline 26 and a heating coil 24 is wound on the valve 23, wherein the valve 23 is used for adjusting the flow rate of the process gas in the gas transmission pipeline 26, and the heating coil 24 is used for heating the process gas flowing in the gas transmission pipeline 26 to enable the temperature of the process gas to reach a preset reaction temperature.
The reaction chamber 30 may be provided with a gas distribution device 31, so that the process gas from the gas generation chamber 20 can be uniformly distributed in the reaction chamber 30 by the distribution device 31.
As previously mentioned, the reaction chamber 30 is provided with a pressure control device. The pressure control device in this embodiment is not particularly limited, and may be a pressure control device that is engaged with the sealed cavity. Referring to fig. 1 and 2, the reaction chamber 30 is connected to an exhaust pipe 32, the exhaust pipe 32 is provided with a pressure relief valve 33, and when the pressure in the reaction chamber 30 exceeds the preset reaction pressure, the pressure relief valve 33 is opened to discharge the gas in the reaction chamber 30 through the exhaust pipe 32.
I.e. the relief valve 33, as pressure control means. In the specific implementation, the pressure relief valve 33 is generally used under high pressure, i.e. the preset reaction pressure is above 1 atm.
The pressure relief valve 32 may be, in particular, an automatic pressure relief valve, so that when the pressure in the reaction chamber 30 exceeds the preset reaction pressure, the automatic pressure relief valve automatically opens to discharge a part of the gas, thereby ensuring that the pressure in the reaction chamber 30 is stably maintained at the preset reaction pressure.
When the gas-solid reaction is performed under vacuum, i.e. the preset reaction pressure is less than 1 atmosphere, the vacuum device 10 can be kept open during the whole gas-solid reaction. Therefore, the vacuum apparatus 10 can be connected to the reaction chamber 30 through the exhaust line 32.
Specifically, the vacuum apparatus 10 may be a vacuum pump or other vacuum equipment that is conventional in the art, and is capable of discharging air, moisture, etc. from the system before the gas-solid reaction, and ensuring that the gas-solid reaction can be smoothly performed under vacuum conditions.
With further reference to fig. 1 and 2, the system may further include an exhaust gas treatment device 50, which may be in particular in communication with the reaction chamber 30 via an exhaust line 32. In this way, the gas exhausted from the reaction chamber 30 can be recovered and processed in the exhaust gas processing device 50, and particularly, after the reaction in the reaction chamber 30 is completed, the reaction exhaust gas can enter the exhaust gas processing device 50 through the exhaust pipe 32 for processing and recovery.
Referring further to fig. 1 and 2, the exhaust gas treatment device 50 may be specifically connected between the reaction chamber 30 and the vacuum device 10, so that air, water vapor, etc. in the exhaust gas treatment device 50 can be exhausted together before the reaction.
Since the gas used as the carrier gas is typically nitrogen or an inert gas, the reaction chamber 30 can be communicated with the carrier gas source 40 through the gas inlet line 34, so that the nitrogen or the inert gas in the carrier gas source 40 can enter the reaction chamber 30 through the gas inlet line 34. Thus, before the gas-solid reaction, inert gas or nitrogen can be introduced into the reaction cavity 30 through the gas inlet pipeline 34; during the gas-solid reaction, inert gas or nitrogen can be supplemented into the reaction chamber 30 through the gas inlet pipeline 34.
Further, a valve 35 may be provided in the inlet line 34 to regulate the flow of nitrogen or inert gas.
Referring further to fig. 1 and 2, the system may further include a preload chamber 61 and an unload chamber 62 connected to the reaction chamber 30. Before the gas-solid reaction, a substrate which is prepared in advance and is loaded with an inorganic film can be placed in a preloading cavity 61, the preloading cavity 61 is vacuumized and heated, after the temperature and the pressure in the reaction cavity 30 reach a preset reaction temperature and a preset reaction pressure respectively, the loaded inorganic film is conveyed into the reaction cavity 30 from the preloading cavity 61, and the inorganic film and a gaseous organic source or an inorganic source are subjected to the gas-solid reaction; after the gas-solid reaction is finished, the substrate with the perovskite absorption layer is conveyed into the unloading cavity 62 from the reaction cavity 30, and an operator or an automatic assembly line can take out the substrate with the perovskite absorption layer from the unloading cavity 62.
Further, the preload chamber 61 and unload chamber 62 can each be in communication with the carrier gas source 40 through respective gas inlet lines 63, and the preload chamber 61 and unload chamber 62 can each be in communication with the vacuum apparatus 10 through respective gas outlet lines 64. Valves 65 may be provided in both the inlet line 63 and the outlet line 64.
Example two
This example provides a method for preparing a perovskite absorption layer, which is a reaction performed under a high pressure route, and for convenience of understanding, the following description will be made in conjunction with the system in the first example, specifically including the following steps:
1. placing a conductive substrate which is prepared in advance and is loaded with a hole transport layer (or an electron transport layer) and an inorganic thin film in a pre-loading cavity 61; a liquid or solid organic source is placed in the gas generation chamber 20 or an organic source that is gaseous at room temperature is connected into the gas generation chamber 20.
2. The vacuum apparatus 10 is turned on to evacuate the entire system, the vacuum apparatus 10 is turned off, and the carrier gas source 40 is turned on to charge the system with carrier gas. And repeatedly vacuumizing and filling carrier gas for 1-10 times, and fully discharging gas which possibly influences the reaction process, such as oxygen, water vapor and the like in the system.
Specifically, a vacuum may be first applied to bring the pressure in the gas generation chamber 20 and the reaction chamber 30 to 10-2About 1torr, and then a carrier gas is introduced to bring the pressure in the gas generation chamber 20 and the reaction chamber 30 to 760torr (i.e., one standard atmosphere).
3. The gas generation cavity 20 is heated to convert the liquid or solid organic source in the gas generation cavity 20 into a gas state, the temperature in the gas generation cavity 20 reaches a preset process temperature, for example, 50 to 300 ℃, and the process gas partial pressure reaches the saturated vapor pressure of the organic source.
4. The reaction chamber 30 is heated, and under the action of the carrier gas, the gaseous organic source in the gas generation chamber 20 enters the reaction chamber 30 through the gas transmission pipeline 26 under the carrying of the carrier gas, the flow rate of the carrier gas can be 10-10000 sccm, and the carrier gas is uniformly distributed in the reaction chamber 30 through the flow dividing device 31, so that the reaction chamber 30 reaches a preset reaction temperature (for example, 50-300 ℃) and a preset reaction pressure (for example, a standard atmospheric pressure to 1 Mpa).
And after stabilizing for about 0.1-60 min, feeding the substrate in the preloading cavity 61 into the reaction cavity 30, wherein an electron transport layer (or a hole transport layer) and an inorganic thin film are formed on the substrate in advance, and reacting the inorganic thin film with a gaseous organic source for 1-120 min, wherein the reaction temperature is the preset reaction temperature, and the reaction pressure is the preset reaction pressure, so that a perovskite absorption layer is formed.
While the reaction is proceeding, a carrier gas is continuously introduced into the reaction chamber 30 through the gas inlet line 34. If the pressure in the reaction chamber 30 exceeds the preset reaction pressure, the pressure release valve 33 is opened, so that the gas in the reaction chamber 30 enters the tail gas treatment device 50 through the exhaust pipeline 32.
5. After the reaction is completed, the temperature in the reaction chamber 30 is adjusted to perform an annealing treatment, wherein the annealing temperature is 50-300 ℃ (step 5 can be omitted according to actual conditions).
6. After the annealing treatment is completed, the exhaust gas in the reaction chamber 30 is pumped out and enters the exhaust gas treatment device 50 through the exhaust pipeline 32. In the tail gas treatment device 60, the temperature can be reduced to change the unreacted gaseous organic source into liquid or solid, and the carrier gas can be discharged into the atmosphere or treated and discharged into the atmosphere.
The substrate on which the perovskite absorption layer is formed enters the unload chamber 62 and is taken out.
EXAMPLE III
This embodiment provides a method for preparing a perovskite absorption layer, which is a reaction performed under vacuum condition, and for convenience of understanding, the following description is made in conjunction with the system in the first embodiment, and specifically includes the following steps:
1. placing a conductive substrate which is prepared in advance and is loaded with a hole transport layer (or an electron transport layer) and an inorganic thin film in a pre-loading cavity 61; a liquid or solid organic source is placed in the gas generation chamber 20 or a gaseous organic source is connected into the gas generation chamber 20.
2. The vacuum apparatus 10 (e.g., vacuum pump) is turned on to evacuate the entire system, the vacuum apparatus 10 is turned off, and the carrier gas source 40 is turned on to charge the system with the carrier gas. And repeatedly vacuumizing and filling carrier gas for 1-10 times, and fully discharging gas which possibly influences the reaction process, such as oxygen, water vapor and the like in the system.
The carrier gas source 30 is turned off, and the vacuum pump is turned on, so that the pressure of the whole system is less than a standard atmospheric pressure, for example, greater than or equal to 0.1Pa and less than a standard atmospheric pressure.
3. The valve 23 on the gas inlet pipeline 21 and the valve 23 on the gas conveying pipeline 26 are closed to ensure that the gas generation cavity 20 is in a vacuum state and prevent the process gas in the subsequent gas generation cavity 20 from entering the reaction cavity 30 under the action of the vacuum device 10. The gas generation cavity 20 is heated to rapidly change the liquid or solid organic source in the gas generation cavity 20 into a gas state, the temperature in the gas generation cavity 20 reaches a preset process temperature, for example, 50 to 300 ℃, and the partial pressure of the process gas reaches the saturated vapor pressure of the organic source.
4. The reaction chamber 30 is heated, the valve 23 and the heating coil 24 on the air inlet pipeline 21 and the valve 23 and the heating coil 24 on the air conveying pipeline 26 are opened, so that the carrier gas in the carrier gas source 40 enters the gas generation chamber 20 through the air inlet pipeline 21, and carries the gaseous organic source to enter the reaction chamber 30 through the air conveying pipeline 26, and then the gaseous organic source is uniformly distributed in the reaction chamber 31 through the flow dividing device 31, so that the reaction chamber 30 reaches a preset reaction temperature (for example, 50-300 ℃) and a preset reaction pressure, for example, greater than or equal to 0.1Pa and less than one standard atmospheric pressure.
And after stabilizing for about 0.1-60 min, feeding the substrate in the preloading cavity 61 into the reaction cavity 30, and reacting the inorganic thin film on the substrate with a gaseous organic source for 1-120 min to form the perovskite absorption layer.
While the reaction is proceeding, the vacuum apparatus 10 is continuously operated to maintain the pressure in the system, particularly, the pressure in the reaction chamber 30 is 0.1Pa or more and less than a standard atmospheric pressure.
5. After the reaction is completed, the temperature in the reaction chamber 30 is adjusted to perform an annealing treatment, wherein the annealing temperature is 50-300 ℃ (step 5 can be omitted according to actual conditions).
6. After the annealing process is completed, the exhaust gas in the reaction chamber 30 is pumped out and enters the exhaust gas treatment device 50 through the exhaust line 32, for example, by lowering the temperature below the freezing point of the gaseous organic source, the unreacted gaseous organic source therein is changed into a liquid or solid state, and the carrier gas can be discharged into the atmosphere.
The substrate on which the perovskite absorption layer is formed enters the unload chamber 62 and is taken out.
Example four
The embodiment provides a processing method of a perovskite solar cell, which comprises the following steps:
forming an electron transport layer (or a hole transport layer) and an inorganic thin film on a substrate in this order;
forming a perovskite absorption layer according to the preparation method provided by the second embodiment or the third embodiment;
a hole transport layer (or an electron transport layer) is formed on the perovskite absorption layer, and then a metal electrode is formed.
The following method for processing a perovskite solar cell is described in detail by specific examples:
Using transparent ITO glass as a substrate, preparing an electron transmission layer on the ITO glass, and then preparing PbI2Film (i.e. BX)2A film).
With CH3NH3I is an organic source (i.e., AX), and a perovskite absorption layer CH is formed on the electron transport layer according to the steps 1to 6 provided in the foregoing example II3NH3PbI3。
In CH3NH3PbI3And sequentially preparing a hole transport layer and an electrode on the film to obtain the perovskite solar cell.
Using transparent ITO glass as substrate, on the ITO glassPreparing electron transmission layer on glass, and preparing PbI2Film (i.e. BX)2A film).
According to the preparation method provided in example two, a perovskite absorption layer is formed on the electron transport layer, wherein CH is used3NH3I and CH (NH)2)2I two solid organic matters are used as organic sources (namely AX), and the perovskite absorption layer (CH) is prepared3NH3)x CH(NH2)1-xPbI3Film, wherein 0 < x < 1.
And forming a hole transport layer and a metal electrode on the perovskite absorption layer to obtain the perovskite solar cell.
Case 3:
using transparent ITO glass as a substrate, preparing an electron transmission layer on the ITO glass, and then preparing PbI2And CsBr composite films.
With CH3NH3I and CH (NH)2)2I is an organic source, and a perovskite absorption layer Cs is formed on the electron transport layer according to the steps 1to 6 provided in the second embodimentx(CH3NH3)y(CH(NH2)2)1-x-yPb(IzBr1-z)3Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x + y is less than 1.
And forming a hole transport layer and a metal electrode on the perovskite absorption layer to obtain the perovskite solar cell.
Case 4:
using transparent ITO glass as substrate, forming electron transmission layer and PbI on ITO glass in sequence2Film (i.e. BX)2A film).
With CH3NH3I is an organic source (i.e., AX), and a perovskite absorption layer CH is formed on the electron transport layer according to steps 1to 6 in the third embodiment3NH3PbI3。
And sequentially forming a hole transport layer and an electrode on the perovskite absorption layer to obtain the perovskite solar cell.
Case 5:
lining with transparent ITO glassBottom, sequentially forming a hole transport layer and PbI on ITO glass2Film (i.e. BX)2A film).
With CH3NH3I and CH (NH)2)2I two substances as organic source (i.e. AX), and following steps 1to 6 of example III, perovskite absorption layer (CH) was prepared3NH3)x(CH(NH2)2)1-xPbI3Wherein x is more than 0 and less than 1.
And forming an electron transport layer and a metal electrode on the perovskite absorption layer in sequence to obtain the perovskite solar cell.
Case 6:
using transparent ITO glass as substrate, forming electron transmission layer and PbI on the ITO glass in sequence2And CsBr.
According to step 1to step 6 of example III, CH is used3NH3I and CH (NH)2)2The two substances are used as organic sources to prepare a perovskite absorption layer Csx(CH3NH3)y(CH(NH2)2)1-x-yPb(IzBr1-z)3Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x + y is less than 1.
And sequentially forming a hole transport layer and a conductive electrode on the perovskite absorption layer to obtain the perovskite solar cell.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a perovskite absorption layer is characterized by comprising the following steps:
forming process gas containing a gaseous organic source or process gas containing an inorganic source in a gas generation cavity, and controlling the temperature of the process gas to reach a preset process temperature;
introducing the process gas reaching a preset process temperature into a reaction cavity from a gas generation cavity, so that the pressure in the reaction cavity reaches a preset reaction pressure and the temperature reaches a preset reaction temperature;
placing the substrate loaded with the inorganic thin film into the reaction cavity, and enabling the inorganic thin film to react with the gaseous organic source or the inorganic source at the preset reaction temperature and the preset reaction pressure so as to form a perovskite absorption layer on the substrate;
the organic source is an amine compound and/or an amidine compound, and the inorganic thin film has the composition of CBX 3, wherein B represents one or more divalent metals, C represents one or more monovalent cations containing hydrogen atoms, and X represents one or more of halide ions, thiocyanato, cyanide and oxygen cyanide;
alternatively, the organic source has a composition of AX, wherein a represents an amino group or an amidino group, and the inorganic thin film has a composition of BX 2;
the inorganic source is of a composition of DX wherein D represents one or more alkali metals, and the inorganic film has a composition of BX 2;
the preset reaction temperature is 50-300 ℃, the reaction time is 1-120 min, the preset reaction pressure is high pressure or low pressure, the high pressure is 0.1013-1 MPa, and the low pressure is not lower than 0.1Pa and less than 1 standard atmospheric pressure;
after the pressure in the reaction chamber reaches the preset reaction pressure and the temperature reaches the preset reaction temperature, the method further comprises the following steps: and stabilizing the process gas in a reaction chamber for 0.1-60 min, and then placing the substrate loaded with the inorganic film into the reaction chamber.
2. The method of claim 1, wherein forming a process gas containing a gaseous organic source or a process gas containing an inorganic source in a gas generation chamber comprises:
injecting the organic source in a gaseous state into the gas generation chamber; alternatively, the first and second electrodes may be,
placing the organic source in a solid or liquid state in the gas generation cavity, and heating to form a gaseous organic source; alternatively, the first and second electrodes may be,
placing the solution dissolved with the organic source in the gas generation cavity, and heating to separate out the organic source to form a gaseous organic source; alternatively, the first and second electrodes may be,
and placing the solution dissolved with the inorganic source in the gas generation cavity, and enabling a carrier gas to pass through the solution dissolved with the inorganic source to form a gas flow with the inorganic source.
3. The method of claim 1 or 2, wherein forming a process gas containing a gaseous organic source or a process gas containing an inorganic source in the gas generation chamber further comprises: introducing carrier gas into the gas generation cavity at the flow rate of 0-10000 sccm;
the carrier gas and the gaseous organic source together constitute the process gas, or the process gas comprises the carrier gas and the inorganic source.
4. The method according to claim 1 or 2, wherein the predetermined process temperature is 50 to 300 ℃.
5. The preparation method according to claim 1 or 2, further comprising a step of annealing after the reaction is completed, wherein the annealing temperature is 50-300 ℃, and the annealing temperature is lower than the preset reaction temperature.
6. A system for realizing the preparation method of any one of claims 1to 4, which comprises a vacuum device, a first closed cavity and a second closed cavity which are connected in series and are communicated, wherein along the trend of the process gas, the first closed cavity is the gas generation cavity, the second closed cavity is the reaction cavity, the gas generation cavity is provided with a temperature control device, the reaction cavity is provided with a temperature control device, a pressure control device and a gas shunting device, and the vacuum device is communicated with the first closed cavity or the second closed cavity.
7. A processing method of a perovskite solar cell is characterized by comprising the following steps:
sequentially forming one of an electron transport layer and a hole transport layer and an inorganic thin film on a substrate;
the production method according to any one of claims 1to 5, forming a perovskite absorption layer on the substrate;
and finally, sequentially forming the other of the electron transport layer and the hole transport layer and an electrode on the perovskite absorption layer.
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