CN115811919A - Perovskite thin film, preparation method thereof and perovskite solar cell - Google Patents
Perovskite thin film, preparation method thereof and perovskite solar cell Download PDFInfo
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Abstract
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite thin film, a preparation method of the perovskite thin film and a perovskite solar cell. The preparation method of the perovskite thin film comprises the following steps: (a) Preparing a metal halide film on a substrate by adopting a vacuum method; using a metal mask in the preparation process; the metal mask is positioned between the substrate and the evaporation source; the metal mask comprises a plate body and a plurality of openings arranged on the plate body, wherein the openings are distributed in an array; (b) Preparing an organic halide film on a surface of the metal halide film; and then annealing is carried out. The invention adopts the metal mask plate to ensure that the surface of the metal halide film has different appearances, the surface area is increased, and the crossed film layer formed at the shielding position of the metal mask plate is looser, and the special appearance is beneficial to the infiltration of organic components and the reaction of the metal halide to form high-quality perovskite crystals so as to improve the film forming quality and improve the performance of devices.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite thin film, a preparation method thereof and a perovskite solar cell.
Background
Perovskite is a material having the same crystal structure as the mineral perovskite titanium oxide (the earliest discovered perovskite crystal). Perovskite crystals are now widely used in ultrasonic machines, memory chips and today's solar cells. The perovskite solar cell is a solar cell using a perovskite-type organic metal halide semiconductor as a light absorbing material, and is often used as a solar cell, i.e., a perovskite solar cell. With the development of scientific technology, the energy conversion efficiency of perovskite battery devices is refreshed from time to time with the highest record. From the earliest 3.8% to today's highest 29.8%, the efficiency limits of the currently most efficient heterojunction, TOPCon, etc. silicon technologies have been exceeded for decades.
The current methods for producing perovskite thin films can be broadly classified into solution methods and vacuum methods. The solution method is the most extensive way to prepare light-absorbing layers, and meets the expectation of preparing high-performance devices at low cost. The perovskite precursor material is dissolved in organic solvents such as N, N-Dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) to form a solution, then a wet film is prepared by a spin coating method, a blade coating method, a spray coating method or a slit-die method (slit-die) and the like, and the perovskite thin film is formed by annealing. And the current high performance devices are all realized based on the laboratory-level spin coating method and the anti-solvent assisted method, which is not matched with the large-area production of the industrial level. In the process of preparing a large-area film by the spin-coating method, the performance is greatly lost. The vacuum method is to prepare the precursor material of perovskite on the substrate directly by one-step co-evaporation or sequential evaporation method in a vacuum state through Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD), and then anneal to promote crystallization to form the perovskite thin film. Although the vacuum method is not affected by the substrate, the film can be prepared in a large area, but the proportion of each component is not easy to be accurately controlled, the utilization rate of the precursor material is low, the production beat is slow, and the energy consumption is high. Therefore, the premise of preparing the perovskite is to solve the problem of how to prepare a large-area perovskite light absorption layer.
In the existing vacuum-solution two-step process, the first step is to prepare a metal halide thin film by a vacuum method (mainly in a PVD manner), and the second step is to prepare an organic halide thin film by a solution method. The extent of reaction of the organic solution with the metal halide film during the second film preparation is most critical, which directly determines the quality of the perovskite film formed. In general, the liquid-phase two-step method can adopt additive treatment to convert a compact metal halide film into a porous state, provide a channel for the permeation of an organic solution and accelerate the high-efficiency conversion of perovskite. However, most of the metal halide films prepared by the vacuum evaporation method are cross-stacked in a nanosheet manner, and under the condition of being thick, the film layer is not loose enough, so that the infiltration of the organic solution in the second step is hindered, the metal halide in the first step and the organic halide in the second step cannot react well, the problem of metal halide residue is easy to occur, the film forming quality is poor, and the performance of the device is affected.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a perovskite thin film, which aims to solve the technical problems of poor penetration of an organic solution in the second step, poor perovskite nucleation crystallization and poor quality of the perovskite thin film in the two-step preparation method of the perovskite thin film in the prior art.
The invention also aims to provide the perovskite thin film prepared by the preparation method of the perovskite thin film.
It is another object of the present invention to provide a perovskite solar cell.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the preparation method of the perovskite thin film comprises the following steps:
(a) Preparing a metal halide film on a substrate by adopting a vacuum method; using a metal mask plate in the process of preparing the metal halide film, wherein the metal mask plate is parallel to the substrate and is positioned between the substrate and the evaporation source;
(b) Preparing an organic halide film on the surface of the metal halide film of step (a) by a solution method or a vacuum method; and then annealing treatment is carried out to obtain the perovskite thin film.
In one embodiment, the metal mask comprises a plate body and a plurality of openings arranged on the plate body, wherein the openings are distributed in an array.
In one embodiment, the shape of the opening of the metal reticle includes a rectangle, a circle, or a triangle.
In one embodiment, the width of the shielding area around a single opening of the metal mask is 200 to 1500nm.
In one embodiment, the distance h between the metal reticle and the substrate satisfies the relation:
wherein w represents the width of a shielding region around a single opening of the metal mask, and θ represents the evaporation angle of the evaporation source material.
In one embodiment, in the step (a), the vacuum process includes at least one of a vacuum evaporation process, a near space sublimation process, an ion sputtering process, and a gas phase transport process.
In one embodiment, in step (a), the vacuum process employs one or more evaporation sources; the plurality of evaporation sources are co-deposited or sequentially deposited, and a metal mask is used in at least one deposition of the sequential deposition.
In one embodiment, during the preparation of the metal halide film, the metal mask is moved vertically and/or horizontally to control the morphology of the metal halide film.
In one embodiment, the source material of the evaporation source includes at least one of lead halide and rubidium halide.
In one embodiment, the source material of the evaporation source further includes cesium halide.
In one embodiment, the evaporation rates of the lead halide and the rubidium halide are 0.1 to 20A/s respectively.
In one embodiment, the cesium halide has an evaporation rate of 0.1 to 1A/s.
In one embodiment, the metal halide film has a thickness of 100 to 800nm.
In one embodiment, the solution process comprises at least one of wire bar spreading, slot coating, spray coating, spin coating, and dipping.
In one embodiment, the solution process employs an organic solution; the organic solution comprises a solute and a solvent; the concentration of the organic solution is 0.1 to 1.5M.
In one embodiment, the solute comprises at least one of iodomethylamine, iodoformamidine, bromomethylamine, bromoformamidine, chloromethylamine, and chloroformamidine.
In one embodiment, the solvent comprises at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol methyl ether, ethyl ether, lutidine N-oxide, ethyl acetate, N-propanol, isopropanol, 1, 2-propanediol, N-butanol, 2-butanol, N-hexane, chlorobenzene, 2-pentanol, methanol, t-butanol, acetonitrile, and ethanol.
In one embodiment, in step (b), the vacuum process comprises one of a vacuum evaporation process, a near space sublimation process, an ion sputtering process, or a gas transport process.
In one embodiment, the organic halide comprises an organic cation comprising a methylamine cation or a formamidine cation and a halogen anion comprising an iodide, a bromide, or a chloride.
In one embodiment, the annealing is a direct high temperature annealing.
In one embodiment, the high temperature annealing is performed at a temperature of 100 to 500 ℃.
In one embodiment, the holding time of the high temperature annealing is 1 to 30min.
In one embodiment, the annealing includes a low temperature annealing and a high temperature annealing performed in sequence.
In one embodiment, the temperature of the low temperature annealing is 25 to 100 ℃.
In one embodiment, the high temperature annealing is performed at a temperature of 100 to 500 ℃.
In one embodiment, the holding time of the high temperature annealing is 1 to 30min.
The perovskite thin film is prepared by the preparation method of the perovskite thin film.
The perovskite solar cell is prepared from the perovskite thin film.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the metal mask plate in the preparation process of the metal halide film, so that the surface of the metal halide film has different appearances, the surface area is increased, and the crossed film layer formed at the shielding position of the metal mask plate is more loose, the special appearance can assist the penetration of organic components to react with the metal halide to form high-quality perovskite crystals, and the perovskite crystals are grown into uniform and smooth films through annealing growth. The invention is suitable for various large-scale or small-scale coating equipment, and is suitable for large-scale application and batch production.
(2) The perovskite thin film obtained by the method has higher quality.
(3) The perovskite solar cell has more excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a side view structure of a metal halide film prepared by evaporation;
FIG. 2 is an overall schematic view of a metal mask of the present invention;
FIG. 3 is a partial schematic view of a metal mask of the present invention;
FIG. 4 is a schematic diagram of controlling the morphology of a metal halide film by adjusting the height of a metal mask from a substrate according to the present invention;
FIG. 5 is a schematic view of a metal halide film of the present invention;
FIG. 6 is a schematic view of another aspect of a metal halide film according to the present invention;
FIG. 7 is an I-V data curve of a battery of example 1 of the present invention;
FIG. 8 is an I-V data curve of a battery of example 2 of the present invention;
FIG. 9 is an I-V data curve of a battery of example 3 of the present invention;
FIG. 10 is an I-V data curve of a battery of example 4 of the present invention;
FIG. 11 is an I-V data curve of a battery of example 5 of the present invention;
FIG. 12 is an I-V data curve of a battery of example 6 of the present invention;
FIG. 13 is a plot of the I-V data for the cell of comparative example 1;
FIG. 14 is a scanning electron micrograph of a metal halide thin film according to example 1 of the present invention;
FIG. 15 is a scanning electron micrograph of a lead iodide thin film prepared by a conventional vacuum process without a mask.
Reference numerals:
1-alignment mechanism, 2-substrate, 3-metal mask, 4-rotary structure, 5-evaporation source and 6-evaporation chamber.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
The preparation method of the perovskite thin film comprises the following steps:
(a) Preparing a metal halide film on a substrate by adopting a vacuum method; using a metal mask in the process of preparing the film of metal chloride; the metal mask (FMM) is parallel to the substrate and is positioned between the substrate and the evaporation source;
(b) Preparing an organic halide film on the surface of the metal halide film of step (a) by a solution method or a vacuum method; and then annealing to obtain the perovskite film.
The metal mask plate is adopted in the preparation process of the metal halide film, so that the surface of the metal halide film has different appearances, the surface area of the metal halide film is increased, and a cross film layer formed at an FMM shielding position is looser, the special appearance can assist organic components to permeate and react with the metal halide to form high-quality perovskite crystals, and the perovskite crystals grow into uniform and smooth films through annealing growth.
The metal mask of the present invention is a fine metal mask made of metal, and generally a metal material such as INVAR36 or other metal having a small thermal expansion coefficient is used. The FMM can be prepared through methods such as an etching process, an electroforming process, an etching + laser composite material, a mixing process and the like, and the mask plate with the opening shape can be prepared.
In one embodiment, the metal mask comprises a plate body and a plurality of openings arranged on the plate body, wherein the openings are distributed in an array. In one embodiment, the shape of the aperture comprises one of a rectangle, a circle, or a triangle.
In one embodiment, the width of the shielding region around a single opening of the metal mask is 200 to 1500nm, such as 200nm, 300nm, 500nm, 800nm, 1000nm, 1500nm, etc.
In one embodiment, the overall structure of the metal mask is schematically shown in fig. 2. The partial schematic diagram of the metal mask is shown in fig. 3, wherein w1 and w2 represent the shielding size of the FMM mask, the size ranges of w1 and w2 are respectively 200nm to 1500nm, d1 and d2 represent the opening size of the FMM, and the size ranges of d1 and d2 are respectively 200nm to 1500nm, such as 200nm, 300nm, 500nm, 800nm, 1000nm and 1500nm. The FMM mask opening shape includes but is not limited to the schematic shape shown in FIG. 3, and the opening shape can be formed by combining other patterns according to the opening size.
In one embodiment, in the schematic diagram of fig. 4, h represents the distance between the substrate and the FMM mask, d represents the FMM opening size, w represents the width of the shielding region around a single opening of the metal mask, b represents the width of shadow (shadow is the thickness of a certain film layer at the shielding position due to the shadow effect, and the thickness of the film is thinner), a represents the distance between the outermost edges of the adjacent openings, and θ represents the evaporation angle of the evaporation source material. b can be calculated from h.cot θ. In one embodiment, the distance h between the metal reticle and the substrate satisfies the relation:
. The a can be calculated by a formula of a = w-2h · cot θ, when h is adjusted to be larger, shadow formed by the film under the FMM becomes larger, and the shape of the film formed by two adjacent openings can be controlled by setting different mask shielding sizes (w is different). Similarly, after the primary evaporation is finished, the blocking position can be shifted through shifting the FMM or the substrate, and the appearance of the film can be further adjusted through secondary evaporation.
In one embodiment, a schematic of the metal halide film of the invention in one form is shown in FIG. 5; another topographical view of the metal halide film of the present invention is shown in fig. 6.
In one embodiment, in the step (a), the vacuum process includes at least one of a vacuum evaporation process, a near space sublimation process, an ion sputtering process, and a gas phase transport process.
In one embodiment, in step (a), the vacuum process employs one or more evaporation sources; the plurality of evaporation sources are co-deposited or sequentially deposited, and a metal reticle is used in at least one deposition of the sequential deposition.
In one embodiment, during the preparation of the metal halide film, the metal mask is moved vertically and/or horizontally to control the morphology of the metal halide film.
In one embodiment, the raw material of the evaporation source includes at least one of lead halide and rubidium halide. The lead halide comprises PbI 2 、PbCl 2 Or PbBr 2 . The rubidium halide comprises RbCl. Further, the source material of the evaporation source further includes cesium halide including CsI, csCl, or CsBr.
In one embodiment, the lead halide and rubidium halide have evaporation rates of 0.1 to 20A/s, such as 0.1A/s, 0.2A/s, 0.5A/s, 1A/s, 2A/s, 5A/s, 10A/s, 15A/s, 18A/s, 19A/s, 20A/s, and the like, respectively.
In one embodiment, the cesium halide has an evaporation rate of 0.1 to 1A/s, such as 0.1A/s, 0.2A/s, 0.3A/s, 0.5A/s, 0.6A/s, 0.7A/s, 0.8A/s, 0.9A/s, or 1A/s, and the like.
In one embodiment, the vacuum method employs a plurality of evaporation sources, e.g., 2, 3, 4, etc.
In one embodiment, the number of evaporation sources is two (evaporation source A and evaporation source B), and a layer of PbI is deposited on the substrate through a mask using evaporation source A 2 And removing the FMM mask plate, and depositing at least one of a layer of CsI, csCl and CsBr on the substrate by using the evaporation source B to obtain the metal halide film with the special morphology.
In one embodiment, the number of evaporation sources is four (evaporation source a, evaporation source B, evaporation source C, and evaporation source D) for evaporation of different materials, and the evaporation deposition may be performed simultaneously or sequentially.
In one embodiment, the metal halide film has a thickness of 100 to 800nm, such as 100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 300nm, 400nm, 500nm, 600nm, 650nm, 700nm, 800nm, and the like.
In one embodiment, an alignment mechanism is used during the process of preparing the metal halide film on the substrate; the alignment mechanism comprises a first support for placing the substrate, a second support for placing the metal mask, a CCD alignment camera and a motion platform. And the CCD contraposition camera is used for grabbing and judging the positions of the evaporation substrate and the metal mask. The moving platform is used for adjusting the height of a gap between the substrate and the metal mask plate so as to control a film pattern formed by the metal mask plate. Meanwhile, the contraposition mechanism can control the evaporation position by performing left-right deviation on a metal mask plate or an evaporation substrate on a single control motion platform.
In one embodiment, the alignment mechanism is further connected with a rotating structure. The rotating mechanism is connected to the upper end of the aligning mechanism, and the thickness uniformity of the film is improved in the evaporation film forming process through rotating the aligning mechanism.
In one embodiment, the solution process comprises at least one of wire bar doctor blade coating, slot-die coating, spray coating, spin coating, and dipping.
In one embodiment, the solution process employs an organic solution; the organic solution comprises a solute and a solvent; the concentration of the organic solution is 0.1 to 1.5M, for example, 0.1M, 0.2M, 0.3M, 0.5M, 0.7M, 0.8M, 1M, 1.2M, 1.5M, etc.
In one embodiment, the solute comprises at least one of iodomethylamine (MAI), iodoformamidine (FAI), bromomethylamine (MABr), bromoformamidine (FABr), chloromethylamine (MACl), and chloromethylamidine (FACl).
In one embodiment, the solvent comprises at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), 1, 3-dimethyl-2-imidazolidinone (DMI), ethylene glycol methyl ether (2-ME), diethyl ether, lutidine N-oxide (DMPO), ethyl acetate, N-propanol, isopropanol (IPA), 1, 2-propanediol, N-butanol, 2-butanol, N-hexane, chlorobenzene, 2-pentanol, methanol, t-butanol, acetonitrile, and ethanol.
In one embodiment, the organic solution employs at least three of the above solutes as solutes and at least two of the above solvents as solvents to form a composite organic solution. In one embodiment, the composite organic solution is reacted with the first-step metal halide thin film through Slot-die and blade coating equipment to prepare a uniform, smooth and large-area perovskite film layer without holes and stripes.
In one embodiment, in step (b), the vacuum process comprises one of a vacuum evaporation process, a near-space sublimation process, an ion sputtering process, or a gas-to-gas transport process. The organic halide film is prepared by vacuum method, and the raw material is organic halide comprising organic cation and halogen anion, wherein the organic cation comprises methylamine cation (MA) + ) Or formamidine cation (FA) + ) The halogen anion includes iodide, bromide or chloride. The organic halide contacts the metal halide film in a steam form, namely the organic halide is heated to form organic halide steam, and the metal halide film is placed in the atmosphere of the organic halide steam, so that the organic halide steam is adsorbed on the metal halide film with the special appearance prepared in the first step to react.
And annealing after the reaction is finished by the two-step method to form the perovskite thin film. In one embodiment, the annealing is a direct high temperature annealing; in one embodiment, the high temperature annealing is performed at a temperature of 100 to 500 ℃, for example, 100 ℃, 200 ℃, 300 ℃, 400 ℃, or 500 ℃. In one embodiment, the high temperature annealing is performed for 1 to 30min, such as 1min, 5min, 10min, 15min, 20min, or 30min.
In another embodiment, the annealing includes a low temperature annealing and a high temperature annealing performed in sequence. In one embodiment, the low temperature annealing is performed at a temperature of 25 to 100 ℃, for example, 25 ℃, 50 ℃, 70 ℃, 80 ℃, 100 ℃, or the like. In one embodiment, the high temperature annealing is performed at a temperature of 100 to 500 ℃, for example, 100 ℃, 200 ℃, 300 ℃, 400 ℃, or 500 ℃. In one embodiment, the high temperature annealing is performed for a holding time of 1 to 30min, such as 1min, 5min, 10min, 15min, 20min or 30min.
According to another aspect of the invention, the invention also relates to a perovskite thin film prepared by the preparation method of the perovskite thin film. The perovskite thin film has excellent film forming quality, and the efficiency of a device is further improved.
According to another aspect, the invention also relates to a perovskite solar cell which is prepared from the perovskite thin film. The perovskite solar cell has more excellent electrochemical performance.
The following is a further explanation with reference to specific examples and comparative examples.
The schematic side view structure of the metal halide film prepared by the evaporation method is shown in fig. 1, the evaporation process is carried out in an evaporation chamber 6 of a vacuum coating machine, and an alignment mechanism 1 is arranged in the evaporation chamber 6; the metal mask 3 and the substrate 2 are placed on the aligning mechanism 1 from bottom to top, the metal mask 3 and the substrate 2 are horizontally arranged, the evaporation source 5 is positioned at the lower part of the metal mask 3, and the number of the evaporation sources 5 is determined according to the arrangement of the specific embodiment; the upper end of the contraposition mechanism 1 is connected with a rotating structure 4.
Example 1
The preparation method of the perovskite thin film comprises the following steps:
(a) Preparing a layer of nickel oxide film (NiOx) on FTO conductive glass by using a magnetron sputtering method, then placing a cleaned metal mask (with a rectangular opening, a width d1 of 400nm, a length d2 of 400nm and evaporation barrier widths w1 and w2 of 400nm respectively) and the FTO glass plated with the NiOx film on an alignment mechanism of a point source vacuum coating machine from bottom to top in sequence, controlling a motion platform to adjust the distance between an FMM and substrate glass to 200nm, closing a valve, vacuumizing a chamber to below 1.0E-4Pa, and then starting to heat a point source evaporation source to prepare for depositing a metal halide film layer. The temperature of the evaporation source is 300 ℃, and the evaporation material is PbI 2 And the thickness is 400nm through evaporation.
(b) Coating organic components on the metal halide film by using a Slot-die or knife coating device, wherein the solutes of the organic solution are FAI, MAI and MACl, the mass ratio of FAI, MAI and MACl is 90.4. After the organic solution is coated, the substrate is transferred into an annealing box to be heated at 140 ℃, so that the organic component and the metal halide are subjected to chemical reaction to form the perovskite film layer.
The preparation method of the perovskite solar cell comprises the following steps: c with a thickness of 20nm was evaporated on each of the perovskite film layers obtained in this example 60 And BCP 5nm thick, and finally a Cu electrode 60nm thick was evaporated.
Example 2
The preparation method of the perovskite thin film comprises the following steps:
(a) Preparing a layer of nickel oxide film (NiOx) on FTO conductive glass by using a magnetron sputtering method, then placing a cleaned FMM mask plate (with a rectangular opening, a width d1 of 400nm, a length d2 of 400nm and evaporation widths w1 and w2 of 400nm respectively) and the FTO glass plated with the NiOx film on an alignment mechanism platform of a point source vacuum coating machine from bottom to top in sequence, controlling a motion platform to adjust the distance between the FMM and the substrate glass to 300nm, closing a valve, vacuumizing a chamber to a certain vacuum degree, and then starting to heat a point source evaporation source to prepare for depositing a metal halide film layer. Evaporation of PbI using evaporation source 2 And the temperature is 300 ℃, the vapor deposition thickness is 400nm, then the motion platform is adjusted to enable the relative position of the FMM and the substrate glass to shift, the shift distance is the FMM opening distance, and then the vapor deposition is continued for 400nm.
(b) Coating an organic component on a metal halide film by using a blade coating device, wherein the solute of the organic solution is FAI, MAI and MACl, the mass ratio of FAI, MAI and MACl is 90.4. And immediately transferring the substrate into an annealing box to be heated at 140 ℃ after the organic solution is coated, so that the organic component and the metal halide are subjected to chemical reaction to form the perovskite film layer.
The preparation method of the perovskite solar cell comprises the following steps: c was evaporated to a thickness of 20nm on each of the perovskite film layers obtained in this example 60 And 5nm thick BCP, and finally evaporating 60nm thickAnd a Cu electrode.
Example 3
The preparation method of the perovskite thin film comprises the following steps:
(a) Preparing a layer of nickel oxide film (NiOx) on FTO conductive glass by using a magnetron sputtering method, then sequentially placing a cleaned FMM mask plate (with a rectangular opening, a width d1 of 400nm, a length d2 of 400nm and evaporation widths w1 and w2 of 400nm respectively) and the FTO glass plated with the NiOx film on an alignment mechanism platform of near space sublimation equipment (CSS) from bottom to top, controlling the motion platform to adjust the distance between the FMM and the substrate glass to 200nm, vacuumizing a chamber to a certain vacuum degree after a valve is closed, and starting to heat an evaporation source to prepare for depositing a metal halide film layer, wherein the evaporation source comprises an evaporation source A and an evaporation source B; evaporating PbI by using evaporation source A 2 At the temperature of 300 ℃, the evaporation rate is 2A/s, the evaporation thickness is 385nm, the moving platform is adjusted, the FMM is removed and is not blocked, the evaporation source B is used for evaporating CsI with the thickness of 15nm, and the evaporation rate is 4A/s.
(b) Coating organic components on the metal halide film by using a knife coating device, wherein the solutes of the organic solution are FAI, MAI and MACl, the mass ratio of the FAI, MAI and MACl is 90.4: 3, the concentration of the organic solution was 0.5mol/L, the coating speed was 30mm/s, the amount of the gel applied per second was 40. Mu.L/s, and the gap was 100. Mu.m. After the organic solution is coated, the substrate is transferred into an annealing box to be heated at 140 ℃, so that the organic component and the metal halide are subjected to chemical reaction to form the perovskite film layer.
The preparation method of the perovskite solar cell comprises the following steps: c with a thickness of 20nm was evaporated on each of the perovskite film layers obtained in this example 60 And BCP 5nm thick, and finally a Cu electrode 60nm thick was evaporated.
Example 4
The perovskite thin film preparation method is the same as the example 3 except that the organic solution is composed of FAI as a solute and isopropanol as a solvent, and the concentration of the isopropanol is 0.5 mol/L.
The perovskite solar cell was fabricated in the same manner as in example 3.
Example 5
The preparation method of the perovskite film comprises the steps of removing evaporation sources including an evaporation source A, an evaporation source B, an evaporation source C and an evaporation source D, and evaporating PbI by using the evaporation source A 2 Evaporating to deposit PbBr with thickness of 410nm, adjusting the motion platform, removing FMM without shielding, and continuing to sequentially use the evaporation source B to evaporate PbBr with thickness of 8nm 2 The same conditions as in example 3 were used except that CsCl having a thickness of 6nm was deposited by using the evaporation source C and RbCl having a thickness of 5nm was deposited by using the evaporation source C.
The perovskite solar cell was prepared as in example 3.
Example 6
The preparation method of the perovskite film comprises the steps that the evaporation source comprises an evaporation source A, an evaporation source B and an evaporation source C, wherein the evaporation source A is PbI 2 The deposition was performed while CsCl as the evaporation source B and RbCl as the evaporation source C, and the thickness of the plating layer was 510nm, except that the conditions were the same as those in example 3.
The perovskite solar cell was prepared as in example 3.
Comparative example 1
The perovskite thin film preparation method does not use metal mask plate, and other conditions are the same as example 3.
The perovskite solar cell was fabricated in the same manner as in example 3.
Examples of the experiments
1. Scanning electron microscope image
The scanning electron microscope image of the metal halide film in the embodiment 1 of the present invention is shown in fig. 14, and the scanning electron microscope image of the lead iodide film prepared by a conventional vacuum method without a mask plate is shown in fig. 15, and as can be seen from fig. 14 and fig. 15, compared with the film prepared without a mask plate, the film prepared by using a mask plate according to the present invention has a loose surface and an increased porosity, which is beneficial to the penetration of the organic halide film of the second component, is beneficial to the sufficient reaction of the metal halide and the organic halide, and avoids the problem of metal halide residue.
2. Electrochemical performance of perovskite solar cells
The electrochemical properties of the perovskite solar cells obtained in the examples of the invention and the comparative examples are shown in table 1. The I-V data curve of the battery of example 1 of the present invention is shown in fig. 7, the I-V data curve of the battery of example 2 is shown in fig. 8, the I-V data curve of the battery of example 3 is shown in fig. 9, the I-V data curve of the battery of example 4 is shown in fig. 10, the I-V data curve of the battery of example 5 is shown in fig. 11, the I-V data curve of the battery of example 6 is shown in fig. 12, and the I-V data curve of the battery of comparative example 1 is shown in fig. 13.
TABLE 1 electrochemical Properties of perovskite solar cells
As can be seen from table 1 and fig. 7 to 13, in each embodiment of the present invention, the metal mask is used in the preparation process of the metal halide film to further prepare the perovskite solar cell, and the perovskite solar cell has excellent electrochemical performance superior to that of the perovskite solar cell prepared in comparative example 1 without using the metal mask.
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 (12)
1. The preparation method of the perovskite thin film is characterized by comprising the following steps:
(a) Preparing a metal halide film on a substrate by a vacuum method; using a metal mask plate in the process of preparing the metal halide film, wherein the metal mask plate is parallel to the substrate and is positioned between the substrate and the evaporation source;
(b) Preparing an organic halide film on the surface of the metal halide film of step (a) by a solution method or a vacuum method; and then annealing to obtain the perovskite film.
2. The production method of the perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The metal mask comprises a plate body and a plurality of openings arranged on the plate body, wherein the openings are distributed in an array;
(2) The shape of the opening of the metal mask plate comprises a rectangle, a circle or a triangle.
3. The method for preparing a perovskite thin film as claimed in claim 2, wherein the width of a shielding region around a single opening of the metal mask is 200 to 1500nm.
4. The method for preparing a perovskite thin film as claimed in claim 3, wherein the distance h between the metal mask and the substrate satisfies the relation:
wherein w represents the width of a shielding region around a single opening of the metal mask, and θ represents the evaporation angle of the evaporation source material.
5. The production method of a perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) In the step (a), the vacuum method includes at least one of a vacuum evaporation method, a near space sublimation method, an ion sputtering method, and a gas phase transport method;
(2) In step (a), the vacuum method employs one or more evaporation sources; a plurality of the evaporation sources are subjected to co-deposition or sequential deposition, and a metal mask is used in at least one deposition of the sequential deposition;
(3) In the process of preparing the metal halide film, the metal mask plate vertically moves and/or horizontally moves to regulate the appearance of the metal halide film.
6. The production method of a perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (5):
(1) The raw material of the evaporation source comprises at least one of lead halide and rubidium halide;
(2) The raw material of the evaporation source further comprises cesium halide;
(3) The evaporation rates of the lead halide and the rubidium halide are respectively 0.1-20A/s;
(4) The evaporation rate of the cesium halide is 0.1 to 1A/s;
(5) The thickness of the metal halide film is 100 to 800nm.
7. The production method of a perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) The solution method comprises at least one of wire bar blade coating, slit coating, spray coating, spin coating and soaking;
(2) The solution method adopts an organic solution; the organic solution comprises a solute and a solvent; the concentration of the organic solution is 0.1 to 1.5M;
(3) The solute comprises at least one of iodomethylamine, iodoformamidine, bromomethylamine, bromoformamidine, chloromethane and chloroformamidine;
(4) The solvent includes at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol methyl ether, diethyl ether, lutidine N-oxide, ethyl acetate, N-propanol, isopropanol, 1, 2-propanediol, N-butanol, 2-butanol, N-hexane, chlorobenzene, 2-pentanol, methanol, t-butanol, acetonitrile, and ethanol.
8. The production method of the perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) In step (b), the vacuum process comprises one of a vacuum evaporation process, a near-space sublimation process, an ion sputtering process, or a gas-to-gas transport process;
(2) The organic halide comprises an organic cation comprising a methylamine cation or a formamidine cation and a halogen anion comprising an iodide ion, a bromide ion or a chloride ion.
9. The production method of a perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The annealing is direct high-temperature annealing;
(2) The temperature of the high-temperature annealing is 100 to 500 ℃;
(3) The heat preservation time of the high-temperature annealing is 1-30min.
10. The production method of a perovskite thin film as claimed in claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) The annealing comprises low-temperature annealing and high-temperature annealing which are sequentially carried out;
(2) The temperature of the low-temperature annealing is 25 to 100 ℃;
(3) The temperature of the high-temperature annealing is 100 to 500 ℃;
(4) The heat preservation time of the high-temperature annealing is 1-30min.
11. A perovskite thin film which is produced by the production method for a perovskite thin film according to any one of claims 1 to 10.
12. A perovskite solar cell, characterized by being produced from the perovskite thin film according to claim 11.
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| CN109742247A (en) * | 2019-03-01 | 2019-05-10 | 苏州协鑫纳米科技有限公司 | The method and photoelectric device of photoelectric device are prepared in any substrate |
| CN113193125A (en) * | 2021-04-15 | 2021-07-30 | 北京大学 | Flexible perovskite solar cell with high power-to-mass ratio and preparation method thereof |
| CN115295732A (en) * | 2022-09-28 | 2022-11-04 | 无锡极电光能科技有限公司 | Perovskite thin film, preparation method and system thereof, and solar cell |
| CN115425148A (en) * | 2022-09-15 | 2022-12-02 | 浙江爱旭太阳能科技有限公司 | Perovskite solar cell and preparation method |
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| CN109742247A (en) * | 2019-03-01 | 2019-05-10 | 苏州协鑫纳米科技有限公司 | The method and photoelectric device of photoelectric device are prepared in any substrate |
| CN113193125A (en) * | 2021-04-15 | 2021-07-30 | 北京大学 | Flexible perovskite solar cell with high power-to-mass ratio and preparation method thereof |
| CN115425148A (en) * | 2022-09-15 | 2022-12-02 | 浙江爱旭太阳能科技有限公司 | Perovskite solar cell and preparation method |
| CN115295732A (en) * | 2022-09-28 | 2022-11-04 | 无锡极电光能科技有限公司 | Perovskite thin film, preparation method and system thereof, and solar cell |
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