CN114792762A - Method for preparing perovskite film under vacuum condition - Google Patents

Method for preparing perovskite film under vacuum condition Download PDF

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Publication number
CN114792762A
CN114792762A CN202210224151.XA CN202210224151A CN114792762A CN 114792762 A CN114792762 A CN 114792762A CN 202210224151 A CN202210224151 A CN 202210224151A CN 114792762 A CN114792762 A CN 114792762A
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perovskite
film
vacuum
perovskite precursor
precursor solution
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不公告发明人
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Shenzhen Heijing Optoelectronic Technology Co ltd
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Shenzhen Heijing Optoelectronic Technology Co ltd
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    • 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
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • H10K71/811—Controlling the atmosphere during processing

Abstract

The invention relates to a method for preparing a perovskite thin film under a vacuum condition, which comprises the following steps: preparing a perovskite wet film, vacuum-assisted perovskite phase formation, and annealing under a vacuum condition. The perovskite wet film is prepared by adopting a slit coating, spin coating or ink-jet printing method, the perovskite intermediate phase film is prepared by a vacuum flash evaporation process, and the perovskite intermediate phase film is annealed under the vacuum state, so that the high-quality perovskite film is prepared. Because the film is formed in the inert gas atmosphere and the vacuum state is kept in the film forming process, the influence of the water-oxygen atmosphere can be effectively isolated, and the prepared perovskite film has good uniformity and stable crystal structure.

Description

Method for preparing perovskite film under vacuum condition
Technical Field
The invention belongs to the technical field of perovskite solar cell preparation, and particularly relates to a method for preparing a perovskite thin film by vacuum-assisted perovskite phase formation and annealing under a vacuum condition.
Background
Perovskite solar cells (perovskite solar cells) are solar cells in which perovskite type organic metal halide semiconductors are used as light absorption materials in the form of thin films, the perovskite thin film forming is greatly influenced by the environment, and the control of temperature, humidity and air atmosphere is all key to influencing the efficiency of devices.
In the preparation of a typical perovskite layer, a perovskite wet film is coated on a substrate and then annealed. In the environment of continuously preparing the perovskite wet film, a large amount of organic solvent influences the preparation process of the film, so that the film formation of the perovskite film becomes difficult. Meanwhile, the perovskite thin film volatilizes an organic solvent in the wet film in the annealing process, and further solvent atmosphere for preparing the thin film is influenced. The annealed perovskite solar cell thin film is also affected by the ambient solvent atmosphere, thereby affecting the efficiency of the device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a perovskite thin film under a vacuum condition, which adopts vacuum flash evaporation to quickly remove a solvent and directly anneals in the vacuum state to obtain the high-quality perovskite thin film.
The invention provides a perovskite thin film prepared under vacuum condition, which comprises the following steps:
preparing a perovskite precursor solution: comprises a perovskite precursor, a ligand and a carrier solvent.
Further, the precursor in the perovskite solution is ABX 3 The perovskite type organic-inorganic composite material is characterized in that A is a positive monovalent element or an organic small molecular group, and comprises one or more cations of Li, Na, K, Rb, Cs, amidino or amino; wherein B is a positive divalent metal element, including but not limited to one or more cations of tungsten W, selenium Se, rhodium Rh, germanium Ge, tin Sn, lead Pb, arsenic As, indium In and antimony Sb; wherein X is a monovalent halogen element, including but not limited to one or more anions of fluorine F, chlorine Cl, bromine Br and iodine I.
Further, the ligand in the perovskite solution includes, but is not limited to, at least one of dimethyl sulfone DMSO, N-methyl pyrrolidone NMP, diphenyl sulfoxide DPSO, dimethyl thiopropionic acid DMSP.
Further, the carrier solvent in the perovskite precursor solution is an organic solvent, and includes but is not limited to one or more of dimethyl sulfone DMSO, ethylene glycol monomethyl ether 2-ME, gamma-inner butyl ester GBL, diphenyl sulfoxide DPSO, N-dimethylformamide DMF, and N-methylpyrrolidone NMP.
Optionally, the mass percentage of the perovskite precursor in the carrier solvent is 15-75 wt%.
Optionally, the molar ratio of the ligand in the perovskite precursor solution to the material B of claim 2 is 1: [0.5-1.5].
Optionally, the perovskite wet film preparation method includes spin coating, blade coating, slit coating, spray coating and the like.
Alternatively, perovskite coated substrates include, but are not limited to, ITO substrates, FTO substrates, Si substrates.
And carrying out vacuum flash evaporation treatment on the prepared perovskite precursor wet film, wherein the vacuum flash evaporation is carried out in a closed bin, a low-pressure state is quickly achieved through a vacuum pump, the boiling point of a solvent in the perovskite solution is reduced, the solvent is quickly boiled and gasified, and then the solvent is pumped away through a vacuum pipeline, so that a solute in the perovskite solution is pre-crystallized to reach an intermediate phase film.
Alternatively, the pressure in the vacuum chamber needs to be 1 × 10 2 Below Pa air pressure;
optionally, the vacuum state during flash evaporation needs to be maintained for more than 5s, preferably, 60s-100 s.
Keeping the vacuum state, moving the intermediate phase film to an annealing platform, and carrying out vacuum annealing. The process from flash evaporation to annealing is a perovskite film stabilization key point, the influence of the external environment on the perovskite film formation is thoroughly isolated in the film formation process, the reaction of water, oxygen and the perovskite film is avoided, the recombination of an organic solvent and the perovskite film is avoided, the crystallization effect of the obtained perovskite film is more compact, and the integral uniformity of the film surface is better.
Optionally, the annealing temperature is 40-250 ℃ and the annealing time is 5-60 min.
Preferably, the thickness of the perovskite film is 200-1000 nm.
Compared with the prior art, the invention has the following advantages:
the annealing device and the film making device are isolated, so that the influence of high temperature generated by continuous heating of the annealing device on the preparation of a perovskite wet film is effectively eliminated; the film is formed in inert gas, so that the compounding of water, oxygen, an organic solvent and a perovskite film in the air is effectively eliminated; the high vacuum state is maintained in the film forming process, the annealing temperature is reduced, the thermal decomposition of perovskite at high temperature is inhibited, and the stoichiometric ratio of the components is maintained.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a perovskite wet film coated on a substrate according to an embodiment of the present invention;
FIG. 2 is a diagram illustrating the formation of a mesophase thin film by a wet perovskite thin film under the action of vacuum flash evaporation according to an embodiment of the present invention;
FIG. 3 shows that the perovskite mesophase thin film in the embodiment of the invention is kept vacuum annealed to form a black uniform thin film.
Detailed Description
The technical solutions in the embodiments of the present invention will be further described below with reference to the drawings of the specification, and it is obvious that the described embodiments are only preferred embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing a perovskite thin film under a vacuum condition, which comprises the following steps:
a. preparing a perovskite precursor solution: comprises a perovskite precursor, a ligand and a carrier solvent;
b. preparing a perovskite wet film;
c. assisting the perovskite precursor film to be converted into an intermediate phase film in a vacuum chamber by a vacuum flash evaporation method;
d. and keeping the vacuum state of the vacuum bin, and annealing the intermediate phase film to obtain the perovskite film.
In the invention, the perovskite precursor in the perovskite precursor solution is ABX 3 The perovskite type organic-inorganic composite material is characterized in that A is a positive monovalent element or an organic small molecular group and comprises one or more cations of Li, Na, K, Rb, Cs, amidino or amino; wherein B is a positive divalent metal element and comprises one or more cations of tungsten W, selenium Se, rhodium Rh, germanium Ge, tin Sn, lead Pb, arsenic As, indium In and antimony Sb; wherein X is a monovalent halogen element, and comprises one or more anions of F, Cl, Br and I.
In the present invention, the ligand in the perovskite precursor solution includes, but is not limited to, at least one of dimethyl sulfone DMSO, N-methylpyrrolidone NMP, diphenyl sulfoxide DPSO, dimethyl thiopropionic acid DMSP.
In the invention, the carrier solvent in the perovskite precursor solution is one or more of ethylene glycol monomethyl ether 2-ME, gamma-inner butyl ester GBL, dimethyl sulfone DMSO, N-dimethylformamide DMF and N-methylpyrrolidone NMP.
In the present invention, in the perovskite precursor solution, the mass percentage content of the perovskite precursor in the carrier solvent is preferably 15 to 75 wt%.
In the present invention, the molar ratio of the ligand substance in the perovskite precursor solution to the B material in claim 2 is preferably 1: [0.5-1.5].
In the present invention, the perovskite coating substrate can be selected from an ITO substrate, an FTO substrate and a Si substrate.
In the present invention, the coating methods can be selected from spin coating, knife coating, slit coating and spray coating.
In the present invention, the air pressure in the vacuum chamber is preferably required to be 1 × 10 2 Pa or less.
In the present invention, the vacuum state during flash evaporation is preferably maintained for 5 seconds or more, and preferably 60 seconds to 100 seconds.
In the present invention, the annealing temperature is preferably 40 to 250 ℃ and the annealing time is preferably 5 to 60 min.
The following details preferred embodiments of the invention:
example 1:
(1) and (3) taking formamidine iodine, cesium iodide, lead iodide, DMF (dimethyl formamide) and DMSO (dimethyl sulfoxide) and uniformly mixing to obtain a perovskite precursor solution with the mass percentage of 30 wt%. Wherein the molar ratio of formamidine iodine, cesium iodide, lead iodide and NMP is 0.8: 0.2: 1.0: 1.0 to give a compound of the formula FA 0.8 Cs 0.2 PbI 3 The yellow perovskite precursor solution of (a).
(2) Coating the perovskite precursor solution on a substrate by adopting a slit coating process, and setting main slit coating parameters: the height of the coating cutter head and the substrate is 30um, the temperature of the base station is 25 ℃, the moving speed of the base station is 10mm/s, and the injection speed of the injection system is 1.5 ml/min.
(3) Performing air pumping and exhausting treatment on the vacuum chamber for more than 3 times, wherein the air pressure of each air pumping is lower than 1 × 10 2 Pa, the inflation gas is preferably nitrogen. Then, a heating table is opened, the set temperature is 90 ℃, after the temperature of the heating table is constant, the prepared perovskite wet film is placed into a bin, a bin door is closed, a vacuum pump is started, the bin body is quickly vacuumized, and when the air pressure in the bin is reduced to 1 multiplied by 10 -1 And keeping the vacuum degree below Pa for 40S, quickly volatilizing the solvent of the perovskite wet film in the bin during the period, and pumping away the solvent through a vacuum pipeline to obtain the brown perovskite intermediate phase film.
(4) The continuous vacuum degree is 1 × 10 -1 And Pa, rapidly moving the prepared intermediate phase film to a hot table for annealing for 15min to obtain a black uniform perovskite layer film with a mirror surface.
Example 2:
(1) and (3) taking formamidine iodine, cesium iodide, lead bromide, NMP and DMF, and uniformly mixing to obtain the perovskite ink with the mass percentage of 15 wt%. Wherein the molar ratio of formamidine iodine, cesium iodide, lead bromide and NMP is 0.95: 0.05: 0.95: 0.05:1.05, perovskite chemical formula FA 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 ) 3 。
(2) Adopting one-step spin coating process to prepare perovskiteSpin coating the precursor solution on the substrate, and setting main parameters of one-step spin coating: the rotating speed of the base station is 5000r/min, and the rotating acceleration of the base station is 1000r/s 2 The total time of the base rotation was 50 seconds.
(3) Performing air-extracting and air-releasing treatment on the vacuum chamber for more than 3 times, wherein the air pressure of air-extracting each time is lower than 1 × 10 2 Pa, the inflation gas is preferably nitrogen. Then, a heating table is opened, the set temperature is 150 ℃, after the temperature of the heating table is constant, the prepared perovskite wet film is placed into a bin, a bin door is closed, a vacuum pump is opened, the bin body is quickly vacuumized, and when the air pressure in the bin is reduced to 1 multiplied by 10 -1 And keeping the vacuum degree below Pa for 15S, quickly volatilizing the solvent of the perovskite wet film in the bin during the period, and pumping away the solvent through a vacuum pipeline to obtain the brown perovskite intermediate phase film.
(4) And filling nitrogen into the vacuum chamber to a normal pressure state, quickly moving the prepared intermediate phase film to a hot table for annealing for 10min to obtain the black uniform perovskite layer film with the mirror surface.
Example 3:
(1) and (3) uniformly mixing formamidine iodine, cesium iodide, lead bromide, DPSO, DMF and DMSO to obtain the perovskite ink with the mass percentage of 30 wt%. Wherein the molar ratio of formamidine iodine, methylamine bromide, cesium iodide, lead bromide and DPSO is 0.7: 0.15: 0.15: 0.85: 0.15:1.00, perovskite chemical formula FA 0.7 MA 0.15 Cs 0.15 Pb(I 0.85 Br 0.15 ) 3 。
(2) And printing the perovskite ink on the substrate by adopting an ink-jet printing process, wherein the temperature of the substrate is controlled at 20 ℃.
(3) Performing air-extracting and air-releasing treatment on the vacuum chamber for more than 3 times, wherein the air pressure of air-extracting each time is lower than 1 × 10 2 Pa, the inflation gas is preferably nitrogen. Then, a heating table is opened, the set temperature is 120 ℃, after the temperature of the heating table is constant, the prepared perovskite wet film is placed into a bin, a bin door is closed, a vacuum pump is started, the bin body is quickly vacuumized, and when the air pressure in the bin is reduced to 1 multiplied by 10 -1 Keeping vacuum degree below Pa for 70S, volatilizing solvent in the wet film in the bin, and pumping away the solvent via vacuum pipeline to obtain the final productBrown perovskite mesophase thin film.
(4) The continuous vacuum degree is 1 × 10 -2 And Pa, rapidly moving the prepared mesophase film to a hot table for annealing for 10min to obtain a black uniform perovskite layer film with a mirror surface. It should be understood that various other changes and modifications to the above-described embodiments may occur to those skilled in the art, and all such changes and modifications are intended to be included within the scope of the present invention.

Claims (10)

1. A method of preparing a perovskite thin film under vacuum conditions, comprising the steps of:
a. preparing a perovskite precursor solution: comprises a perovskite precursor, a ligand and a carrier solvent;
b. preparing a perovskite wet film;
c. assisting the perovskite precursor film to be converted into an intermediate phase film in a vacuum bin by a vacuum flash evaporation method;
d. and keeping the vacuum state of the vacuum bin, and annealing the intermediate phase film to obtain the perovskite film.
2. The method according to claim 1, wherein in step a, the perovskite precursor in the perovskite precursor solution is ABX 3 The perovskite type organic-inorganic composite material is characterized by comprising a perovskite type organic-inorganic composite perovskite, wherein A is a positive monovalent element or an organic small molecular group and comprises one or more cations of lithium Li, sodium Na, potassium K, rubidium Rb, cesium Cs, amidino or amino; wherein B is a positive divalent metal element and comprises one or more cations of tungsten W, selenium Se, rhodium Rh, germanium Ge, tin Sn, lead Pb, arsenic As, indium In and antimony Sb; wherein X is a monovalent halogen element, and comprises one or more anions of fluorine F, chlorine Cl, bromine Br and iodine I.
3. The method according to claim 1, wherein in step a, the ligand in the perovskite precursor solution comprises at least one of but not limited to dimethyl sulfone (DMSO), N-methylpyrrolidone (NMP) diphenyl sulfoxide (DPSO), dimethyl thiopropionic acid (DMSP).
4. The method according to claim 1, wherein in step a, the carrier solvent in the perovskite precursor solution is one or more of ethylene glycol monomethyl ether 2-ME, gamma-butyrolactone GBL, dimethyl sulfone DMSO, N-dimethylformamide DMF, and N-methylpyrrolidone NMP.
5. The process according to claim 1, wherein in step a, the perovskite precursor is present in the perovskite precursor solution in an amount of 15 to 75 wt% based on the mass of the perovskite precursor in the carrier solvent.
6. The method according to claim 1, wherein in step a, the molar ratio of the ligand species in the perovskite precursor solution to the B material of claim 2 is 1: [0.5-1.5].
7. The method of claim 1, wherein in step b, the perovskite coated substrate comprises an ITO substrate, an FTO substrate, a Si substrate.
8. The method of claim 1, wherein in step b, the coating comprises spin coating, blade coating, slit coating, or spray coating.
9. The method of claim 1, wherein in step c, the pressure in the vacuum chamber is required to be 1 x 10 2 Below Pa air pressure; the vacuum state needs to be maintained for 5-300s during flash evaporation.
10. The method of claim 1, wherein in step d, the annealing temperature is 40-250 ℃ and the annealing time is 5-60 min.
CN202210224151.XA 2022-03-07 2022-03-07 Method for preparing perovskite film under vacuum condition Pending CN114792762A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115347125A (en) * 2022-10-18 2022-11-15 中国华能集团清洁能源技术研究院有限公司 Rapid in-situ annealing method and annealing device for perovskite material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115347125A (en) * 2022-10-18 2022-11-15 中国华能集团清洁能源技术研究院有限公司 Rapid in-situ annealing method and annealing device for perovskite material

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