CN106159097B - A method of improving perovskite thin film quality - Google Patents
A method of improving perovskite thin film quality Download PDFInfo
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- CN106159097B CN106159097B CN201510184150.7A CN201510184150A CN106159097B CN 106159097 B CN106159097 B CN 106159097B CN 201510184150 A CN201510184150 A CN 201510184150A CN 106159097 B CN106159097 B CN 106159097B
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Abstract
The present invention relates to a kind of methods improving perovskite thin film.The invention belongs to the preparation methods of thin-film material, it is characterized in that perovskite thin film is handled certain time through organic amine gas or Amine Solutions, to improve the quality of perovskite thin film, the defect of perovskite thin film can be effectively repaired through processing, surface roughness is reduced, film forming is improved.Perovskite thin film thickness prepared by this technique is uniform, and roughness is low, good crystallinity, and this technological operation is simple, of low cost, is suitably applied large area and prepares efficient perovskite solar cell, light emitting diode, light-sensitive element and laser device.
Description
Technical field
The invention belongs to the preparation methods of thin-film material, and in particular to a method of improving perovskite thin film quality.
Background technology
Organic inorganic hybridization perovskite is since its unique light, electricity, magnetic property and preparation process are simple, raw material dosage
Less, the features such as at low cost, has been a concern, especially since first time in 2009 is applied in solar cell,
Perovskite solar cell rapidly rises to current 20.1% by 3.8%, and perovskite is in the necks such as diode and laser device
Domain also receives the extensive concern of people.In these devices, perovskite active material is its core, perovskite film it is good
Bad is therefore the key factor of influence device performance is of great significance to the research of perovskite film forming.
The film forming of perovskite and the preparation process of perovskite are closely related.Usually, the film-forming process master of perovskite
It wants that solwution method, the combination of evaporation and the two can be divided into.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 for preparing perovskite solar cell.A but traditional step solwution method
The perovskite thin film film forming of preparation is poor.To improve its film forming, to perovskite precursor solution（PbI2:CH3NH3I=1:1) in
Additive is added（Such as CH3NH3Cl, NH4Cl, HI etc.）The film forming and crystal property of perovskite can be effectively improved.In addition, introducing
PbCl2And PbAc2Also the film forming of perovskite can be effectively improved.The anti-solvent method reported recently can largely improve calcium
The film forming of titanium ore, but such method, to technological requirement harshness, not easy to operate, the method will realize that large-scale production is that comparison is tired
Difficult.Two step infusion methods are also to prepare the common method of efficient perovskite solar cell.But lead iodide turns completely in infusion method
It is relatively difficult to turn to perovskite, long period of soaking may destroy perovskite film again, then prepare efficient perovskite thin film by infusion method
It is higher to technological requirement.
Evaporation mainly has double source vapor deposition, continuous vapor deposition, chemical vapor deposition and single source heat melting method etc..By
The perovskite film crystallinity and film forming of the preparations such as the gas phase assisted solution method that evaporation is combined with evaporation and solwution method are good
It is good, but this evaporation and pyroprocess increase the cost for preparing perovskite, to limit the extensive system of perovskite thin film
It is standby.Then, it is still particularly important to develop more cheap easily-controllable perovskite film-forming process.
Invention content
The object of the present invention is to provide a kind of methods improving perovskite thin film quality.
The technical solution adopted by the present invention is to achieve the above object：A method of improving perovskite thin film quality, it is main
The step is wanted to be：At a certain temperature, perovskite thin film is handled into certain time through organic amine gas or Amine Solutions, to change
The quality of kind perovskite thin film.
The perovskite structure formula is ABX3, A is CH in formula3NH3、NH2-CH=NH2One or both of it is compound
Object, the compound of one or both of B Pb, C I, Br, Cl.
The organic amine is methylamine, carbonamidine, ethamine, triethylamine, and propylamine is one or two kinds of or two or more in hydrazine
Mixture.
The time range of the processing is between 0.1s to 100h.
The solvent of the Amine Solutions be chlorobenzene, benzene, toluene, ether, isopentane, pentane, petroleum ether, hexane,
Hexamethylene, isooctane, pentamethylene, heptane, butyl chloride, trichloro ethylene, carbon tetrachloride, propyl ether, paraxylene, o-dichlorohenzene, two
One or two kinds of or two or more mixture in chloromethanes, chloroform, tetrachloromethane, pyridine.
The Amine Solutions concentration is between 0 between saturated concentration.
Described handle perovskite thin film with Amine Solutions can be that perovskite film is soaked in Amine Solutions,
Can also be that Amine Solutions are added dropwise on perovskite thin film.
Temperature of the perovskite thin film through organic amine gas and when being handled through Amine Solutions is -50oC to 200oC
Between.
The perovskite film is in solar cell, diode, the application in gas sensor and laser.
Advantage for present invention：
The present invention handles perovskite thin film by organic amine, and solid-state perovskite thin film becomes liquid due to having adsorbed organic amine
Body state, since liquid flows, to make film realize all standing.After perovskite thin film is removed from organic amine environment,
Due to the effumability of organic amine gas, under room temperature, organic amine is just easily evaporated from liquid, to become again cube
Perovskite Phase film.
Since perovskite film prepared by liquid flowing is extremely smooth, and high uniformity, defect is few, and roughness is low, reduces
Exciton it is compound, after tested the roughness of film up to 3nm hereinafter, there is fabulous flatness.In addition, under organic amine room temperature just
It can be evaporated from liquid, prepared by the room temperature that perovskite film may be implemented in this method, and calcium titanium prepared by this room temperature
Mine film has and good crystallinity and has good crystal lattice orientation, then this method prepare perovskite thin film with more universality and
Better photoelectric properties.
This technique is more easier to operate than evaporation and successive sedimentation method, and cost is less expensive, more conducively mass produces.It is this
Technique has compared with a step solwution method film forming to be greatly improved, and crystallinity greatly improves.This film can be competent at a variety of device architectures, such as
Mesoporous and plane perovskite solar cell, diode, gas sensor and laser.
Description of the drawings
XRD of the attached drawing 1 through methylamine gas perovskite film before and after the processing.
SEM and AFM of the attached drawing 2 through methylamine gas perovskite film before and after the processing；Wherein, (a) is the SEM figures before processing,
(b) (c) is treated SEM figure, and (d) (e) be the AFM figures before processing, and (f) (g) is that treated AFM schemes.
IV curve of the attached drawing 3 through methylamine gas perovskite film before and after the processing.
The SEM of the perovskite film after the processing of the chlorobenzene solution of methylamine of attached drawing 4.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
First, sol-gal process prepares TiO2Colloid is spun on the FTO glass cleaned, and then 500oC heats
30 min obtain fine and close TiO2Film.Spin coating TiO on a dense film2Slurry, TiO2Granular size ~ 20 nm, then again
Further 500oC heats 30 min, obtains TiO2Mesopore film.Secondly, according to molar percentage 1:1 by PbI2With
CH3NH3I is dissolved in DMF solution, is prepared the solution that mass ratio is 40%, is then spin coated onto in mesoporous TiO2On film, it is heated to 100oC, 10 min, evaporation of solvent, then by the CH of preparation3NH3PbI3Film smokes 2-6s with methylamine gas, and it is good to obtain compact crystal
Good perovskite thin film.Finally spin coating hole transmission layer spiro, vapor deposition silver electrode on calcium titanium ore bed, are assembled into solar-electricity
Pond device.
The perovskite film that obtained to the present embodiment and thus the solar cell of film preparation characterizes, as passed through in Fig. 1
The XRD of methylamine gas perovskite film before and after the processing shows that there is the crystallinity of perovskite film after methylamine gas is smoked greatly improves.Such as
SEM and AFM through methylamine gas perovskite film before and after the processing in Fig. 2 show there there is the flatness of perovskite film after methylamine gas is smoked
Greatly improve, roughness become smoked by the 153nm before smoked after 6.53nm.As in Fig. 3 through methylamine gas calcium titanium before and after the processing
The IV curves of mine film show that 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 the FTO glass cleaned, and then 500oC heats
30 min obtain fine and close TiO2Film.Secondly, according to molar percentage 1:1 by PbI2And CH3NH3I is dissolved in DMF solution
In, the solution that mass ratio is 40% is prepared, is then spin coated onto in mesoporous TiO2On film, it is heated to 100oC, 10 min are vapored away molten
Agent, then to the CH of preparation3NH3PbI3The chlorobenzene solution of methylamine is added dropwise on film, it is good to obtain compact crystal for naturally dry
Perovskite thin film.Finally spin coating hole transmission layer spiro, vapor deposition gold electrode on calcium titanium ore bed, are assembled into solar cell device
Part.If the SEM of the perovskite film before and after the processing of the chlorobenzene solution through methylamine in Fig. 4 is shown, the perovskite film of preparation has good
Crystallinity.
Claims (5)
1. a kind of method improving perovskite thin film quality, mainly comprises the following steps：At any temperature between -50 DEG C to 200 DEG C,
Perovskite thin film is handled into certain time through organic amine gas or Amine Solutions, to improve the quality of perovskite thin film；Its
Middle perovskite structure formula is ABX3, A is CH in formula3NH3、NH2-CH=NH2One or both of compound, B Pb, X I,
The compound of one or both of Br, Cl, organic amine are methylamine, carbonamidine, ethamine, triethylamine, propylamine, one kind in hydrazine or
Two or more mixture, the time range of processing is between 0.1s to 100h.
2. a kind of method improving perovskite thin film quality according to claim 1, the solvents of Amine Solutions be chlorobenzene,
Benzene, toluene, ether, isopentane, pentane, petroleum ether, hexane, hexamethylene, isooctane, pentamethylene, heptane, butyl chloride, trichlorine
One kind in ethylene, carbon tetrachloride, propyl ether, paraxylene, o-dichlorohenzene, dichloromethane, chloroform, tetrachloromethane, pyridine
Or two or more mixture.
3. a kind of method improving perovskite thin film quality according to claim 1, Amine Solutions concentration arrive full between 0
Between concentration.
4. a kind of method improving perovskite thin film quality according to claim 1, molten by perovskite thin film organic amine
Liquid processing, the specific steps are：Perovskite film is soaked in Amine Solutions or Amine Solutions are added dropwise in perovskite thin film
On.
5. perovskite thin film prepared by a kind of method of improvement perovskite thin film quality described in claim 1 is in solar-electricity
Pond, diode, the application in gas sensor and laser.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106711335B (en) * | 2017-01-04 | 2019-02-05 | 上海黎元新能源科技有限公司 | A kind of perovskite presoma 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 |
| CN107331774B (en) * | 2017-04-21 | 2020-01-17 | 青岛科技大学 | Novel perovskite solar cell structure and preparation method |
| CN107146849B (en) * | 2017-06-08 | 2019-12-17 | 华中科技大学 | 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 |
| CN111435705B (en) * | 2019-06-12 | 2023-04-07 | 杭州纤纳光电科技有限公司 | Repairing agent and repairing method thereof and method for preparing photoelectric 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 |
| 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 |
| CN111816770B (en) * | 2020-06-12 | 2022-07-12 | 北京大学 | Perovskite thin film preparation method, perovskite thin film and solar cell device |
| CN112687807B (en) * | 2020-12-28 | 2022-08-02 | 河北工业大学 | 2D/3D hybrid perovskite solar cell prepared based on two-step method |
| CN115623835A (en) * | 2022-10-21 | 2023-01-17 | 华中科技大学 | Tin-based perovskite thin film based on stress regulation and control, preparation method thereof and photoelectric device |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881832A (en) * | 2012-09-20 | 2013-01-16 | 浙江大学 | Preparation method for inverse organic solar battery preparation method |
| CN102903853A (en) * | 2012-10-24 | 2013-01-30 | 中国科学院长春应用化学研究所 | Ink-jet printing preparation method of organic solar battery optical active layer film |
| WO2014067233A1 (en) * | 2012-10-30 | 2014-05-08 | 中国科学院长春光学精密机械与物理研究所 | Preparation method for high-conductivity organic transparent conductive film |
-
2015
- 2015-04-19 CN CN201510184150.7A patent/CN106159097B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881832A (en) * | 2012-09-20 | 2013-01-16 | 浙江大学 | Preparation method for inverse organic solar battery preparation method |
| CN102903853A (en) * | 2012-10-24 | 2013-01-30 | 中国科学院长春应用化学研究所 | Ink-jet printing preparation method of organic solar battery optical active layer film |
| WO2014067233A1 (en) * | 2012-10-30 | 2014-05-08 | 中国科学院长春光学精密机械与物理研究所 | Preparation method for high-conductivity organic transparent conductive film |
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