CN114456642B - Perovskite ink and preparation method of perovskite film - Google Patents
Perovskite ink and preparation method of perovskite film Download PDFInfo
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- CN114456642B CN114456642B CN202210098181.0A CN202210098181A CN114456642B CN 114456642 B CN114456642 B CN 114456642B CN 202210098181 A CN202210098181 A CN 202210098181A CN 114456642 B CN114456642 B CN 114456642B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 238000007641 inkjet printing Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 56
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 43
- 150000001768 cations Chemical class 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 16
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LAAFGFCPKSXKEM-UHFFFAOYSA-N 1-pentylsulfinylpentane Chemical compound CCCCCS(=O)CCCCC LAAFGFCPKSXKEM-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000002577 pseudohalo group Chemical group 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- DFPOZTRSOAQFIK-UHFFFAOYSA-N S,S-dimethyl-beta-propiothetin Chemical compound C[S+](C)CCC([O-])=O DFPOZTRSOAQFIK-UHFFFAOYSA-N 0.000 claims 1
- 239000013590 bulk material Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 229960001196 thiotepa Drugs 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000007664 blowing Methods 0.000 description 8
- SBMMOLKBPGETHC-UHFFFAOYSA-N [I].NC=N Chemical compound [I].NC=N SBMMOLKBPGETHC-UHFFFAOYSA-N 0.000 description 6
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 4
- RRUMKKGRKSSZKY-UHFFFAOYSA-N 2-carboxyethyl(dimethyl)sulfanium;chloride Chemical compound [Cl-].C[S+](C)CCC(O)=O RRUMKKGRKSSZKY-UHFFFAOYSA-N 0.000 description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GBMPPHPJKKUMPS-UHFFFAOYSA-N [Br].CN Chemical compound [Br].CN GBMPPHPJKKUMPS-UHFFFAOYSA-N 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- 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
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- 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 perovskite ink and a preparation method of a perovskite film, wherein the method comprises the following steps: uniformly mixing a perovskite precursor, a ligand solvent and a carrier solvent to prepare the perovskite ink; printing the perovskite ink on a substrate under a preparation environment by adopting an ink-jet printing process to obtain a perovskite wet film; maintaining a gas flow rate above the substrate to enable the perovskite wet film to be naturally nucleated, so as to form a perovskite pre-crystallization dry film; and under the annealing condition, crystallizing and solidifying the perovskite pre-crystallized dry film to form a perovskite film. According to the invention, the perovskite ink is configured, so that the perovskite film can be rapidly formed by an ink-jet printing technology, and the perovskite film is accurately controlled.
Description
Technical Field
The invention relates to the technical field of solar energy, in particular to perovskite ink and a preparation method of a perovskite film.
Background
The perovskite material has the characteristics of high carrier mobility, adjustable band gap, simple preparation and synthesis process, low cost and the like, has quite large application prospect in the field of solar photovoltaics, and the photoelectric conversion efficiency of the perovskite battery of the current laboratory index is over 25 percent. In order to realize industrial production and commercial application of perovskite materials in the photovoltaic field, the large-area deposition process of perovskite thin films is very critical.
In terms of preparation process, the perovskite thin film can be realized by various methods such as evaporation, silk screen printing, spin coating, knife coating, slit coating, ink jet printing and the like, wherein the evaporation cost is high, the precision and the thickness of the silk screen printing are difficult to control, and the spin coating is not suitable for mass production.
At present, the uniform coating of the perovskite film is mainly realized in a slit coating mode in the industry, the precision requirement of the technology on equipment is very high, and the defects of uneven thickness and the like of coating liquid are often caused by unstable stress. Secondly, the crystallization phase formation of the perovskite film is often realized by adopting an anti-solvent extraction or vacuum flash evaporation mode, so that the cost is increased, and meanwhile, the reliability is difficult to ensure. How to nucleate perovskite naturally and combine with the ink-jet printing technology is the key of large-scale continuous low-cost industrial production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides perovskite ink and a preparation method of a perovskite film.
In order to solve the above problems, the present invention proposes a perovskite ink including: perovskite precursor, ligand and carrier solvent, perovskite precursor is the perovskite material based on ABX3 structure, wherein: a is a monovalent cation, B is a divalent cation, and X is a monovalent anion;
the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%;
the molar ratio of the ligand to the B material in ABX3 is 1: [0.5-1.5].
The A is one or more cations in potassium, cesium, rubidium, methylamino or formamidino;
the B is one or more cations in lead and tin;
and X is one or more anions of halogen elements and halogen-like elements.
The halogen elements are as follows: iodine, bromine, chlorine.
The ligand comprises at least one of dimethyl sulfoxide DMSO and nitrogen methyl pyrrolidone NMP, DPSO, DMSP.
The carrier solvent comprises at least one of dimethylformamide DMF, dimethyl sulfoxide DMSO, gamma butyrolactone GBL,2-ME, gamma valerolactone E.
Correspondingly, the invention also provides a preparation method of the perovskite thin film, which comprises the following steps:
uniformly mixing a perovskite precursor, a ligand solvent and a carrier solvent to prepare the perovskite ink;
printing the perovskite ink on a substrate under a preparation environment by adopting an ink-jet printing process to obtain a perovskite wet film;
maintaining a gas flow rate above the substrate to enable the perovskite wet film to be naturally nucleated, so as to form a perovskite pre-crystallization dry film;
and under the annealing condition, crystallizing and solidifying the perovskite pre-crystallized dry film to form a perovskite film.
The preparation environment is an air or inert gas environment with humidity less than 40%; the temperature of the substrate is controlled to be 10-80 ℃.
The gas flow rate is 0-5m/s.
The annealing conditions are one or more steps of thermal annealing.
The annealing temperature of the annealing condition is 60-200 ℃.
According to the invention, the perovskite ink is prepared, and the perovskite film required by the formation on the substrate can be rapidly formed by combining the prepared perovskite ink with an inkjet printing technology, so that the thickness and the position of the perovskite film can be accurately controlled in a micron level under the control of inkjet printing; the perovskite film can be industrially produced in a large scale and continuously at low cost by natural nucleation of perovskite and combination with an ink-jet printing technology.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing a perovskite thin film according to an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The perovskite ink according to the embodiment of the invention comprises: perovskite precursor, ligand and carrier solvent, perovskite precursor is the perovskite material based on ABX3 structure, wherein: a is a monovalent cation, B is a divalent cation, and X is a monovalent anion; the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%; the molar ratio of the ligand to the B material in ABX3 is 1: [0.5-1.5]. The ligand needs to coordinate with the substances in the perovskite precursor, namely the perovskite precursor can reduce the crystallization condition when the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%, so that the molar ratio of the ligand to the B material in the ABX3 is 1: [0.5-1.5] and the like define the concentration of the ink through mass ratio descriptions, and the perovskite ink is more suitable for inkjet printing, so that the perovskite ink can be combined with a film forming method which is given later, is easier to form a film, and cannot be suitable for inkjet printing and cannot form a titanium ore film under the condition that the range of the interval is not limited.
The A is one or more cations of potassium, cesium, rubidium, methylamino or formamidino; b is one or more cations in lead and tin; the X is one or more anions selected from halogen elements and halogen-like elements.
The halogen elements are as follows: iodine, bromine, chlorine.
The ligand includes at least one of dimethyl sulfoxide DMSO, nitrogen methyl pyrrolidone NMP, dipentyl sulfoxide DPSO, and dimethyl-beta-propionine DMSP.
The carrier solvent includes at least one of dimethylformamide DMF, dimethyl sulfoxide DMSO, gamma-butyrolactone GBL,2-ME, and gamma-valerolactone E.
It is noted that the perovskite precursor comprises three materials of A, B and X and has a general formula of ABX 3 Wherein a is a monovalent cation: including but not limited to one or more cations of potassium (K), cesium (Cs), rubidium (Rb), methylamino or formamidino, B is a divalent cation: including but not limited to one or more of lead (Pb), tin (Sn)Cation, X is a monovalent anion: including but not limited to halogen elements: one or more anions selected from iodine (I), bromine (Br), chlorine (Cl) and halogen-like elements.
In particular, the perovskite precursor may include one or more mixtures of iodides, bromides, chlorides, and pseudohalides.
Based on the perovskite ink, the perovskite film is easier to form on the substrate through an ink-jet printer, and the perovskite film is convenient to prepare.
The perovskite precursor is used as a perovskite light absorption layer material, the ligand can form coordination with the perovskite precursor to promote perovskite crystallization, and the carrier solvent can dissolve the perovskite precursor and the ligand to form perovskite ink, so that the preparation of the perovskite film is realized by the convenient ink-jet printing technology.
Example two
Fig. 1 shows a flowchart of a preparation method of a perovskite thin film according to an embodiment of the invention, the preparation method includes:
s11, uniformly mixing a perovskite precursor, a ligand solvent and a carrier solvent to prepare perovskite ink;
the perovskite ink includes: perovskite precursor, ligand and carrier solvent, perovskite precursor is the perovskite material based on ABX3 structure, wherein: a is a monovalent cation, B is a divalent cation, and X is a monovalent anion; the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%; the molar ratio of the ligand to the B material in ABX3 is 1: [0.5-1.5]. The ligand needs to coordinate with the substances in the perovskite precursor, namely the perovskite precursor can reduce the crystallization condition when the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%, so that the molar ratio of the ligand to the B material in the ABX3 is 1: [0.5-1.5] and the like define the concentration of the ink through mass ratio descriptions, and the perovskite ink is more suitable for inkjet printing, so that the perovskite ink can be combined with a film forming method which is given later, is easier to form a film, and cannot be suitable for inkjet printing and cannot form a titanium ore film under the condition that the range of the interval is not limited.
The perovskite precursor is used as a perovskite light absorption layer material, the ligand can form coordination with the perovskite precursor to promote perovskite crystallization, and the carrier solvent can dissolve the perovskite precursor and the ligand to form perovskite ink, so that the preparation of the perovskite film is realized by the convenient ink-jet printing technology.
The A is one or more cations of potassium, cesium, rubidium, methylamino or formamidino; b is one or more cations in lead and tin; the X is one or more anions selected from halogen elements and halogen-like elements.
The halogen elements are as follows: iodine, bromine, chlorine.
The ligand includes at least one of dimethyl sulfoxide DMSO, nitrogen methyl pyrrolidone NMP, dipentyl sulfoxide DPSO, and dimethyl-beta-propionine DMSP.
The carrier solvent includes at least one of dimethylformamide DMF, dimethyl sulfoxide DMSO, gamma-butyrolactone GBL,2-ME, and gamma-valerolactone E.
It is noted that the perovskite precursor comprises three materials of A, B and X and has a general formula of ABX 3 Wherein a is a monovalent cation: including but not limited to one or more cations of potassium (K), cesium (Cs), rubidium (Rb), methylamino or formamidino, B is a divalent cation: including but not limited to one or more cations of lead (Pb), tin (Sn), X being a monovalent anion: including but not limited to halogen elements: one or more anions selected from iodine (I), bromine (Br), chlorine (Cl) and halogen-like elements.
In particular, the perovskite precursor may include one or more mixtures of iodides, bromides, chlorides, and pseudohalides.
Based on the perovskite ink, the perovskite film is easier to form on the substrate through an ink-jet printer, and the perovskite film is convenient to prepare.
S12, printing the perovskite ink on a substrate by adopting an ink-jet printing process under a preparation environment to obtain a perovskite wet film;
the preparation environment is air or inert gas environment with humidity less than 40%; the temperature of the substrate is controlled to be 10-80 ℃.
S13, maintaining the gas flow rate above the substrate to enable the perovskite wet film to be naturally nucleated, so as to form a perovskite pre-crystallization dry film;
the gas flow rate was 0 to 5m/s.
S14, under the annealing condition, crystallizing and solidifying the perovskite pre-crystallized dry film to form a perovskite film.
The annealing condition is one or more steps of heating annealing, and the annealing temperature of the annealing condition is 60-200 ℃.
Example III
Step 31: and uniformly mixing formamidine iodine, cesium iodide, lead iodide, NMP and DMF to obtain the perovskite ink with the mass percent of 30 weight percent. Wherein the mole ratio of formamidine iodine, cesium iodide and lead iodide, NMP is 0.8:0.2:1.0:1.0 to give a formula FA 0.8 Cs 0.2 PbI 3 Is a yellow perovskite ink. Step 32: the perovskite ink is printed on the substrate by adopting an ink-jet printing process, and the temperature of the substrate is controlled at 40 ℃.
Step 33: the wet perovskite film is uniformly purged by means including, but not limited to, blowing, air blowing, and the like, so that the yellow wet perovskite film is converted into a brown phase pre-crystallized dry film.
Step 34: and (3) annealing the perovskite pre-crystallization dry film for 30 minutes at 150 ℃ to crystallize and solidify the perovskite pre-crystallization dry film to form a perovskite film.
Example IV
S41, uniformly mixing formamidine iodine, cesium iodide, lead bromide, NMP and DMF to obtain the perovskite ink with the mass percentage of 15 wt%. Wherein the mole ratio of formamidine iodine, cesium iodide, lead bromide and NMP is 0.95:0.05:0.95:0.05:1.05, perovskite formula FA0.95Cs0.05Pb (I0.95Br0.05) 3.
S42, printing perovskite ink on a substrate by adopting an ink-jet printing process, wherein the temperature of the substrate is controlled at 20 DEG C
S43, uniformly blowing the perovskite wet film by means including but not limited to blowing, air blowing and the like to convert the yellow perovskite wet film into a brown phase pre-crystallized dry film
S44, carrying out three-stage annealing at 70 ℃ for 30 seconds, 100 ℃ for 2 minutes and 150 ℃ for 5 minutes on the perovskite pre-crystallization dry film, and crystallizing and solidifying the perovskite pre-crystallization dry film to form the perovskite thin film.
Example five
S51, taking formamidine iodine, cesium iodide, lead bromide and DPSO, DMF, DMSO, and uniformly mixing to obtain the perovskite ink with the mass percent of 30 wt%. Wherein the mole ratio of formamidine iodine, methylamine bromine, cesium iodide, lead bromide and DPSO is 0.7:0.15:0.15:0.85:0.15:1.00, perovskite formula is FA 0.7 MA 0.15 Cs 0.15 Pb(I 0.85 Br 0.15 ) 3 。
S52, printing perovskite ink onto a substrate by adopting an ink-jet printing process, wherein the temperature of the substrate is controlled at 70 ℃.
And S53, uniformly blowing the perovskite wet film by means of blowing, air blowing and the like, so that the yellow perovskite wet film is converted into a brown phase pre-crystallized dry film.
And S54, annealing the perovskite pre-crystallization dry film for 10 minutes at 120 ℃ to crystallize and solidify the perovskite pre-crystallization dry film to form a perovskite film.
According to the embodiment of the invention, the perovskite ink is configured, and the perovskite film required by the formation on the substrate can be rapidly formed by combining the perovskite ink with the inkjet printing technology, so that the thickness and the position of the perovskite film can be accurately controlled in a micron level under the control of inkjet printing; the perovskite film can be industrially produced in a large scale and continuously at low cost by natural nucleation of perovskite and combination with an ink-jet printing technology.
The foregoing has outlined rather broadly the more detailed description of embodiments of the invention, wherein the principles and embodiments of the invention are explained in detail using specific examples, the description of the embodiments being merely intended to facilitate an understanding of the method of the invention and its core concepts; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (6)
1. A method for producing a perovskite thin film, comprising: uniformly mixing a perovskite precursor, a ligand solvent and a carrier solvent to prepare perovskite ink;
printing the perovskite ink on a substrate under a preparation environment by adopting an ink-jet printing process to obtain a perovskite wet film;
maintaining a gas flow rate above the substrate to enable the perovskite wet film to be naturally nucleated, so as to form a perovskite pre-crystallization dry film;
under the annealing condition, carrying out three-stage annealing at 70 ℃ for 30 seconds, 100 ℃ for 2 minutes and 150 ℃ for 5 minutes on the perovskite pre-crystallization dry film, so that the perovskite pre-crystallization dry film is crystallized and solidified to form a perovskite film;
the perovskite ink includes: perovskite precursor, ligand and carrier solvent, wherein the perovskite precursor is based on ABX 3 A perovskite material of the structure, wherein: a is a monovalent cation, B is a divalent cation, and X is a monovalent anion;
the mass percentage of the perovskite precursor in the carrier solvent is 10-80wt%;
the ligand and ABX 3 The mol ratio of the B material in the preparation is 1:0.5-1.5]；
The perovskite precursor includes one or more of iodide, bromide, chloride, and pseudohalide mixtures.
2. The method of claim 1, wherein a is one or more cations of potassium, cesium, rubidium, methylamino, or formamidino;
the B is one or 2 cations in lead and tin;
and X is one or more anions in halogen elements and halogen-like elements.
3. The method for producing a perovskite thin film as claimed in claim 2, wherein the halogen element is: iodine, bromine, chlorine.
4. The method for producing a perovskite thin film as claimed in claim 1, wherein the compounding is
The bulk material comprises at least one of dimethyl sulfoxide DMSO, N-methyl pyrrolidone NMP, dipentyl sulfoxide DPSO and dimethyl-beta-thiotepa DMSP.
5. The method of preparing a perovskite thin film as claimed in claim 1, wherein the carrier solvent comprises at least one of dimethylformamide DMF, dimethylsulfoxide DMSO, gamma-butyrolactone GBL.
6. The method of claim 1, wherein the preparation environment is an air or inert gas environment with humidity less than 40%; the temperature of the substrate is controlled to be 10-80 ℃.
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