CN106159097A - A kind of new method improving perovskite thin film quality - Google Patents
A kind of new method improving perovskite thin film quality Download PDFInfo
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Abstract
The present invention relates to a kind of new method improving perovskite thin film.The invention belongs to the preparation method of thin-film material, it is characterized by through organic amine gas or organic amine solution, perovskite thin film is processed certain time, improve the quality of perovskite thin film, the treated defect that can effectively repair perovskite thin film, reduce surface roughness, improve film property.Perovskite thin film thickness prepared by this technique is homogeneous, and roughness is low, good crystallinity, and this technological operation is simple, with low cost, is suitably applied large area and prepares efficient perovskite solaode, light emitting diode, light-sensitive element and Laser Devices.
Description
Technical field
The invention belongs to the preparation method of thin-film material, be specifically related to a kind of new method improving perovskite thin film quality.
Background technology
Organic inorganic hybridization perovskite is due to optical, electrical, the magnetic property of its uniqueness and the feature such as preparation technology is simple, raw material dosage is few, low cost, receive much concern always, particularly since within 2009, being applied in solaode for the first time, perovskite solaode is rapidly risen to current 20.1% by 3.8%, and perovskite also receives the extensive concern of people in the field such as diode and Laser Devices.In these devices, perovskite active material is its core, and the quality of perovskite film is the key factor affecting device performance, and therefore, the research to perovskite film property is significant.
The film property of perovskite is closely related with the preparation technology of perovskite.As a rule, the film-forming process of perovskite can be divided mainly into solwution method, evaporation, and both combinations.Solwution method mainly has a step solwution method and two step infusion methods.One step solwution method is a kind of the most cheap and easily operated method preparing perovskite solaode.But perovskite thin film film property prepared by a traditional step solwution method is poor.For improving its film property, to perovskite precursor solution (PbI2:CH3NH3I=1:1) additive is added in (such as CH3NH3Cl, NH4Cl, HI etc.) film property and the crystal property of perovskite can be effectively improved.It addition, introduce PbCl2And PbAc2Also the film property of perovskite can be effectively improved.The anti-solvent method of report can largely improve the film property of perovskite recently, but this kind of method is harsh to technological requirement, is difficult to operation, and the method large-scale production to be realized is relatively difficult.Two step infusion methods are also to prepare the common method of efficient calcium titanium ore solaode.But to be fully converted to perovskite relatively difficult for lead iodide in infusion method, long period of soaking may destroy again perovskite film, is then prepared efficient perovskite thin film by infusion method higher to technological requirement.
Evaporation mainly has double source vapour deposition, continuous vapour deposition, chemical gaseous phase deposition and single source heat melting method etc..The perovskite film crystallinity of the preparation such as the gas phase assisted solution method being combined with evaporation and solwution method by evaporation and film property are all good, but this evaporation and pyroprocess add the cost preparing perovskite, thus limit the extensive preparation of perovskite thin film.Then, develop the most easily-controllable perovskite film-forming process and be still particularly important.
Summary of the invention
It is an object of the invention to provide a kind of new method improving perovskite thin film quality.
The technical solution used in the present invention is for achieving the above object: a kind of new method improving perovskite thin film quality, mainly comprise the following steps: at a certain temperature, perovskite thin film is processed certain time through organic amine gas or organic amine solution, improves the quality of perovskite thin film.
Described perovskite structure formula is ABX3, in formula, A is CH3NH3、NH2-CH=NH2In one or both complex, B be Pb, X be one or both the complex in I, Br, Cl.
Described organic amine is methylamine, carbonamidine, ethamine, triethylamine, propylamine, the one or two kinds of in hydrazine or two or more mixture.
The time range of described process is between 0.1s to 100h.
The solvent of described organic amine solution is the one or two kinds of in chlorobenzene, benzene, toluene, ether, isopentane, pentane, petroleum ether, hexane, hexamethylene, isobutyltrimethylmethane., Pentamethylene., heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, propyl ether, xylol, o-dichlorohenzene, benzene, dichloromethane, chloroform, tetrachloromethane, pyridine or two or more mixture.
Described organic amine solution concentration is between 0 to saturated concentration.
Described being processed by perovskite thin film organic amine solution can be to be soaked in organic amine solution by perovskite thin film, it is also possible to is to be dripped on perovskite thin film by organic amine solution.
Described perovskite thin film is-50 through organic amine gas or the temperature when organic amine solution processesoC to 200oBetween C.
The application in solaode, diode, gas sensor and laser instrument of the described perovskite thin film.
Advantage for present invention:
The present invention processes perovskite thin film by organic amine, and solid-state perovskite thin film becomes liquid condition owing to having adsorbed organic amine, owing to liquid flows, so that film realizes all standing.After perovskite thin film removes from organic amine environment, due to the effumability of organic amine gas, under room temperature, organic amine the most easily evaporates from liquid, thus again becomes cubic perovskite phase thin film.
Owing to the perovskite film of liquid flowing preparation is the most smooth, and uniformity is high, and defect is few, and roughness is low, decreases the compound of exciton, and the roughness of film is up to below 3nm after tested, has fabulous flatness.Additionally, just can evaporate from liquid under organic amine room temperature, this method can realize the room temperature of perovskite film and prepare, and perovskite film prepared by this room temperature has good crystallinity and has good crystal lattice orientation, the most this method to prepare perovskite thin film to have more universality and more preferable photoelectric properties.
This technique is more easy to operation than evaporation and successive sedimentation method, and cost is less expensive, more conducively large-scale production.A this technique relatively step solwution method film property has had and has been greatly improved, and degree of crystallinity greatly improves.This film can be competent at multiple device architecture, such as mesoporous and plane perovskite solaode, diode, gas sensor and laser instrument.
Accompanying drawing explanation
Accompanying drawing 1 is the XRD of perovskite film before and after methylamine gas processes.
Accompanying drawing 2 is SEM and AFM of perovskite film before and after methylamine gas processes；Wherein, (a) is SEM before treatment figure, and (b) (c) is the SEM figure after processing, and (d) (e) is AFM before treatment figure, and (f) (g) is the AFM figure after processing.
Accompanying drawing 3 is the IV curve of perovskite film before and after methylamine gas processes.
Accompanying drawing 4 is the SEM of perovskite film after the chlorobenzene solution of methylamine processes.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited to following example.
Embodiment 1
First, sol-gal process prepares TiO2Colloid, is spun on cleaned FTO glass, and then 500oC heat treated 30 min, obtains the TiO of densification2Thin film.Spin coating TiO on a dense film2Slurry, TiO2Granular size ~ 20 nm, the most further 500oC heat treated 30 min, obtains TiO2Mesopore film.Secondly, according to molar percentage 1:1 by PbI2And CH3NH3I is dissolved in DMF solution, and preparation mass ratio is the solution of 40%, is then spin coated onto at mesoporous TiO2On film, it is heated to 100oC, 10 min, evaporation of solvent, then by the CH of preparation3NH3PbI3Film methylamine gas smokes 2-6s, obtains the perovskite thin film that compact crystal is good.Last spin coating hole transmission layer spiro, evaporation silver electrode on calcium titanium ore bed, is assembled into solar cell device.
The perovskite film obtaining the present embodiment and the solaode of thus film preparation characterize, as in Fig. 1 before and after methylamine gas processes the XRD of perovskite film show, the smoked crystallinity of perovskite film afterwards of methylamine gas has had and has been greatly improved.As in Fig. 2 before and after methylamine gas processes SEM and AFM of perovskite film show, after methylamine gas is smoked, the flatness of perovskite film has had and has been greatly improved, and roughness is become the 6.53nm after smoking by the 153nm before smoking.As in Fig. 3 before and after methylamine gas processes the IV curve of perovskite film show, the efficiency of perovskite battery is risen to 15.4% after smoking by 3.8% before smoking.
Embodiment 2
First, sol-gal process prepares TiO2Colloid, is spun on cleaned FTO glass, and then 500oC heat treated 30 min, obtains the TiO of densification2Thin film.Secondly, according to molar percentage 1:1 by PbI2And CH3NH3I is dissolved in DMF solution, and preparation mass ratio is the solution of 40%, is then spin coated onto at mesoporous TiO2On film, it is heated to 100oC, 10 min, evaporation of solvent, then to the CH of preparation3NH3PbI3Drip the chlorobenzene solution of methylamine on film, naturally dry, obtain the perovskite thin film that compact crystal is good.Last spin coating hole transmission layer spiro, gold evaporation electrode on calcium titanium ore bed, is assembled into solar cell device.As the SEM of perovskite film shows before and after in Fig. 4, chlorobenzene solution through methylamine processes, the perovskite film of preparation has good crystallinity.
Claims (9)
1. improve a new method for perovskite thin film quality, mainly comprise the following steps:
At a certain temperature, perovskite thin film is processed certain time through organic amine gas or organic amine solution, improves the quality of perovskite thin film.
A kind of new method improving perovskite thin film quality the most according to claim 1, perovskite structure formula is ABX3, in formula, A is CH3NH3、NH2-CH=NH2In one or both complex, B be Pb, X be one or both the complex in I, Br, Cl.
A kind of new method improving perovskite thin film quality the most according to claim 1, organic amine is methylamine, carbonamidine, ethamine, triethylamine, propylamine, the one or two kinds of in hydrazine or two or more mixture.
A kind of new method improving perovskite thin film quality the most according to claim 1, the time range of process is between 0.1s to 100h.
A kind of new method improving perovskite thin film quality the most according to claim 1, the solvent of organic amine solution is the one or two kinds of in chlorobenzene, benzene, toluene, ether, isopentane, pentane, petroleum ether, hexane, hexamethylene, isobutyltrimethylmethane., Pentamethylene., heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, propyl ether, xylol, o-dichlorohenzene, benzene, dichloromethane, chloroform, tetrachloromethane, pyridine or two or more mixture.
A kind of new method improving perovskite thin film quality the most according to claim 1, organic amine solution concentration is between 0 to saturated concentration.
A kind of new method improving perovskite thin film quality the most according to claim 1, being processed by perovskite thin film organic amine solution can be to be soaked in organic amine solution by perovskite thin film, it is also possible to be to be dripped on perovskite thin film by organic amine solution.
A kind of new method improving perovskite thin film quality the most according to claim 1, perovskite thin film is-50 through organic amine gas or the temperature when organic amine solution processesoC to 200oBetween C.
9. the application in solaode, diode, gas sensor and laser instrument of the perovskite thin film described in claim 1.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711335A (en) * | 2017-01-04 | 2017-05-24 | 苏州黎元新能源科技有限公司 | Perovskite precursor and preparation method thereof |
| CN106757371A (en) * | 2016-12-19 | 2017-05-31 | 山东大学 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
| CN107146849A (en) * | 2017-06-08 | 2017-09-08 | 华中科技大学 | A kind of recycling processing method of perovskite solar cell |
| CN107331774A (en) * | 2017-04-21 | 2017-11-07 | 青岛科技大学 | The perovskite solar cell of double passivation layer structures |
| CN108011046A (en) * | 2017-11-14 | 2018-05-08 | 浙江理工大学 | A kind of method of perovskite surface in situ method growth perovskite nano wire and a kind of perovskite solar cell |
| CN108461632A (en) * | 2017-02-21 | 2018-08-28 | 华邦电子股份有限公司 | Perovskite composite construction |
| CN109904322A (en) * | 2019-03-08 | 2019-06-18 | 中国科学院青岛生物能源与过程研究所 | A method of preparing full-inorganic perovskite thin film |
| CN111403610A (en) * | 2020-03-19 | 2020-07-10 | 武汉理工大学 | High-performance organic-inorganic hybrid perovskite photoelectric material and preparation method and application thereof |
| CN111435708A (en) * | 2019-06-25 | 2020-07-21 | 杭州纤纳光电科技有限公司 | Method for repairing defect of perovskite thin film |
| CN111435705A (en) * | 2019-06-12 | 2020-07-21 | 杭州纤纳光电科技有限公司 | Repairing agent and repairing method thereof and method for preparing photoelectric film |
| CN111816770A (en) * | 2020-06-12 | 2020-10-23 | 北京大学 | Perovskite thin film preparation method, perovskite thin film, solar cell device using perovskite thin film, and magnetron sputtering instrument |
| CN112242490A (en) * | 2019-07-16 | 2021-01-19 | 中国科学院青岛生物能源与过程研究所 | Post-repair method of formamidine-based perovskite thin film |
| CN112687807A (en) * | 2020-12-28 | 2021-04-20 | 河北工业大学 | 2D/3D hybrid perovskite solar cell prepared based on two-step method |
| CN116390517A (en) * | 2023-04-18 | 2023-07-04 | 北京高德品创科技有限公司 | Perovskite light-emitting transistor and preparation method thereof |
| WO2024082372A1 (en) * | 2022-10-21 | 2024-04-25 | 华中科技大学 | Tin-based perovskite thin film based on stress regulation and preparation method therefor, and photoelectric device |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106757371A (en) * | 2016-12-19 | 2017-05-31 | 山东大学 | A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere |
| CN106711335A (en) * | 2017-01-04 | 2017-05-24 | 苏州黎元新能源科技有限公司 | Perovskite precursor and preparation method thereof |
| CN108461632A (en) * | 2017-02-21 | 2018-08-28 | 华邦电子股份有限公司 | Perovskite composite construction |
| CN107331774A (en) * | 2017-04-21 | 2017-11-07 | 青岛科技大学 | The perovskite solar cell of double passivation layer structures |
| CN107146849A (en) * | 2017-06-08 | 2017-09-08 | 华中科技大学 | A kind of recycling processing method of perovskite solar cell |
| CN108011046A (en) * | 2017-11-14 | 2018-05-08 | 浙江理工大学 | A kind of method of perovskite surface in situ method growth perovskite nano wire and a kind of perovskite solar cell |
| CN109904322A (en) * | 2019-03-08 | 2019-06-18 | 中国科学院青岛生物能源与过程研究所 | A method of preparing full-inorganic perovskite thin film |
| CN111435705A (en) * | 2019-06-12 | 2020-07-21 | 杭州纤纳光电科技有限公司 | Repairing agent and repairing method thereof and method for preparing photoelectric film |
| CN111435708A (en) * | 2019-06-25 | 2020-07-21 | 杭州纤纳光电科技有限公司 | Method for repairing defect of perovskite thin film |
| CN111435708B (en) * | 2019-06-25 | 2022-09-13 | 杭州纤纳光电科技有限公司 | Method for repairing defect of perovskite thin film |
| CN112242490A (en) * | 2019-07-16 | 2021-01-19 | 中国科学院青岛生物能源与过程研究所 | Post-repair method of formamidine-based perovskite thin film |
| CN112242490B (en) * | 2019-07-16 | 2023-01-20 | 中国科学院青岛生物能源与过程研究所 | Post-repair method of formamidine-based perovskite thin film |
| CN111403610A (en) * | 2020-03-19 | 2020-07-10 | 武汉理工大学 | High-performance organic-inorganic hybrid perovskite photoelectric material and preparation method and application thereof |
| CN111816770A (en) * | 2020-06-12 | 2020-10-23 | 北京大学 | Perovskite thin film preparation method, perovskite thin film, solar cell device using perovskite thin film, and magnetron sputtering instrument |
| CN111816770B (en) * | 2020-06-12 | 2022-07-12 | 北京大学 | Perovskite thin film preparation method, perovskite thin film and solar cell device |
| CN112687807A (en) * | 2020-12-28 | 2021-04-20 | 河北工业大学 | 2D/3D hybrid perovskite solar cell prepared based on two-step method |
| WO2024082372A1 (en) * | 2022-10-21 | 2024-04-25 | 华中科技大学 | Tin-based perovskite thin film based on stress regulation and preparation method therefor, and photoelectric device |
| CN116390517A (en) * | 2023-04-18 | 2023-07-04 | 北京高德品创科技有限公司 | Perovskite light-emitting transistor and preparation method thereof |
| CN116390517B (en) * | 2023-04-18 | 2023-09-19 | 北京高德品创科技有限公司 | Perovskite light-emitting transistor and preparation method thereof |
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