CN113451516A - Device and method for producing perovskite absorption layers and use thereof - Google Patents
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Abstract
The invention discloses a device and a method for preparing a perovskite absorption layer and application thereof, wherein the device for preparing the perovskite absorption layer comprises the following steps: the inorganic deposition chamber comprises an inorganic chamber, a deposition chamber and an organic chamber, wherein a first air inlet and a first pressure regulating port are formed in the inorganic chamber, a first evaporation boat is arranged in the inorganic chamber, and an inorganic precursor is contained on the first evaporation boat; the deposition chamber is communicated with the inorganic chamber, a first valve is arranged at the joint of the deposition chamber and the inorganic chamber, a substrate carrying table is arranged in the deposition chamber, a rotatable baffle plate is arranged above the substrate carrying table, the inclination angle of the substrate carrying table is adjustable, and an exhaust port is arranged on the deposition chamber; the organic chamber is communicated with the deposition chamber, a second valve is arranged at the joint of the organic chamber and the deposition chamber, a second air inlet and a second pressure regulating port are formed in the organic chamber, a second evaporation boat is arranged in the organic chamber, and the second evaporation boat is used for containing organic precursors.
Description
Technical Field
The invention belongs to the field of perovskite solar cells, and particularly relates to equipment and a method for preparing a perovskite absorption layer and application of the perovskite absorption layer.
Background
Solar energy is an inexhaustible clean energy, and a perovskite solar cell is a novel solar cell developed in recent years. The perovskite novel solar cell has high visible light absorption, simple film forming process and fast improvement of photoelectric conversion efficiency, so the perovskite novel solar cell is concerned all over the world.
At present, a plurality of methods for preparing the perovskite solar cell are available, such as a spin coating method, a vacuum method, a blade coating method, a spraying method and the like. These methods can be roughly classified into a solution method in which a perovskite precursor material is completely dissolved in an organic solvent such as N, N-Dimethylformamide (DMF) or Dimethylsulfoxide (DMSO), and a perovskite film layer is prepared by spin coating, blade coating, spray coating, slit-die coating, or the like; the vacuum method is to directly prepare the precursor material of the perovskite on a substrate in a vacuum state by a thermal evaporation method, a sputtering method or a near space sublimation method, and the like, and no solvent is involved in the whole process. Solution processes are difficult to achieve complete coverage on rough or defective substrates and are therefore not suitable for producing uniform film layers on textured and non-planar substrates. The vacuum method can deposit the perovskite film layer on the substrate with different roughness or appearance in a shape-preserving way, but the traditional vacuum evaporation method is not easy to accurately control the proportion of each component.
In the case of a perovskite solar cell, the structure of which corresponds to a thin film cell, each layer is a thin film, it is difficult to achieve very good quality uniformity of the entire thin film as the cell area increases, and in the case of a perovskite material itself, which is a polycrystalline material, defects are easily introduced, causing severe recombination in the thin film. How to prepare a large-area uniform and compact film is a key problem to be solved.
The prior art for preparing perovskite film layers has mainly focused on solution processes and vacuum evaporation processes. Because the solution has fluidity, if the perovskite film layer is prepared on the textured substrate or the uneven substrate with larger roughness by adopting a solution method, a thin film layer or even a film layer with holes is formed on the top of the textured surface or the particle bulges, and further the prepared perovskite film layer has a large number of pinholes or holes. Therefore, the solution method is only suitable for preparing a small-area perovskite battery by a spin coating method or preparing a small perovskite component on a substrate with a small area by blade coating or slit-die coating (Slot-die), but is not suitable for preparing uniform perovskite thin films on textured substrates and uneven substrates. In addition, in the process of preparing the perovskite film layer by the solution method, a solvent is introduced, so that the processes of adding the solvent and removing the solvent are added in the production, and the volatilization of a large amount of the solvent causes environmental pollution, so that the green production is not easy to realize. The vacuum evaporation method is not easy to accurately control the proportion of each component and is not easy to continuously feed.
Therefore, the existing technology for preparing perovskite film layer needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide an apparatus and a method for preparing a perovskite absorption layer, and an application thereof, wherein the apparatus is used for preparing the perovskite absorption layer, which is independent of the flatness of a substrate, can be used for preparing a large-area uniform perovskite film layer on a textured substrate or a substrate with a large roughness, and can be used for obtaining a perovskite solar cell doped with both organic components and inorganic components, thereby greatly improving the stability of the perovskite solar cell.
In one aspect of the invention, an apparatus for producing a perovskite absorber layer is provided. According to an embodiment of the invention, the apparatus comprises:
the device comprises an inorganic chamber, a first pressure regulating port, a first pressure regulating valve, a second pressure regulating valve and a third pressure regulating valve, wherein a first air inlet and a first pressure regulating port are formed in the inorganic chamber, a first evaporation boat is arranged in the inorganic chamber, and an inorganic precursor is placed on the first evaporation boat;
the deposition chamber is communicated with the inorganic chamber, a first valve is arranged at the joint of the deposition chamber and the inorganic chamber, a substrate carrying table is arranged in the deposition chamber, a rotatable baffle plate is arranged above the substrate carrying table, the inclination angle of the substrate carrying table is adjustable, and an exhaust port is arranged on the deposition chamber;
the organic chamber is communicated with the deposition chamber, a second valve is arranged at the joint of the organic chamber and the deposition chamber, a second air inlet and a second pressure regulating port are formed in the organic chamber, a second evaporation boat is arranged in the organic chamber, and an organic precursor is placed on the second evaporation boat.
According to the equipment for preparing the perovskite absorption layer, the inorganic chamber, the deposition chamber and the organic chamber are sequentially communicated, the inorganic chamber is internally provided with the first evaporation boat, and the first evaporation boat is used for containing an inorganic precursor; meanwhile, a second evaporation boat is arranged in the organic chamber, the second evaporation boat is used for containing an organic precursor, a substrate carrying table is arranged in the deposition chamber, the inclination angle of the substrate carrying table is adjustable, for example, when an inorganic layer is required to be deposited, a second valve at the joint of the organic chamber and the deposition chamber is closed, a first valve at the joint of the deposition chamber and the inorganic chamber is opened, the inorganic precursor on the first evaporation boat in the inorganic chamber is evaporated to enter the deposition chamber, the inorganic layer is deposited on the substrate carrying table, after the deposition of the inorganic layer is finished, the first valve at the joint of the deposition chamber and the inorganic chamber is closed, the second valve at the joint of the organic chamber and the deposition chamber is opened, the organic precursor on the second evaporation boat in the organic chamber is evaporated to enter the deposition chamber, the organic layer is deposited on the inorganic layer, or the organic chamber is opened to deposit the organic layer on the substrate first, and finally, starting a temperature control assembly on a bearing platform of the substrate to ensure that the inorganic layer and the organic layer react and simultaneously dope organic components and inorganic components, thereby greatly improving the stability of the perovskite solar cell. Meanwhile, the organic layer and/or the inorganic layer formed on the substrate by the equipment of the application are deposited, so that the perovskite absorption layer is prepared independently of the flatness of the substrate, and a large-area uniform perovskite film layer can be prepared on the textured substrate or the substrate with larger roughness. In addition, pressure adjusting ports are formed in the inorganic chamber and the organic chamber, and the inclination angle of the substrate carrying platform is adjustable, so that the doping content of the inorganic precursor and the doping content of the organic precursor can be accurately controlled, the inorganic layer and the organic layer can be fully reacted, and the high-quality perovskite crystal film can be obtained.
In addition, the apparatus for manufacturing a perovskite absorption layer according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, pressure detectors are independently disposed in the inorganic chamber, the deposition chamber, and the organic chamber, respectively. Therefore, the precise doping of the content of the inorganic precursor and/or the organic precursor can be realized, so that the inorganic layer and the organic layer can be fully reacted, and the high-quality perovskite crystal film is obtained.
In some embodiments of the present invention, the substrate stage is adjustable between a tilt angle of-45 degrees and 45 degrees. Thereby, a uniformly distributed thin film can be formed on the substrate.
In some embodiments of the invention, the substrate stage is rotatably arranged and the substrate stage is provided with a deposition rate and film thickness monitor. Thereby, a uniformly distributed thin film can be formed on the substrate.
In some embodiments of the present invention, a plurality of the first evaporation boats are disposed in the inorganic chamber, and a plurality of the second evaporation boats are disposed in the organic chamber. Therefore, doping of various inorganic components and various organic components can be realized, and the stability of the perovskite solar cell is greatly improved.
In some embodiments of the present invention, the first evaporation boat, the second evaporation boat and the substrate stage are each independently provided with a temperature control component thereon. Thereby, precise doping of the inorganic component and the organic component can be achieved.
In some embodiments of the present invention, the above apparatus for preparing a perovskite absorption layer further comprises: the preparation chamber is arranged at the upstream of the deposition chamber and is communicated with the deposition chamber, and a third valve is arranged at the joint of the preparation chamber and the deposition chamber; and the sheet outlet chamber is arranged at the downstream of the deposition chamber and communicated with the deposition chamber, and a fourth valve is arranged at the joint of the sheet outlet chamber and the deposition chamber. Therefore, the continuous production of the equipment can be realized.
In a second aspect of the invention, the invention provides a method of producing a perovskite absorber layer using the apparatus described above. According to an embodiment of the invention, the method comprises:
(1) placing a substrate on the substrate stage;
(2) forming an organic layer and an inorganic layer on the substrate;
(3) and starting the temperature control assembly on the substrate carrying platform to enable the inorganic layer and the organic layer to react so as to obtain the perovskite absorption layer.
According to the method for preparing the perovskite absorption layer, the perovskite absorption layer is prepared independently of the flatness of the substrate, a large-area uniform perovskite film layer can be prepared on a textured substrate or a substrate with larger roughness, and by adopting the method, organic components and inorganic components can be doped simultaneously, so that the stability of the perovskite solar cell is greatly improved. In addition, the doping content of the inorganic precursor and the organic precursor can be accurately controlled, so that the inorganic layer and the organic layer can be fully reacted, and the high-quality perovskite crystal film can be obtained.
In addition, the method for preparing the perovskite absorption layer according to the above embodiment of the invention may further have the following additional technical features:
in some embodiments of the invention, step (2) is performed according to the following steps: closing the second valve, opening the first valve, supplying a first working gas through the first gas inlet so that the inorganic precursor on the first evaporation boat in the inorganic chamber is evaporated into the deposition chamber to deposit and form an inorganic layer on the substrate, then closing the first valve, opening the second valve, and supplying a second working gas through the second gas inlet so that the organic precursor on the second evaporation boat in the organic chamber is evaporated into the deposition chamber to form an organic layer on the inorganic layer; or closing the first valve, opening the second valve, supplying a second working gas through the second gas inlet, so that the organic precursor on the second evaporation boat in the organic chamber is evaporated and enters the deposition chamber to form an organic layer on the substrate, then closing the second valve, opening the first valve, supplying a first working gas through the first gas inlet, so that the inorganic precursor on the first evaporation boat in the inorganic chamber is evaporated and enters the deposition chamber to deposit and form an inorganic layer on the organic layer.
In some embodiments of the present invention, in the step (2), the flow rate of the first working gas and the second working gas ranges from 10 to 5000 sccm. Thereby, a uniformly distributed thin film can be formed on the substrate.
In some embodiments of the invention, in step (2), the organic precursor comprises at least one of a halomethyl ether and a halomethylamine.
In some embodiments of the present invention, in the step (2), the thickness of the organic layer is 1 to 100 nm.
In some embodiments of the invention, in step (2), the inorganic precursor comprises at least one of a lead halide and a cesium halide.
In some embodiments of the present invention, in the step (2), the inorganic layer has a thickness of 1 to 600 nm.
In a third aspect of the invention, a perovskite absorber layer is presented. According to an embodiment of the present invention, the perovskite layer is prepared by the above method. Therefore, the perovskite absorption layer has higher crystal quality and purity, so that the electrical property of the perovskite solar cell can be improved.
In a fourth aspect of the invention, a perovskite solar cell is presented. According to an embodiment of the invention, the perovskite solar cell comprises:
a substrate;
a first charge transport layer disposed on the substrate;
a perovskite absorption layer disposed on the first charge transport layer;
a second charge transport layer disposed on the perovskite absorption layer;
a back electrode disposed on the second charge transport layer,
wherein the perovskite absorption layer is the perovskite absorption layer.
Therefore, the perovskite solar cell has high electrical performance by adopting the perovskite absorption layer with high purity and crystal quality.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural view of an apparatus for producing a perovskite absorption layer according to one embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating the inclination of a substrate stage in an apparatus for producing a perovskite absorption layer according to an embodiment of the present invention;
FIG. 3 is a top view of an apparatus for producing a perovskite absorption layer according to still another embodiment of the invention;
fig. 4 is a schematic structural diagram of a perovskite solar cell according to one embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, an apparatus for producing a perovskite absorber layer is provided. According to an embodiment of the invention, with reference to fig. 1, the apparatus comprises: an inorganic chamber 100, a deposition chamber 200, and an organic chamber 300.
According to an embodiment of the present invention, referring to fig. 1, a first gas inlet 101 and a first pressure regulating port 102 are disposed on an inorganic chamber 100, a first evaporation boat 11 is disposed in the inorganic chamber 100, the first evaporation boat 11 holds an inorganic precursor, i.e., a working gas, such as nitrogen or an inert gas such as argon, is supplied into the inorganic chamber 100 through the first gas inlet 101, and a flow rate of the working gas is 10 to 5000sccm, a pressure detector 12 is disposed in the inorganic chamber 100 to monitor a pressure in the inorganic chamber 100 in real time, and the working gas is filled into the first pressure regulating port 102 at a certain flow rate to regulate and control a pressure in the inorganic chamber 100, preferably, the pressure is regulated through the first pressure regulating port 102 at a pressure range of 0.1 to 1000pa, the inorganic precursor on the first evaporation boat 11 is evaporated into a gaseous state, wherein the inorganic precursor includes at least one of lead halide and cesium halide, such as lead chloride, lead bromide, lead iodide, cesium chloride, cesium bromide, cesium iodide.
Further, referring to fig. 1, a plurality of first evaporation boats 11 may be disposed in the inorganic chamber 100, and each first evaporation boat 11 may contain a different inorganic precursor or the same inorganic precursor or a mixture of several inorganic precursors, and each first evaporation boat 11 is independently provided with a temperature control component (not shown), that is, the temperature control component controls the evaporation temperature of each first evaporation boat 11, and the evaporation amount of the inorganic precursor of each first evaporation boat 11 is controlled, so as to precisely control the doping amount of the inorganic precursor. Preferably, the temperature control range of the first evaporation boat 11 is 100 to 1000 ℃.
According to an embodiment of the present invention, referring to fig. 1, a deposition chamber 200 is communicated with an inorganic chamber 100, a first valve 21 is disposed at a connection position between the deposition chamber 200 and the inorganic chamber 100, a substrate stage 20 is disposed in the deposition chamber 200, a rotatable baffle plate 22 is disposed above the substrate stage 20, and referring to fig. 2, an inclination angle of the substrate stage 20 is adjustable between-45 degrees and 45 degrees, and an exhaust port 201 is disposed on the deposition chamber 200, that is, when inorganic precursor deposition is performed, the first valve 21 is disposed at a connection position between the deposition chamber 200 and the inorganic chamber 100, the inclination angle of the substrate stage 20 is adjusted to incline toward the inorganic chamber 100 (refer to a diagram in fig. 2, the inclination angle is 0 degree to 45 degrees), and then the exhaust port 201 of the deposition chamber 200 is opened, such that inorganic precursor evaporants evaporated by a first evaporation boat 11 of the inorganic chamber 100 enter the deposition chamber 200 and are deposited on a substrate on the substrate stage 20, an inorganic layer (10-600 nm) is formed on the substrate. Specifically, the exhaust port 201 is connected to a mechanical vacuum pump, and the pumping speed of the mechanical vacuum pump is adjustable.
Further, the substrate carrier 20 can be rotatably disposed, so that the film layer is more uniform, and the rotation speed of the substrate carrier 20 can be adjusted. Meanwhile, a baffle plate 22 is arranged in a range of 1 cm-5 cm above the substrate carrying table 20, the baffle plate 22 can be used for controlling the whole shielding and the whole exposure of the substrate carrying table 20, the thickness of a sediment layer on the substrate is controlled by rotating the baffle plate 22, and preferably, a deposition rate and film thickness monitor 23 is arranged on the substrate carrying table to monitor the real-time rate and the film thickness of a deposition material on the substrate carrying table 20 and feed monitoring information back to the first evaporation boat 11 in the inorganic chamber, so that the evaporation capacity of the inorganic precursor is adjusted by controlling the temperature of the first evaporation boat 11. Meanwhile, a pressure detector 24 is provided in the deposition chamber 200 to monitor the pressure in the deposition chamber 200 in real time. In addition, a temperature control component (not shown) is disposed on the substrate stage 20, and the temperature control range of the substrate stage 20 is preferably 20-300 ℃.
According to an embodiment of the present invention, referring to fig. 1, an organic chamber 300 is communicated with a deposition chamber 200, a second valve 31 is disposed at a connection position of the organic chamber 300 and the deposition chamber 200, a second gas inlet 301 and a second pressure adjusting port 302 are disposed on the organic chamber 300, a second evaporation boat 32 is disposed in the organic chamber 300, the second evaporation boat 32 contains an organic precursor, i.e., a working gas, such as an inert gas like nitrogen or argon, is supplied into the organic chamber 300 through the second gas inlet 301, a flow rate of the working gas ranges from 10 sccm to 5000sccm, a pressure detector 33 is disposed in the organic chamber 300 to monitor the pressure in the organic chamber 300 in real time, and the working gas with a certain flow rate is filled into the second pressure adjusting port 302 to adjust the pressure in the organic chamber 300, preferably, the pressure adjusting range is 0.1 pa to 1000pa through the second pressure adjusting port 302, the organic precursor on the second evaporation boat 32 is evaporated to be in a gaseous state, wherein the organic precursor includes at least one of methyl halide and methyl halide, such as methyl chloride, methyl bromide, methyl iodide, methyl chloride, methyl bromide, and methyl iodide. Specifically, when depositing the organic precursor, a first valve 21 is disposed at a joint between the deposition chamber 200 and the inorganic chamber 100, a second valve 31 at a joint between the organic chamber 300 and the deposition chamber 200 is adjusted, an inclination angle of the substrate stage 20 is adjusted to incline toward the organic chamber 300 (referring to fig. 2 b, the inclination angle is-45 to 0 degrees), and then an exhaust port 201 of the deposition chamber 200 is opened, so that the organic precursor evaporant evaporated by the second evaporation boat 32 of the organic chamber 300 enters the deposition chamber 200 and is deposited on the substrate or the inorganic layer on the substrate stage 20, that is, an organic layer (10 to 100nm) is formed on the substrate or the inorganic layer. Meanwhile, the deposition rate and film thickness monitor 23 on the substrate stage 20 monitors the deposition rate and film thickness of the organic deposition material on the substrate stage 20 in real time, and feeds back the monitoring information to the second evaporation boat 32 in the organic chamber 300, so as to adjust the evaporation amount of the organic precursor by controlling the temperature of the second evaporation boat 32.
Further, referring to fig. 1, a plurality of second evaporation boats 32 may be disposed in the organic chamber 300, each second evaporation boat 32 may contain a different organic precursor or the same organic precursor or a mixture of several organic precursors, and each second evaporation boat 32 is independently provided with a temperature control device (not shown), that is, the temperature control device controls the evaporation temperature of each second evaporation boat 32, and controls the evaporation amount of the organic precursor of each second evaporation boat 32, so as to precisely control the doping amount of the organic precursor. Preferably, the temperature control range of the second evaporation boat 32 is 50-300 ℃. And the working gas in the inorganic chamber 100 is the same as the working gas in the first gas inlet 101, the first pressure regulating port 102, the second gas inlet 301 on the organic chamber 300 and the second pressure regulating port 302.
According to the embodiment of the present invention, the shapes of the inorganic chamber 100, the deposition chamber 200, and the organic chamber 300 include, but are not limited to, a cubic shape, and all possible geometric shapes such as a cylindrical shape, a spherical shape, a conical shape, and the like. The first valve 21 and the second valve 31 may be baffle structures with controllable opening angles, or may be arranged in gas paths with controllable flow rate, and the gas paths may be arranged and communicated in a single-path or multi-path array manner.
After the deposition of the organic layer and the inorganic layer on the substrate is completed, the temperature control assembly on the substrate carrier 20 is turned on, so that the organic layer and the inorganic layer react: when the inorganic layer comprises PbI2The organic layer comprises MAI, and the reaction is PbI2+MAI→MAPbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI, and the reaction is PbI2+FAI→FAPbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI and MAI, and the reaction is PbI2+MAI+FAI→MAxFA(1-x)PbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI, MABr and MACl, and reacts to PbI2+FAI+MABr+MACl→MAxFA(1-x)PbIyBrzCl(3-y-zx)(ii) a When the inorganic layer comprises PbI2And CsI, the organic layer comprises FAI, MABr and MACl, the reaction taking place as PbI2+CsI+FAI+MABr+MACl→MAxFAyCs(1-x-y)PbImBrnCl(3-m-n)。
According to the equipment for preparing the perovskite absorption layer, the inorganic chamber 100, the deposition chamber 200 and the organic chamber 300 are sequentially communicated, the first evaporation boat 11 is arranged in the inorganic chamber 100, and the inorganic precursor is placed on the first evaporation boat 11; meanwhile, a second evaporation boat 32 is arranged in the organic chamber 300, the second evaporation boat 32 is used for containing organic precursors, a substrate carrying table 20 is arranged in the deposition chamber 200, and the inclination angle of the substrate carrying table 20 is adjustable, for example, when an inorganic layer needs to be deposited, the second valve 31 at the joint of the organic chamber 300 and the deposition chamber 200 is closed, the first valve 21 at the joint of the deposition chamber 200 and the inorganic chamber 100 is opened, the inorganic precursors on the first evaporation boat 11 in the inorganic chamber 100 are evaporated to enter the deposition chamber 200, the inorganic layer is deposited on the substrate carrying table 20, after the deposition of the inorganic layer is finished, the first valve 21 at the joint of the deposition chamber 200 and the inorganic chamber 100 is closed, the second valve 31 at the joint of the organic chamber 300 and the deposition chamber 200 is opened, the organic precursors on the second evaporation boat 32 in the organic chamber 300 are evaporated to enter the deposition chamber 200, and the organic layer is deposited on the inorganic layer, or the organic chamber 300 is started first to deposit an organic layer on the substrate, the inorganic chamber 100 is started to deposit an inorganic layer on the organic layer, multiple organic layers and multiple inorganic layers can be deposited on the substrate according to requirements, and finally the temperature control assembly on the substrate carrying platform 20 is started to enable the inorganic layer and the organic layer to react and dope organic components and inorganic components, so that the stability of the perovskite solar cell is greatly improved. Meanwhile, the organic layer and/or the inorganic layer formed on the substrate by the equipment of the application are deposited, so that the perovskite absorption layer is prepared independently of the flatness of the substrate, and a large-area uniform perovskite film layer can be prepared on the textured substrate or the substrate with larger roughness. In addition, the inorganic chamber 100 and the organic chamber 200 of the present application are both provided with pressure adjusting ports, and the inclination angle of the substrate carrier 20 is adjustable, so that the doping content of the inorganic precursor and the organic precursor can be accurately controlled, and the inorganic layer and the organic layer can fully react, thereby obtaining a high-quality perovskite crystal thin film.
Further, with reference to fig. 3, in order to achieve continuous production of the perovskite absorption layer, the above apparatus further comprises: a preparation chamber 400 and a sheet exit chamber 500.
According to an embodiment of the present invention, the preparation chamber 400 is provided upstream of the deposition chamber 200, and the preparation chamber 400 communicates with the deposition chamber 200, and the connection of the preparation chamber 400 and the deposition chamber 200 is provided with a third valve 41, and before deposition, the third valve 41 is opened, and the substrate stage 20 is transferred from the preparation chamber 400 to the deposition chamber 200 by a transfer device (not shown).
According to the embodiment of the present invention, the wafer discharging chamber 500 is disposed downstream of the deposition chamber 200, the wafer discharging chamber 500 is communicated with the deposition chamber 200, the fourth valve 51 is disposed at the connection between the wafer discharging chamber 500 and the deposition chamber 200, and after the deposition chamber 200 completes the reaction of the organic layer and the inorganic layer, the fourth valve 51 is opened, and the substrate carrier 20 is driven from the deposition chamber to the wafer discharging chamber 500 through the driving device.
In a second aspect of the invention, the invention provides a method of producing a perovskite absorber layer using the above apparatus. According to an embodiment of the invention, the method comprises:
s100: placing a substrate on a substrate stage
In this step, a substrate is placed on the substrate stage 20 by the rotating means, and then the substrate stage 20 is transferred to the deposition chamber 200.
S200: forming an organic layer and an inorganic layer on a substrate
Specifically, the second valve 31 is closed, the first valve 21 is opened, the first working gas is supplied through the first gas inlet 101, so that the inorganic precursors on the first evaporation boat 11 in the inorganic chamber 100 are evaporated into the deposition chamber 200 to deposit and form an inorganic layer on the substrate, then the first valve 21 is closed, the second valve 31 is opened, and the second working gas is supplied through the second gas inlet 301, so that the organic precursors on the second evaporation boat in the organic chamber 300 are evaporated into the deposition chamber 200 to form an organic layer on the inorganic layer; or closing the first valve 21, opening the second valve 31, supplying the second working gas through the second gas inlet 301, so that the organic precursor on the second evaporation boat 32 in the organic chamber 300 is evaporated into the deposition chamber 200, and forming an organic layer on the substrate, then closing the second valve 31, opening the first valve 21, supplying the first working gas through the first gas inlet 101, so that the inorganic precursor on the first evaporation boat 11 in the inorganic chamber 100 is evaporated into the deposition chamber 200, and depositing an inorganic layer on the organic layer.
Furthermore, the flow ranges of the first working gas and the second working gas are 10-5000 sccm, the pressure in the inorganic chamber 100 is adjusted to 0.1-1000 pa through the first pressure adjusting port 102, and the pressure in the organic chamber 100 is adjusted to 0.1-1000 pa through the second pressure adjusting port 302. And the thickness of the organic matter layer on the substrate is controlled to be 1-100 nm and the thickness of the inorganic matter layer is controlled to be 1-600 nm by controlling the temperature of the first evaporation boat 11 and the second evaporation boat 32.
S300: opening the temperature control assembly on the substrate carrier to allow the inorganic layer and the organic layer to react
In this step, after the deposition of the organic layer and the inorganic layer on the substrate is completed, the temperature control assembly on the substrate stage 20 is turned on, so that the organic layer and the inorganic layer react to obtain the perovskite absorption layer. In particular, when the inorganic layer comprises PbI2The organic layer comprises MAI, and the reaction is PbI2+MAI→MAPbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI, and the reaction is PbI2+FAI→FAPbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI and MAI, and the reaction is PbI2+MAI+FAI→MAxFA(1-x)PbI3(ii) a When the inorganic layer comprises PbI2The organic layer comprises FAI, MABr and MACl, and reacts to PbI2+FAI+MABr+MACl→MAxFA(1-x)PbIyBrzCl(3-y-zx)(ii) a When the inorganic layer comprises PbI2And CsI, the organic layer comprises FAI, MABr and MACl, the reaction taking place as PbI2+CsI+FAI+MABr+MACl→MAxFAyCs(1-x-y)PbImBrnCl(3-m-n)。
According to the method for preparing the perovskite absorption layer, the perovskite absorption layer is prepared independently of the flatness of the substrate, a large-area uniform perovskite film layer can be prepared on a textured substrate or a substrate with larger roughness, and by adopting the method, organic components and inorganic components can be doped simultaneously, so that the stability of the perovskite solar cell is greatly improved. In addition, the doping content of the inorganic precursor and the organic precursor can be accurately controlled, so that the inorganic layer and the organic layer can be fully reacted, and the high-quality perovskite crystal film can be obtained. It should be noted that the features and advantages described above with respect to the apparatus for producing a perovskite absorption layer are also applicable to the method for producing a perovskite absorption layer and will not be described in detail here.
In a third aspect of the invention, a perovskite absorber layer is presented. According to an embodiment of the present invention, the perovskite layer is prepared by the above method. Therefore, the perovskite absorption layer has higher crystal quality and purity, so that the electrical property of the perovskite solar cell can be improved. It should be noted that the features and advantages described above with respect to the apparatus and method for producing a perovskite absorption layer are equally applicable to the perovskite absorption layer and will not be described in further detail herein.
In a fourth aspect of the invention, a perovskite solar cell is presented. According to an embodiment of the present invention, referring to fig. 4, a perovskite solar cell includes: a substrate 100A, a first charge transport layer 200A, a perovskite absorption layer 300A, a second charge transport layer 400A, and a back electrode 500A.
According to an embodiment of the present invention, the substrate 100A comprises a conductive glass including, but not limited to, a tin-doped indium oxide (ITO) conductive glass or a fluorine-doped tin oxide (FTO) conductive glass, or a textured substrate including, but not limited to, a crystalline silicon textured substrate of a perovskite-silicon tandem solar cell.
According to an embodiment of the present invention, a first charge transport layer 200A is disposed on the substrate 100A, wherein the first charge transport layer 200A includes, but is not limited to, cuprous thiocyanate (CuSCN), cuprous iodide (CuI), cuprous oxide (CuO),Nickel oxide (NiO) and vanadium pentoxide (V)2O5) Molybdenum trioxide (MoO)3) Spiro-OMeTAD (22'77' -tetrakis [ NN-bis (4-methoxyphenyl) amino)]-99' -spirobifluorene), P3HT (poly (3-hexylthiophene-2, 5-diyl), PTAA (poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]) PEDOT PSS (poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)), titanium dioxide (TiO)2) Tin dioxide (SnO)2) Fullerene (C)60) Zinc oxide (ZnO), PCBM (fullerene derivative), and the like. The first charge transport layer 200A is prepared by an evaporation method, a sputtering method, a chemical bath deposition method, a precursor solution spin coating method or a precursor solution blade coating method, a Slot-die method, or the like, and the first charge transport layer 200A has a thickness in a range of 0.1nm to 500 nm.
According to an embodiment of the present invention, a perovskite absorption layer 300A is provided on the first charge transport layer 200A, wherein the perovskite absorption layer 300A is the perovskite absorption layer described above.
According to an embodiment of the present invention, a second charge transport layer 400A is disposed on the perovskite absorption layer 300A, wherein the second charge transport layer 400A includes, but is not limited to, cuprous thiocyanate (CuSCN), cuprous iodide (CuI), cuprous oxide (CuO), nickel oxide (NiO), vanadium pentoxide (V)2O5) Molybdenum trioxide (MoO)3) Spiro-OMeTAD (22'77' -tetrakis [ NN-bis (4-methoxyphenyl) amino)]-99' -spirobifluorene), P3HT (poly (3-hexylthiophene-2, 5-diyl), PTAA (poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine]) PEDOT PSS (poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)), titanium dioxide (TiO)2) Tin dioxide (SnO)2) Fullerene (C)60) Zinc oxide (ZnO), PCBM (fullerene derivative), and the like. The first charge transport layer 200A is prepared by an evaporation method, a sputtering method, a chemical bath deposition method, a precursor solution spin coating method or a precursor solution blade coating method, a Slot-die method, or the like, and the first charge transport layer 200A has a thickness in a range of 1nm to 500 nm.
According to an embodiment of the present invention, a back electrode 500A is disposed on the second charge transport layer 400A, wherein the back electrode 500A includes, but is not limited to, at least one of a silver electrode (Ag), a copper electrode (Cu), a gold electrode (Au), an aluminum electrode (Al), a molybdenum electrode (Mo), and a chromium electrode (Cr), and the thickness of the metal back electrode is in a range of 10nm to 500 nm. And the metal back electrode can be prepared by an evaporation method, a sputtering method and the like. Meanwhile, the back electrode 500A includes, but is not limited to, a transparent back electrode such as tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide, etc. The thickness range of the transparent back electrode is 10nm-500 nm. The transparent back electrode is prepared by sputtering method.
Therefore, the perovskite solar cell has high electrical performance by adopting the perovskite absorption layer with high purity and crystal quality. It should be noted that the features and advantages described above for the perovskite absorption layer apply equally to this perovskite solar cell and are not described in further detail here.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
A layer of cuprous thiocyanate film (thickness 20nm) was prepared on ITO conductive glass by spin-coating, and the sample was transferred to the substrate stage 20 of the apparatus of FIG. 1, where the first valve 21 was closed, the second valve 31 was opened, the substrate stage 20 was tilted at-10 °, N2Entering from the second inlet 301, the temperature of the second evaporation boat 32 is 120 ℃ (MAI is held by the second evaporation boat 32), the temperature of the substrate stage 20 is 50 ℃, and N is2The flow rate is 40sccm, the pressure of the organic chamber 300 is stabilized at 100Pa by adjusting the second pressure adjusting port 302, MAI is deposited on the substrate to a thickness of 5nm, then the second valve 31 is closed, the first valve 21 is opened, the tilt angle of the substrate stage 20 is +/-10 DEG, and N is set2Entering from the first inlet 101, the inorganic chamber 100 is provided with two first evaporation boats 11, the temperatures of the two first evaporation boats 11 are 460 ℃ (the first evaporation boat 11 contains PbI)2) And 520 deg.C (the first evaporation boat 11 contains CsBr), the temperature of the substrate stage 20 is 100 deg.C, and N is2The inorganic chamber 100 was stabilized at a pressure of 10Pa through the first pressure regulating port 102 at a flow rate of 100sccm, and simultaneous deposition of PbI was started2And CsBr, deposited to a thickness of 250nm, and finally closing the first valve 21 and opening the second valveValve 22, base stage 20 tilt angle is-10, N2Entering from the second inlet 301, the temperature of the second evaporation boat 32 is 150 ℃ (MAI/FAI contained in the second evaporation boat 32), the temperature of the substrate carrier is 120 ℃, and N is2The flow rate is 50sccm, the pressure of the organic chamber is stabilized at 10Pa by regulating and controlling the second pressure regulating port 302, MAI/FAI deposition is started, the deposition thickness is 250nm, the organic precursor layer and the inorganic precursor layer are subjected to chemical reaction under the heating action of the substrate carrying platform 20 to form a perovskite film layer, and C with the thickness of 20nm is evaporated on the perovskite film layer60Layer of, then C60And evaporating the layer to form a Cu electrode with the thickness of 60nm, and preparing the perovskite solar cell.
Example 2
Preparing a nickel oxide film (with the thickness of 20nm) on FTO conductive glass by a sputtering method, then transferring a sample onto a substrate carrying table 20 of the device shown in the figure 1, wherein the first valve 21 is closed, the second valve 31 is opened, the inclination angle of the substrate carrying table 20 is-15 degrees, Ar enters from a second air inlet 301, the temperature of a second evaporation boat 32 is 100 ℃ (MAI is contained on the second evaporation boat 32), the temperature of the substrate carrying table 20 is 60 ℃, the Ar flow is 40sccm, the pressure of an organic chamber is stabilized at 100Pa by regulating a second pressure regulating port 302, and a thin layer of MAI starts to be deposited, wherein the deposition thickness is 10 nm; then, the second valve 31 is closed, the first valve 21 is opened, the inclination angle of the substrate stage 20 is +/-15 °, Ar enters from the first air inlet 101, the inorganic chamber 100 is provided with three first evaporation boats 11, the temperatures of the three first evaporation boats 11 are 460 ℃ (the first evaporation boat 11 contains PbI)2) 520 ℃ (the first evaporation boat 11 contains CsBr) and 500 ℃ (the first evaporation boat 11 contains CsI), the temperature of the substrate carrier 20 is 100 ℃, the Ar flow is 100sccm, the pressure of the inorganic chamber 100 is stabilized at 10Pa by regulating the first pressure regulating port 102, and PbI starts to be deposited simultaneously2CsBr and CsI, the deposition thickness is 230nm, finally the first valve 21 is closed again, the second valve 22 is opened, the inclination angle of the substrate carrier 20 is-15 degrees, Ar enters from the second air inlet 301, three second evaporation boats 32 are placed in the organic chamber 300, wherein the temperatures of the three second evaporation boats 32 are respectively 140 ℃ (the second evaporation boat 32 holds MAI), 120 ℃ (the second evaporation boat 32 holds FAI) and 110 ℃ (the second evaporation boat 32 holds FAI)The boat 32 holds MACl) and the deposition thickness is 300 nm. Under the heating action of the substrate carrying platform 20, the organic precursor and the inorganic precursor are subjected to chemical reaction to form a perovskite film layer, PCBM with the thickness of 20nm is evaporated on the perovskite film layer, an Ag electrode with the thickness of 50nm is formed by evaporation on the PCBM layer, and finally the perovskite solar cell is prepared.
Example 3
A layer of a PTAA film (15 nm thick) was prepared on ITO conductive glass by evaporation, and the sample was transferred to the substrate stage 20 of the apparatus of FIG. 1, where the first valve 21 was closed and the second valve 31 was opened, and the substrate stage 20 was tilted at-15 °, N2The temperature of the second evaporation boat 32 is 110 ℃ from the second inlet 301 (FAI is held by the second evaporation boat 32), the temperature of the substrate stage 20 is 50 ℃, and N is2The flow rate is 50sccm, and the pressure in the organic chamber 300 is stabilized at 60Pa by adjusting the second pressure adjustment port 302, so as to start to deposit a thin FAI layer with a thickness of 5 nm. Then close second valve 31, open first valve 21, the tilt angle of base stage 20 is + 15 °, N2Entering from the first inlet 101, the inorganic chamber 100 is provided with two first evaporation boats 11, the temperatures of the two first evaporation boats 11 are respectively 450 ℃ (the first evaporation boat 11 contains PbI)2) And 500 deg.C (the first evaporation boat 11 holding CsI), the substrate stage temperature is 100 deg.C, N2The flow rate is 100sccm, and the pressure in the inorganic chamber 100 is stabilized at 15Pa by adjusting the first pressure adjustment port 102. Start of simultaneous deposition of PbI2And CsI with a deposition thickness of 250nm, and finally closing the first valve 21 and opening the second valve 22, the substrate carrier 20 having an inclination of-15 DEG, N2Entering from the second inlet 301, the temperature of the second evaporation boat 32 is 150 deg.C (the second evaporation boat 32 holds MABr/FAI/MACl), the temperature of the substrate stage 20 is 100 deg.C, and N is2The flow rate is 50sccm, the pressure of the organic chamber 302 is stabilized at 10Pa by regulating the second pressure regulating port 302, and MABr/FAI/MACl deposition is started to a thickness of 250 nm. Under the heating action of the substrate carrying platform 20, the organic precursor and the inorganic precursor are subjected to chemical reaction to form a perovskite film layer, and C with the thickness of 20nm is evaporated on the perovskite film layer respectively60Layer of, then C60The layer is evaporated to form 5nm thick BCP, and finally evaporated on the BCP layerAnd forming a Cu electrode with the thickness of 60nm to finally prepare the perovskite solar cell.
Comparative example
Preparing a layer of nickel oxide film (with the thickness of 20nm) on FTO conductive glass by a sputtering method, spin-coating a perovskite precursor solution on a nickel oxide substrate, annealing on a hot plate at 150 ℃ for 15min, and evaporating to form C with the thickness of 20nm on the perovskite film layer60Layer of, then C60And evaporating the layer to form BCP with the thickness of 5nm, and finally evaporating the layer to form a Cu electrode with the thickness of 60nm on the BCP layer to finally prepare the perovskite solar cell.
The perovskite solar cells obtained in examples 1 to 3 and comparative example were evaluated for electrical properties, and each example and comparative example was tested in two groups, and the evaluation data is shown in table 1.
TABLE 1
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. An apparatus for producing a perovskite absorption layer, comprising:
the device comprises an inorganic chamber, a first pressure regulating port, a first pressure regulating valve, a second pressure regulating valve and a third pressure regulating valve, wherein a first air inlet and a first pressure regulating port are formed in the inorganic chamber, a first evaporation boat is arranged in the inorganic chamber, and an inorganic precursor is placed on the first evaporation boat;
the deposition chamber is communicated with the inorganic chamber, a first valve is arranged at the joint of the deposition chamber and the inorganic chamber, a substrate carrying table is arranged in the deposition chamber, a rotatable baffle plate is arranged above the substrate carrying table, the inclination angle of the substrate carrying table is adjustable, and an exhaust port is arranged on the deposition chamber;
the organic chamber is communicated with the deposition chamber, a second valve is arranged at the joint of the organic chamber and the deposition chamber, a second air inlet and a second pressure regulating port are formed in the organic chamber, a second evaporation boat is arranged in the organic chamber, and an organic precursor is placed on the second evaporation boat.
2. The apparatus of claim 1, wherein pressure detectors are independently disposed in the inorganic chamber, the deposition chamber, and the organic chamber, respectively.
3. The apparatus of claim 1, wherein the substrate stage is adjustable between a tilt angle of-45 degrees and 45 degrees.
4. An apparatus according to claim 1 or 3, characterized in that the substrate stage is rotatably arranged and that the substrate stage is provided with a deposition rate and film thickness monitor.
5. The apparatus of claim 1, wherein a plurality of said first evaporation boats are disposed in said inorganic chamber, and a plurality of said second evaporation boats are disposed in said organic chamber;
optionally, the first evaporation boat, the second evaporation boat and the substrate carrying platform are respectively and independently provided with a temperature control assembly.
6. The apparatus of claim 1, further comprising:
the preparation chamber is arranged at the upstream of the deposition chamber and is communicated with the deposition chamber, and a third valve is arranged at the joint of the preparation chamber and the deposition chamber;
and the sheet outlet chamber is arranged at the downstream of the deposition chamber and communicated with the deposition chamber, and a fourth valve is arranged at the joint of the sheet outlet chamber and the deposition chamber.
7. A method of producing a perovskite absorber layer using the apparatus of any one of claims 1 to 6, comprising:
(1) placing a substrate on the substrate stage;
(2) forming an organic layer and an inorganic layer on the substrate;
(3) and starting the temperature control assembly on the substrate carrying platform to enable the inorganic layer and the organic layer to react so as to obtain the perovskite absorption layer.
8. The method of claim 7, wherein step (2) is performed according to the steps of: closing the second valve, opening the first valve, supplying a first working gas through the first gas inlet so that the inorganic precursor on the first evaporation boat in the inorganic chamber is evaporated into the deposition chamber to deposit and form an inorganic layer on the substrate, then closing the first valve, opening the second valve, and supplying a second working gas through the second gas inlet so that the organic precursor on the second evaporation boat in the organic chamber is evaporated into the deposition chamber to form an organic layer on the inorganic layer; or
Closing the first valve, opening the second valve, supplying a second working gas through the second gas inlet, so that the organic precursor on the second evaporation boat in the organic chamber is evaporated and enters the deposition chamber to form an organic layer on the substrate, then closing the second valve, opening the first valve, supplying a first working gas through the first gas inlet, so that the inorganic precursor on the first evaporation boat in the inorganic chamber is evaporated and enters the deposition chamber to deposit and form an inorganic layer on the organic layer;
optionally, in the step (2), the flow rate of the first working gas and the second working gas ranges from 10 sccm to 5000 sccm;
optionally, in step (2), the organic precursor includes at least one of a halomethyl ether and a halomethylamine;
optionally, in the step (2), the thickness of the organic material layer is 1-100 nm;
optionally, in step (2), the inorganic precursor includes at least one of lead halide and cesium halide;
optionally, in the step (2), the thickness of the inorganic layer is 1 to 600 nm.
9. A perovskite absorber layer, wherein the perovskite layer is produced by the method of claim 7 or 8.
10. A perovskite solar cell, comprising:
a substrate;
a first charge transport layer disposed on the substrate;
a perovskite absorption layer disposed on the first charge transport layer;
a second charge transport layer disposed on the perovskite absorption layer;
a back electrode disposed on the second charge transport layer,
wherein the perovskite absorption layer is the perovskite absorption layer as defined in claim 9.
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CN110047998A (en) * | 2018-01-17 | 2019-07-23 | 杭州纤纳光电科技有限公司 | A kind of immersion prepares the equipment and application method of perovskite solar battery |
CN110098333A (en) * | 2019-05-08 | 2019-08-06 | 蜂巢能源科技有限公司 | The processing method of the preparation method and perovskite solar battery of perovskite absorbed layer |
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