CN116507138A - Perovskite film preparation method, perovskite film and photoelectric device - Google Patents
Perovskite film preparation method, perovskite film and photoelectric device Download PDFInfo
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- CN116507138A CN116507138A CN202310355020.XA CN202310355020A CN116507138A CN 116507138 A CN116507138 A CN 116507138A CN 202310355020 A CN202310355020 A CN 202310355020A CN 116507138 A CN116507138 A CN 116507138A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000010409 thin film Substances 0.000 claims abstract description 153
- 239000000463 material Substances 0.000 claims abstract description 145
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 230000005693 optoelectronics Effects 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- -1 polydimethylsiloxane Polymers 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 47
- 238000004528 spin coating Methods 0.000 description 16
- 230000005540 biological transmission Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 7
- 238000005530 etching Methods 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- 239000012296 anti-solvent Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 4
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- 230000005012 migration Effects 0.000 description 4
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- 239000004065 semiconductor Substances 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
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- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- FBUIIWHYTLCORM-UHFFFAOYSA-N 3-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CN=C1 FBUIIWHYTLCORM-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a perovskite film preparation method, a perovskite film and a photoelectric device, wherein the perovskite film preparation method comprises the following steps: providing a substrate and forming a first perovskite thin film on the substrate; providing a stamp body having a patterned first surface and forming a second perovskite thin film on the first surface, the second perovskite thin film comprising a second perovskite material; imprinting the second perovskite thin film of the stamp body into the first perovskite thin film under preset pressure so as to diffuse ions in the second perovskite material into the first perovskite thin film at the corresponding imprinting position, thereby forming a third perovskite material at the imprinting position, wherein the solubility of the third perovskite material is greater than that of the first perovskite material; the third perovskite material is removed with a solvent to form a patterned first perovskite thin film. The method effectively avoids redundant residues on the substrate after imprinting is finished, has high preparation yield and low cost, and is convenient for the integrated preparation of the subsequent photoelectric device.
Description
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to a perovskite film preparation method, a perovskite film and a photoelectric device.
Background
The organic lead halogen perovskite material is widely focused on the related fields as a new generation of organic-inorganic hybrid semiconductor material, is widely applied to the fields of photovoltaic devices, luminescence devices, detection devices, lasers and the like, and particularly, the authentication efficiency of a solar cell based on a perovskite thin film is up to more than 25 percent, which is comparable with that of a commercial silicon-based solar cell, so that research and exploration of the perovskite material/thin film in various application fields of photoelectricity are well conducted.
However, the existing perovskite film preparation method is large and complex in process difficulty, and the problem of perovskite residues is easy to occur, so that the preparation yield of the perovskite film is affected.
Therefore, a new perovskite thin film preparation method, perovskite thin film and photoelectric device are needed.
Disclosure of Invention
The perovskite thin film preparation method provided by the embodiment of the invention can effectively avoid redundant residues on a substrate after imprinting is finished, and is high in preparation yield and low in cost of the patterned first perovskite thin film, and meanwhile, the integrated preparation of a subsequent photoelectric device is facilitated.
In one aspect, the embodiment of the invention provides a perovskite thin film preparation method, which comprises the following steps: providing a substrate and forming a first perovskite thin film on the substrate, wherein the first perovskite thin film comprises a first perovskite material; providing a stamp body having a patterned first surface and forming a second perovskite thin film on the first surface, wherein the second perovskite thin film comprises a second perovskite material; imprinting the second perovskite thin film of the stamp body in the first perovskite thin film under a preset pressure, so that ions in the second perovskite material diffuse into the first perovskite thin film of the corresponding imprinting position to form a third perovskite material at the imprinting position, wherein the solubility of the third perovskite material is greater than that of the first perovskite material; the third perovskite material is removed with a solvent to form a patterned first perovskite thin film.
According to one aspect of the invention, the first perovskite material comprises ABCl 3 A comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (B) comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2 + 、Zn 2+ 、Cd 2+ 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of (a); and/or the second perovskite material comprises CDX 3 X includes I － 、Br － Or a combination thereof, C comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (a), D comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2+ 、Zn 2+ 、Cd 2+ 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of the group.
According to one aspect of the present invention, the step of providing a substrate and forming a first perovskite thin film on the substrate includes the steps of: providing a substrate; and coating a solution comprising a first perovskite material on the substrate, and forming a first perovskite film through annealing treatment, wherein the first perovskite film comprises the first perovskite material.
According to one aspect of the present invention, the step of providing a stamp body having a patterned first surface and forming a second perovskite thin film on the first surface includes the steps of: providing a stamp body having a patterned first surface; performing hydrophilic treatment on the first surface of the seal body; and coating a solution comprising a second perovskite material on the first surface, and forming a second perovskite film through annealing treatment, wherein the second perovskite film comprises the second perovskite material.
According to one aspect of the present invention, the step of imprinting the second perovskite thin film of the stamp body in the first perovskite thin film under a preset pressure to diffuse ions in the second perovskite material into the first perovskite thin film of the corresponding imprint location to form a third perovskite material at the imprint location, includes the steps of: imprinting the second perovskite thin film of the stamp body in the first perovskite thin film under preset pressure and preset temperature so as to diffuse ions in the second perovskite material into the first perovskite thin film at the corresponding imprinting position, thereby forming a third perovskite material at the imprinting position; or, imprinting the second perovskite thin film of the seal body into the first perovskite thin film under a preset pressure, and performing annealing treatment to diffuse ions in the second perovskite material into the first perovskite thin film at the corresponding imprinting position so as to form a third perovskite material at the imprinting position; the preset pressure is 0-100 MPa, and the preset temperature is 70-300 ℃; the annealing treatment temperature is 70-300 ℃.
According to one aspect of the invention, the step of removing the third perovskite material using a solvent comprises the steps of: removing the third perovskite material by a solvent flushing method or a solvent soaking method; the solvent comprises at least one of dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, chlorobenzene and diethyl ether.
According to one aspect of the present invention, the material of the substrate includes at least one of transparent conductive glass, oxide material, and polymer material; and/or the material of the seal body comprises at least one of polydimethylsiloxane, polymethyl methacrylate and sapphire.
According to one aspect of the present invention, between the step of imprinting the second perovskite thin film of the stamp body in the first perovskite thin film under the preset pressure and the step of removing the third perovskite material using a solvent, further comprising: and forming a transmission material layer on one side of the third perovskite film, which is away from the substrate, and one side of the first perovskite film, which is away from the substrate.
The embodiment of the invention also provides a perovskite film prepared by the perovskite film preparation method in any embodiment.
In yet another aspect, an embodiment of the present invention provides an optoelectronic device, including the perovskite thin film in the above embodiment.
Compared with the prior art, the perovskite thin film preparation method provided by the embodiment of the invention forms the second perovskite thin film on the first surface of the seal body, and then the second perovskite thin film of the seal body is stamped in the first perovskite thin film by utilizing the high ion migration capability of perovskite, so that ions in the second perovskite material are diffused into the first perovskite thin film at the corresponding stamping position, and a third perovskite material is formed at the stamping position. Because the ion diffusion in the second perovskite material, the solubility of the third perovskite material is larger than that of the first perovskite material, and then the third perovskite material can be removed through a solvent by utilizing the solubility difference of the third perovskite material and the first perovskite material so as to form a patterned first perovskite film. And meanwhile, the integrated preparation of the subsequent photoelectric device is also convenient.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a flow chart of a method for preparing a perovskite thin film according to one embodiment of the invention;
FIG. 2 is a schematic cross-sectional view of the structure obtained in step S110 in the perovskite thin film manufacturing method according to one embodiment of the invention;
FIG. 3 is a schematic cross-sectional view of the structure obtained in step S110 in a perovskite thin film manufacturing method according to another embodiment of the invention;
FIG. 4 is a schematic cross-sectional view of the structure obtained in step S120 in the perovskite thin film manufacturing method according to one embodiment of the invention;
FIG. 5 is a schematic cross-sectional view of the structure obtained in step S120 in a perovskite thin film manufacturing method according to another embodiment of the invention;
FIG. 6 is a schematic cross-sectional view of the structure obtained in step S130 in the perovskite thin film manufacturing method according to one embodiment of the invention;
FIG. 7 is a schematic cross-sectional view of the structure obtained in step S130 in a perovskite thin film manufacturing method according to another embodiment of the invention;
FIG. 8 is a schematic cross-sectional view of the structure obtained in step S140 in the perovskite thin film manufacturing method according to one embodiment of the invention;
FIG. 9 is a schematic cross-sectional view of a structure obtained during the preparation of a perovskite thin film according to one embodiment of the invention;
FIG. 10 is a schematic cross-sectional view of a structure obtained during the preparation of a perovskite thin film according to another embodiment of the invention;
FIG. 11 is a schematic cross-sectional view of a structure obtained during the preparation of a perovskite thin film according to still another embodiment of the invention.
In the accompanying drawings:
1-a substrate; 2-a first perovskite thin film; 21-a first perovskite material; 3-a seal body; 4-a second perovskite thin film; 41-a second perovskite material; 5-a third perovskite material; 6-a transport layer; 61-a layer of a transmission material; 7-an electrode layer; p1-first surface.
Detailed Description
Features and exemplary embodiments of various aspects of the invention are described in detail below. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the invention by showing examples of the invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
In the prior art, perovskite patterning techniques are largely divided into two main categories: a bottom-up growth method and a top-down etching method. The top-down etching method is to carry out electron beam/ion beam etching on the perovskite material which is formed into a film to construct a pattern, but the perovskite belongs to an ionic compound semiconductor, and the etching greatly reduces the quality of the perovskite pattern and is not suitable for processing the perovskite material basically. The bottom-up growth method can be further divided into: inkjet printing, laser direct writing, nanoimprinting, substrate pre-patterning, and template assisted. The ink-jet printing method has higher requirements on equipment and the perovskite patterning unit has poorer film forming quality and resolution; the patterns prepared by the laser direct writing method are flexible, but the perovskite quality is very poor and uncontrollable; the perovskite pattern prepared by the substrate pre-patterning method has better quality and controllable growth condition, but the pre-patterning process is complex and has special requirements on the substrate; the template-assisted method is generally directed to perovskite patterns constructed by vapor deposition, but the quality of the perovskite material itself obtained by vapor deposition is poor.
The nanoimprint method is a process of growing a perovskite material/thin film solution, and imprinting confinement is performed on a liquid film in a "soft" state thereof, thereby obtaining a desired perovskite pattern. However, it is difficult to ensure whether there is an excessive residue on the substrate after the imprinting is finished by the existing nanoimprinting method, and the main phenomenon is that the imprinting process needs to finely control the pressure to avoid the growth of unnecessary perovskite residues at the non-preset pattern positions; meanwhile, the stripping of the nano seal also affects the quality and yield of the pattern, perovskite tends to nucleate and grow at the position which is adhered to the seal wall in the process of limited-area growth, so that the stripping process of the nano seal is likely to affect the formed pattern, the yield of the pattern is reduced, and the whole process is relatively complex; in addition, perovskite patterns grown based on the existing nanoimprint method are poor in quality, and subsequent photoelectric devices based on the patterns are difficult to prepare and integrate.
In order to solve the problems, according to the perovskite thin film preparation method provided by the embodiment of the invention, the third perovskite material is removed through the solvent by utilizing the solubility difference of the third perovskite material and the first perovskite material so as to form the patterned first perovskite thin film, the process steps are simple and easy to operate, and compared with the existing nano imprinting method, the perovskite thin film preparation method provided by the embodiment of the invention can effectively avoid redundant residues on a substrate after imprinting is finished, and the preparation yield of the patterned first perovskite thin film is high and the cost is low. And meanwhile, the integrated preparation of the subsequent photoelectric device is also convenient.
In order to better understand the present invention, a perovskite thin film manufacturing method, a perovskite thin film, and an optoelectronic device according to an embodiment of the present invention are described in detail with reference to fig. 1 to 11.
Referring to fig. 1 to 8, the embodiment of the invention provides a perovskite thin film preparation method, which comprises the following steps:
s110: providing a substrate 1 and forming a first perovskite thin film 2 on the substrate 1, wherein the first perovskite thin film 2 comprises a first perovskite material 21, as shown in fig. 2 and 3;
s120: providing a stamp body 3 having a patterned first surface P1, and forming a second perovskite thin film 4 on the first surface P1, wherein the second perovskite thin film 4 includes a second perovskite material 41, as shown in fig. 4 and 5;
s130: imprinting the second perovskite thin film 4 of the stamp body 3 in the first perovskite thin film 2 under a preset pressure so that ions in the second perovskite material 41 diffuse into the first perovskite thin film 2 at corresponding imprinting positions to form a third perovskite material 5 at the imprinting positions, wherein the solubility of the third perovskite material 5 is greater than that of the first perovskite material 21, as shown in fig. 6 and 7;
s140: the third perovskite material 5 is removed with a solvent to form the patterned first perovskite thin film 2, as shown in fig. 8.
According to the perovskite thin film preparation method provided by the embodiment of the invention, the second perovskite thin film 4 is formed on the first surface P1 of the stamp body 3, and then the second perovskite thin film 4 of the stamp body 3 is stamped in the first perovskite thin film 2 by utilizing the high ion migration capability of perovskite, so that ions in the second perovskite material 41 are diffused into the first perovskite thin film 2 at the corresponding stamping position, and a third perovskite material 5 is formed at the stamping position. Because of ion diffusion in the second perovskite material 41, the solubility of the third perovskite material 5 is greater than that of the first perovskite material 21, and then the third perovskite material 5 can be removed by using the solubility difference between the third perovskite material 5 and the first perovskite material 21 through a solvent to form the patterned first perovskite film 2.
It should be noted that, because the solubility of the first perovskite material 21 is relatively low and is not easy to be removed by the solvent, the embodiment of the present invention uses the second perovskite material 41 and the first perovskite material 21 to perform ion diffusion, so as to increase the solubility of the formed third perovskite material 5, further reduce the difficulty of removing the third perovskite material 5 by the solvent, and facilitate forming the required patterned first perovskite thin film 2.
In step S110, the material of the substrate 1 includes, but is not limited to, one or more of various insulating, semiconductor, etc., organic or inorganic materials. For example, the material of the substrate 1 includes at least one of transparent conductive glass, oxide material, and polymer material. Specifically, the transparent conductive glass comprises ITO (Indium Tin Oxide), FTO (fluorine doped Tin dioxide), IZO (Indium Zinc Oxide ), etc., and the Oxide material comprises Al 2 O 3 、TiO 2 、SnO 2 ZnO, etc., organic polymeric materials PMMA (polymethyl methacrylate), PDMS (polydimethylsiloxane), etc., as well as a range of composites. Wherein, the material of the substrate 1 needs to satisfy good wettability to ensure that the first perovskite film 2 thereon can obtain a uniform and compact film; in addition, to meet the requirements of subsequent fabrication of optoelectronic devices, the substrate 1 may be a pre-fabricated device structure.
The first perovskite thin film 2 includes the first perovskite material 21, and may be specifically formed by a coating process, for example, spin coating, blade coating, slit coating, vacuum evaporation, or the like, without particular limitation.
Optionally, the first perovskite material 21 comprises ABCl 3 A comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (B) comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2+ 、Zn 2+ 、Cd 2 + 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of the group.
Specifically, the first perovskite material 21 includes CsPbCl 3 、MAPbCl 3 、FAPbCl 3 In addition, two-dimensional, one-dimensional or even zero-dimensional Pb-Cl perovskite components are also included. The composition of the first perovskite material 21 may be specifically selected as needed, and is not particularly limited.
In step S120, as shown in fig. 4, the stamp body 3 has a patterned first surface P1, and the specific pattern of the first surface P1 needs to be selected according to the pattern of the first perovskite thin film 2 to be formed, and is not particularly limited. Subsequent imprinting is facilitated by forming the second perovskite thin film 4 on the first surface P1 such that the second perovskite thin film 4 forms a desired pattern.
In the present embodiment, the second perovskite material 41 includes CDX 3 X includes I － 、Br － Or a combination thereof, C comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (a), D comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2+ 、Zn 2+ 、Cd 2+ 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of the group. Wherein, C and D may be any ion satisfying perovskite structure, and are not particularly limited.
Specifically, the second perovskite material 41 includes MAPbI 3 、MAPbBr 3 、FAPbI 3 、FAPbBr 3 、MAPbI 2 Br、FAPbBr 2 I、FA 0.5 MA 0.5 PbI 3 、MASnI 3 And the like. CDX (compact digital X) 3 The coating preparation method of (2) includes, but is not limited to, spin coating, blade coating, slit coating, vacuum evaporation, and the like.
It should be noted that the solubility of the second perovskite material 41 to be used may be greater than the solubility of the first perovskite material 21, or may be less than the solubility of the first perovskite material 21, so long as the solubility of the third perovskite material 5 formed by subsequent ion diffusion is ensured to be greater than the solubility of the first perovskite material 21, and is not particularly limited.
Optionally, the material of the stamp body 3 includes at least one of PDMS (polydimethylsiloxane), PMMA (polymethyl methacrylate), and sapphire. The material which is convenient for forming the patterned first surface P1 and is not easily deformed may be applied to the stamp body 3, and is not particularly limited.
The pattern preparation method of the stamp body 3 can adopt common pattern etching preparation processes such as photoetching, electron beam etching and the like. It should be noted that the patterned first surface P1 of the stamp body 3 should satisfy a certain wettability so as to ensure uniform preparation of the second perovskite thin film 4.
In step S130, as shown in fig. 6 and 7, ions in the second perovskite material 41 diffuse into the first perovskite thin film 2 at the corresponding imprint positions to form the third perovskite material 5 at the imprint positions, for example, where the first perovskite material 21 is ABCl 3 The second perovskite material 41 is CDX 3 C, B, X component ABCl 3 The third perovskite material 5 formed by reasonable diffusion in the film is correspondingly (A/C) (B/D) (Cl/X) 3 The mixed ionic perovskite, i.e. the conversion of the fully Cl-based first perovskite material 21 into mixed ionic perovskite, has a mixed ionic nature that greatly increases its solubility and can therefore be subsequently removed by washing with common solvents.
In step S140, as shown in fig. 8, the third perovskite material 5 may be specifically removed by a solvent rinsing method or a solvent soaking method to leave a portion of the first perovskite thin film 2 that is not imprinted, thereby forming the patterned first perovskite thin film 2.
When the solvent washing method is used, the amount of the solvent to be used and the number of times of washing may be controlled, for example, 10 mL/5 times of washing at the time of washing, but of course, other amounts and the number of times of washing may be used without particular limitation.
Optionally, the solvent comprises at least one of dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, chlorobenzene, and diethyl ether. The solvent may be one of the above solvents, or a mixed solution of at least two of the above solvents, and the specific mixing ratio may be set as required. For example, the third perovskite material 5 may be washed with a DMF (dimethylformamide)/CB (chlorobenzene) (DMF: cb=4:6) mixed solvent. Of course, other mixed solvents may be used, and are not particularly limited.
Optionally, the cleaning temperature is in the range of 20 ℃ to 80 ℃.
In some alternative embodiments, the step of providing the substrate 1 and forming the first perovskite thin film 2 on the substrate 1 includes the steps of: providing a substrate 1; a solution including a first perovskite material 21 is coated on a substrate 1, and is subjected to an annealing treatment to form a first perovskite thin film 2, wherein the first perovskite thin film 2 includes the first perovskite material 21.
In this embodiment, the solution including the first perovskite material 21 may be coated on the substrate 1 by a spin coating process, and spin coating parameters may be adjusted according to practical situations, for example, spin coating parameters are 4000rpm, 2000rpm/s, 30s, 0.1mL of chlorobenzene anti-solvent is added dropwise at the beginning of the procedure for 15s, and the preparation of the first perovskite thin film 2 is completed after the spin coating is completed with annealing treatment at 100 ℃ for 20 min. Of course, parameters such as the coating process, the coating parameters, the annealing temperature, and the annealing time can be adjusted according to the actual situation, and are not particularly limited.
In some alternative embodiments, the step of providing the stamp body 3 having the patterned first surface P1 and forming the second perovskite thin film 4 on the first surface P1 includes the steps of: providing a stamp body 3 having a patterned first surface P1; hydrophilic treatment is carried out on the first surface P1 of the stamp body 3; a solution including a second perovskite material 41 is coated on the first surface P1, and the second perovskite thin film 4 is formed through an annealing process, wherein the second perovskite thin film 4 includes the second perovskite material 41.
The first surface P1 of the stamp body 3 is subjected to hydrophilic treatment to improve wettability and adhesion of the solution including the second perovskite material 41 on the first surface P1 of the stamp body 3, for example, the first surface P1 of the stamp body 3 may be treated with an ultraviolet ozone treatment method for 10 minutes to improve wettability of the first surface P1.
Specifically, the second perovskite thin film 4 can be prepared by depositing on the first surface P1 of the seal body 3 by spin coating, wherein spin coating parameters can be 5000rpm, 2000rpm/s and 20s, 0.1mL of chlorobenzene anti-solvent is dropwise added at 15s at the beginning of spin coating, and annealing is carried out at 105 ℃ for 15min after spin coating is finished. Of course, parameters such as the coating process, the coating parameters, the annealing temperature, and the annealing time can be adjusted according to the actual situation, and are not particularly limited.
It should be noted that, adding chlorobenzene anti-solvent can slow down crystallization rate and rinse residual organic solvent to obtain a relatively flat film, but the dripping time needs to be controlled to obtain a film with a relatively good morphology.
In some alternative embodiments, the step of imprinting the second perovskite thin film 4 of the stamp body 3 in the first perovskite thin film 2 under a preset pressure to diffuse ions in the second perovskite material 41 into the first perovskite thin film 2 at corresponding imprint positions to form the third perovskite material 5 at the imprint positions includes the steps of: the second perovskite thin film 4 of the stamp body 3 is imprinted in the first perovskite thin film 2 at a preset pressure and a preset temperature, so that ions in the second perovskite material 41 are diffused into the first perovskite thin film 2 at the corresponding imprinting position, and a third perovskite material 5 is formed at the imprinting position.
It will be appreciated that in this embodiment, the second perovskite thin film 4 of the stamp body 3 needs to be stamped into the first perovskite thin film 2 at a preset pressure and a preset temperature, that is, the annealing is adopted to accelerate ion migration and perovskite phase formation during stamping, and the preset temperature is selected to be typically 70-300 ℃. Of course, different preset temperatures and heating times can be selected according to different experimental environments and conditions.
The preset pressure can be adjusted according to different perovskite components, and optionally, the range of the preset pressure is 0-100 MPa, and it is noted that when the preset pressure is 0MPa, that is, no additional pressure is applied in the imprinting process, and the specific preset pressure can be selected according to actual conditions.
In addition to the annealing mode used in the imprinting process, the annealing can be performed after the imprinting. Specifically, the second perovskite thin film 4 of the stamp body 3 is stamped in the first perovskite thin film 2 under a preset pressure, and then annealed to diffuse ions in the second perovskite material 41 into the first perovskite thin film 2 at the corresponding stamping position, so as to form the third perovskite material 5 at the stamping position.
In this embodiment, the second perovskite thin film 4 of the stamp body 3 is stamped on the first perovskite thin film 2 under a preset pressure of 0MPa to 100MPa, and the annealing treatment temperature is 70 ℃ to 300 ℃. For example, the preset pressure may be 0.5Mpa for 1min, and then the annealing treatment is performed, and the annealing may be performed at a temperature of 100 ℃ for 5min.
Of course, the preset pressure, duration, annealing temperature and annealing time may be adjusted according to the actual perovskite composition, and are not particularly limited.
As shown in fig. 9, in order to facilitate the subsequent preparation of the optoelectronic device, in some alternative embodiments, between the step of imprinting the second perovskite thin film 4 of the stamp body 3 in the first perovskite thin film 2 and the step of removing the third perovskite material 5 with a solvent, under a preset pressure, further comprises: a transport material layer 61 is formed on the side of the third perovskite thin film facing away from the substrate 1 and the side of the first perovskite thin film 2 facing away from the substrate 1.
It should be noted that, when the transmission material layer 61 is formed, the TPB (4-tert-butylpyridine) material may be coated on the side of the third perovskite film facing away from the substrate 1 and the side of the first perovskite film 2 facing away from the substrate 1, then the hole transporting/blocking layer of MoO3 is evaporated, and then the third perovskite film is rinsed and removed by the solvent, and the transmission material layer 61 above the third perovskite film is correspondingly broken and removed along with the solvent, so that the transmission material layer 61 forms the patterned transmission layer 6, as shown in fig. 10, and the perovskite/transmission layer 6 integrated device structure may be obtained.
As shown in fig. 11, optionally, after the perovskite/transmission layer 6 integrated device structure is obtained, a functional film layer such as an electrode layer 7 may be evaporated on a side of the transmission layer 6 away from the substrate 1 to complete the preparation of an LED (Light-Emitting Diode) device.
The following will further explain the principles and steps of the invention by referring to specific examples, but the invention is not limited to the following examples.
First, a first perovskite thin film 2 such as MAPbCl is prepared 3 Thin film and second perovskite thin film 4 such as MAPbI 3 A film. MAPbCl of 0.8mol/L 3 H of (2) 2 Spin-coating O solution onto the prepared ITO/ZnO/PEIE transparent conductive substrate 1, wherein spin-coating parameters are 4000rpm, 2000rpm/s and 30s, dropwise adding 0.1mL of chlorobenzene anti-solvent at 15s at the beginning of the procedure, and annealing at 100deg.C for 20min after spin-coating to complete MAPbCl 3 Preparing a film; for MAPbI 3 The preparation of the film first requires hydrophilic treatment of the first surface P1 of the nano-stamp body 3 already provided with the appropriate pattern.
For example, the first surface P1 of the PMMA nano seal body 3 is treated with an ultraviolet ozone treatment method for 10 minutes to improve wettability of the first surface P1. Subsequently 1.0mol/L MAPbI was added 3 (DMF: dmso=9:1) solution was deposited on the first surface P1 of the PMMA nano stamp body 3 by spin coating with spin coating parameters of 5000rpm, 2000rpm/s, 20s, dropwise adding 0.1mL of chlorobenzene anti-solvent at 15s from the beginning of the procedure, and annealing at 105 ℃ for 15min after spin coating was completed to complete MAPbI 3 And (3) preparing a film.
Thereafter, it is coated with MAPbCl 3 Film substrate 1 and MAPbI coated substrate 3 The nano stamp body 3 of the film is contacted and a pressure of 0.5MPa is applied for 1min, then annealing is carried out at 100 ℃ for 5min for the stamped film, and the stamping and annealing processes are all used for ensuring MAPbI 3 Film and MAPbCl 3 Ion migration before film and final contact area MAPb (I/Cl) 3 Perovskite formation. After annealing, separating the nano stamp from the substrate 1Can be obtained to include MAPbCl 3 And MAPb (I/Cl) 3 Is a patterned film of (a).
Finally, the formed film can be used for preparing the film comprising MAPbCl 3 And MAPb (I/Cl) 3 Is applied to the preparation of LED devices. In the presence of MAPbCl 3 And MAPb (I/Cl) 3 Is coated with a TPB transmission layer 6 and evaporated with 7nm MoO 3 The film was then washed 5 times with 10 mL/wash using a DMF/CB (DMF: CB=4:6) solvent mixture to remove the high solubility MAPb (I/Cl) from the imprinted region 3 Washing and removing perovskite to obtain MAPbCl 3 /TPB/MoO 3 The perovskite/transport layer 6 of the integrated device structure. Subsequently, 80nm Au is evaporated as a driving electrode to complete the patterning MAPbCl 3 And (3) preparing a purple light LED device.
The embodiment of the invention also provides a perovskite film, which is prepared by adopting the perovskite film preparation method in any embodiment.
Compared with the existing nano imprinting method, when the perovskite thin film provided by the embodiment of the invention is prepared by adopting the perovskite thin film preparation method in any embodiment, the excessive residues on the substrate 1 after imprinting is finished can be effectively avoided, the preparation yield of the patterned first perovskite thin film 2 is high, the cost is low, and meanwhile, the integrated preparation of a subsequent photoelectric device is also facilitated.
The embodiment of the invention also provides an optoelectronic device, which comprises the perovskite thin film in any embodiment.
The photoelectric device provided by the embodiment of the invention has the technical effects of the perovskite thin film in any one of the embodiments, and the same or corresponding structure and explanation of terms as those of the embodiment are not repeated here.
In the foregoing, only the specific embodiments of the present invention are described, and it will be clearly understood by those skilled in the art that, for convenience and brevity of description, the specific working processes of the systems, modules and units described above may refer to the corresponding processes in the foregoing method embodiments, which are not repeated herein. It should be understood that the scope of the present invention is not limited thereto, and any equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present invention, and they should be included in the scope of the present invention.
It should also be noted that the exemplary embodiments mentioned in this disclosure describe some methods or systems based on a series of steps or devices. However, the present invention is not limited to the order of the above-described steps, that is, the steps may be performed in the order mentioned in the embodiments, or may be performed in a different order from the order in the embodiments, or several steps may be performed simultaneously.
Claims (10)
1. The preparation method of the perovskite thin film is characterized by comprising the following steps of:
providing a substrate (1) and forming a first perovskite thin film (2) on the substrate (1), wherein the first perovskite thin film (2) comprises a first perovskite material (21);
providing a stamp body (3) having a patterned first surface (P1), and forming a second perovskite thin film (4) on the first surface (P1), wherein the second perovskite thin film (4) comprises a second perovskite material (41);
imprinting the second perovskite thin film (4) of the stamp body (3) in the first perovskite thin film (2) under a preset pressure so as to diffuse ions in the second perovskite material (41) into the first perovskite thin film (2) at corresponding imprinting positions to form a third perovskite material (5) at the imprinting positions, wherein the solubility of the third perovskite material (5) is greater than that of the first perovskite material (21);
the third perovskite material (5) is removed with a solvent to form a patterned first perovskite thin film (2).
2. The method for producing a perovskite thin film according to claim 1, wherein,
the first perovskite material (21) comprises ABCl 3 A comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (B) comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2+ 、Zn 2+ 、Cd 2+ 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of (a); and/or the number of the groups of groups,
the second perovskite material (41) comprises CDX 3 X includes I － 、Br － Or a combination thereof, C comprises Li + 、Na + 、K + 、Rb + 、Cs + 、CH 3 NH 3 + 、CH 3 CH 2 NH 3 + 、CH(NH 2 ) 2 + 、C 4 H 11 N + 、C 8 H 12 N + At least one cation of (a), D comprises Pb 2+ 、Sn 2+ 、Ge 2+ 、Mn 2+ 、Zn 2+ 、Cd 2+ 、Co 2+ 、Cu 2+ 、Ni 2+ At least one cation of the group.
3. The method of producing a perovskite thin film according to claim 1, wherein the step of providing a substrate (1) and forming a first perovskite thin film (2) on the substrate (1) comprises the steps of:
providing a substrate (1);
coating a solution comprising a first perovskite material (21) on the substrate (1), and forming a first perovskite thin film (2) through annealing treatment, wherein the first perovskite thin film (2) comprises the first perovskite material (21).
4. The method of producing a perovskite thin film as claimed in claim 1, wherein the step of providing a stamp body (3) having a patterned first surface (P1) and forming a second perovskite thin film (4) on the first surface (P1) comprises the steps of:
providing a stamp body (3) having a patterned first surface (P1);
hydrophilic treatment is carried out on the first surface (P1) of the seal body (3);
coating a solution comprising a second perovskite material (41) on the first surface (P1), and forming a second perovskite thin film (4) through annealing treatment, wherein the second perovskite thin film (4) comprises the second perovskite material (41).
5. The method of producing a perovskite thin film according to claim 1, wherein the step of imprinting the second perovskite thin film (4) of the stamp body (3) in the first perovskite thin film (2) under a preset pressure to diffuse ions in the second perovskite material (41) into the first perovskite thin film (2) at the corresponding imprint location to form a third perovskite material (5) at the imprint location includes the steps of:
imprinting the second perovskite thin film (4) of the stamp body (3) in the first perovskite thin film (2) under a preset pressure and a preset temperature so as to diffuse ions in the second perovskite material (41) into the first perovskite thin film (2) at the corresponding imprinting position to form a third perovskite material (5) at the imprinting position; or alternatively, the first and second heat exchangers may be,
imprinting the second perovskite thin film (4) of the stamp body (3) in the first perovskite thin film (2) under a preset pressure, and performing annealing treatment to diffuse ions in the second perovskite material (41) into the first perovskite thin film (2) at the corresponding imprinting position so as to form a third perovskite material (5) at the imprinting position;
the preset pressure is 0-100 MPa, and the preset temperature is 70-300 ℃;
the annealing treatment temperature is 70-300 ℃.
6. A method of producing a perovskite thin film according to claim 1, characterized in that the step of removing the third perovskite material (5) using a solvent comprises the steps of:
removing the third perovskite material (5) by a solvent flushing method or a solvent soaking method;
the solvent comprises at least one of dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, chlorobenzene and diethyl ether.
7. The method for producing a perovskite thin film according to claim 1, wherein,
the material of the substrate (1) comprises at least one of transparent conductive glass, oxide material and polymer material; and/or the number of the groups of groups,
the material of the seal body (3) comprises at least one of polydimethylsiloxane, polymethyl methacrylate and sapphire.
8. The method according to claim 1, characterized by further comprising, between the step of imprinting the second perovskite thin film (4) of the stamp body (3) in the first perovskite thin film (2) and the step of removing the third perovskite material (5) with a solvent, under the preset pressure:
a layer of transport material (61) is formed on the side of the third perovskite thin film facing away from the substrate (1) and on the side of the first perovskite thin film (2) facing away from the substrate (1).
9. A perovskite thin film prepared by the method of any one of claims 1 to 8.
10. An optoelectronic device comprising the perovskite thin film of claim 9.
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