CN106128954A - A kind of method promoting perovskite crystalline - Google Patents

A kind of method promoting perovskite crystalline Download PDF

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Publication number
CN106128954A
CN106128954A CN201610575139.8A CN201610575139A CN106128954A CN 106128954 A CN106128954 A CN 106128954A CN 201610575139 A CN201610575139 A CN 201610575139A CN 106128954 A CN106128954 A CN 106128954A
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perovskite
thin film
crystalline
dimethyl sulfoxide
annealing
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CN106128954B (en
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郭小伟
柳邦
周勇
李绍荣
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a kind of method promoting perovskite thin film crystal property, it is in perovskite preparation process, anneals under dimethyl sulfoxide solvent atmosphere, improves a kind of method of perovskite crystalline.During annealing, perovskite sample is placed under dimethyl sulfoxide atmosphere and can promote grain growth, generate crystalline property excellence, the perovskite thin film of defect concentration reduction.This thin film can reduce the Carrier recombination of perovskite solaode and promote the performance of perovskite solaode.Annealing relative to conventional steam and dimethylformamide equal solvent, dimethyl sulfoxide has lower vapour pressure and higher boiling point, has bigger advantage in terms of strengthening perovskite crystalline.

Description

A kind of method promoting perovskite crystalline
Technical field
The present invention relates to the solaode based on hybrid inorganic-organic perovskite material, be specifically related to one and carry Rise the method for annealing of perovskite crystalline.
Background technology
Solar-photovoltaic technology is the important component part of green energy resource, in the solaode of current various species, Ca-Ti ore type solaode, with excellent characteristics such as its high absorbance, high carrier mobility, with low cost, technique are simple, is subject to To the concern of numerous scientific research personnel, and it it is considered as the Novel photovoltaic battery of great development prospect.Ca-Ti ore type photovoltaic electric at present The conversion efficiency in pond has reached more than 20%, has reached business silion cell peer-level.
Perovskite-type material mainly uses a step spin-coating method, two-step method, altogether steaming method to be prepared at present.But these systems Preparation Method is all difficult to prepare the perovskite thin film of high crystalline.For prepared high efficiency perovskite solar cell device, perovskite Light absorbing zone should have good spreadability, excellent flatness and sufficiently crystallinity.The crystallinity of perovskite thin film Well contribute to reducing its defect state density, reducing the compound of carrier.Through obtaining preferably crystallization frequently with annealing Property.
Perovskite conventional annealing methods is in a nitrogen atmosphere (thermal annealing), uses 100 degree celsius temperature heating crystalline.This In individual crystallization process, methylpyridinium iodide ammonium (MAI) can be with lead iodide (PbI2) react to each other, generate perovskite crystal.Nitrogen is at this In play the effect of protective gas, prevent perovskite from meeting water, oxygen decomposes.Solvent anneal method can be obviously improved perovskite thin film Crystal property, through frequently with solvent atmosphere have aqueous vapor, dimethylformamide etc..Although perovskite component can divide under aqueous vapor atmosphere Solve, form unnecessary lead iodide and methylpyridinium iodide ammonium, but it can dissolve crystal grain, and promote that perovskite is thin to a certain extent The crystal property of film.Dimethylformamide, as the solvent of perovskite precursor, can play good enhancing crystal property, but Being that its volatility is higher, boiling point is relatively low, these characteristics hinder its application in solvent anneal.The present invention propose two Annealing under methyl sulfoxide atmosphere can be obviously enhanced the crystal property of perovskite thin film.The method is applied to perovskite photovoltaic Battery can be obviously improved the energy conversion efficiency of device.
Summary of the invention
In order to solve the background technology dissatisfactory problem of perovskite thin film crystal property, it is an object of the invention to provide one Kind can promote the method for annealing of perovskite crystalline: the solvent anneal under dimethyl sulfoxide atmosphere.
The technical solution used in the present invention is a kind of method promoting perovskite crystalline: the method is first heavy in substrate Long-pending perovskite thin film, is then placed in the dimethyl sulfoxide atmosphere that temperature is 100 DEG C annealing crystallization 2 minutes~2 little by this thin film Time.
Such scheme use solution spin coating or vapour deposition process to prepare the perovskite that thickness range is 50~600nm thin Film.
The perovskite crystalline thin film that method for annealing described in such scheme obtains is applied in battery structure: transparent lead Electrolemma, hole transmission layer, perovskite thin film, electron transfer layer, metal electrode.
The present invention uses solvent anneal method, and perovskite thin film is placed in annealing crystallization under dimethyl sulfoxide atmosphere.Whole Course of reaction power consumption is low, preparation technology is simple.The crystallinity of the perovskite crystalline thin film prepared is remarkably reinforced, and crystallite dimension expands Big and reduce the defect state density of crystalline membrane.The perovskite crystalline thin film prepared by the method is applied to solaode In can substantially reduce carrier defect state density, there is prospects for commercial application widely.
Advantages of the present invention:
1, reaction condition is gentle, energy consumption is low.Perovskite gets final product annealing crystallization at 100 DEG C.
2, the crystal property of thin film, and the energy conversion efficiency of boost device can be obviously improved.
3, the annealing under dimethyl sulfoxide atmosphere has high duplication, and energy stable application is in commercial production.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention;
Fig. 2 is the schematic diagram of the present invention;
Fig. 3 is that the Electronic Speculum pattern that in the present invention, thermal annealing is annealed with dimethyl sulfoxide compares;
Fig. 4 is the perovskite battery performance of dimethyl sulfoxide annealing in the present invention.
Fig. 5 be surface topography that in the present invention, perovskite thin film is annealed under different atmosphere (upper row) with Cross Section Morphology (under Row) photo.It is followed successively by thermal annealing (nitrogen environment N from left to right2, aqueous vapor annealing H2O, gamma-hydroxybutyric acid lactone ambient anneal GBL, dimethylformamide ambient anneal DMF and dimethyl sulfoxide ambient anneal DMSO.
Detailed description of the invention
The invention will be further described with example below in conjunction with the accompanying drawings.
The substrate of glass that will be covered with ITO is washed 30 minutes with detergent, acetone, EtOH Sonicate successively, blows by nitrogen gun Dry.Spin-coating method is used to prepare the CH3NH3PbI that thickness is 300nm3-xClxPerovskite light absorbing zone.5 points are heated under 100 degrees Celsius Clock.Sample complete for preannealing is transferred on the warm table of 100 DEG C.The crucible of a diameter 1cm is placed, with shifting on warm table Liquid rifle extracts 10 μ l dimethyl sulfoxide and instills crucible, then covers sample and crucible with glass cover rapidly.Crucible is heated, the inside Solvent become steam raising out, in lid, define dimethyl sulfoxide solvent atmosphere.The solvent anneal time is 30min. As shown in Figure 1.
Annealing theory under dimethyl sulfoxide solvent atmosphere is as shown in Figure 2.Perovskite thin film is placed on an airtight sky In, solvent molecule can condense in film surface dissolving films composition, simultaneously high temperature substrate can allow again these condense molten Agent is evaporated again, and condensation-evaporation that cover inside occurs is a dynamic thermal balance process.Thin film on flat plate heat is with limited Vapor pressure solvent jointly act on, the solvent molecule of evaporation can't cause the dissolving on a large scale of thin film, but cause surface and Perforated forms liquid or semi liquid state phase.This liquid phase can act the adhesive effect being similar to glue, bond two crystal grain it Between contiguous zone.Perovskite atom enters in liquid phase adhesive and at liquid-solid interface recrystallization.This recrystallization process can be led Cause the polymerization of crystal grain in thin film, grow bigger crystal grain.
Fig. 3 gives the perovskite grain size obtained of annealing under different atmosphere.Upper row is perovskite thin film surface shape Looks, lower row is corresponding Cross Section Morphology.It is followed successively by from left to right in thermal annealing (nitrogen environment), aqueous vapor annealing, gamma-hydroxybutyric acid Ester ambient anneal, dimethylformamide ambient anneal and dimethyl sulfoxide ambient anneal.It can be seen that the nitrogen of routine from figure Crystallite dimension obtained by thermal annealing after about 300nm, amplification as shown in Figure 4.Annealing under water vapour atmosphere is the brightest The aobvious crystal property improving thin film, similar with thermal annealing.Gamma-hydroxybutyric acid lactone ambient anneal and dimethylformamide atmosphere are moved back Fire is remarkably improved grain size, the most about 500nm, but compared with dimethyl sulfoxide atmosphere, the crystal property brought carries Rise limited.Perovskite thin film anneal under dimethyl sulfoxide solvent atmosphere after crystallite dimension up to 1000nm.
The performance of the perovskite thin film for being formed under checking different solvents atmosphere, above-mentioned several perovskite thin films are done by we Become solaode.The battery structure used in the present embodiment is: indium tin oxide transparent conductive semiconductor film/3,4-ethylene two Oxygen thiophene monomer polymer: poly styrene sulfonate/perovskite/fullerene derivate/silver electrode.Wherein, 3,4-enedioxies Thiophene monomer polymer: poly styrene sulfonate is hole mobile material, fullerene derivate is common electron transport material. It makes is spin coating hole transmission layer, perovskite, electron transfer layer successively on nesa coating, finally uses vapour deposition method deposition The silver electrode of a layer thickness about 100nm.
Fig. 5 show under different solvents atmosphere the perovskite solar cell photoelectric characteristic curve of correspondence of annealing.Nitrogen gas Lower its open-circuit voltage of respective devices of atmosphere annealing is 0.93V, and short-circuit current density is 16.9mA/cm2, fill factor, curve factor is 0.53, energy Amount conversion efficiency is 8.34%.Under water ambient anneal, its open-circuit voltage of respective devices is 0.95V, and short-circuit current density is 18.7mA/cm2, fill factor, curve factor is 0.51, and energy conversion efficiency is 8.99%.Gamma-hydroxybutyric acid lactone ambient anneal correspondence device Its open-circuit voltage of part is 0.92V, and short-circuit current density is 20.9mA/cm2, fill factor, curve factor is 0.64, and energy conversion efficiency is 12.29%.Dimethylformamide its open-circuit voltage of ambient anneal respective devices is 0.91V, and short-circuit current density is 20.2mA/ cm2, fill factor, curve factor is 0.62, and energy conversion efficiency is 11.29%.Dimethyl sulfoxide annealing its open-circuit voltage of respective devices is 0.93V, short-circuit current density is 20.9 mA/cm2, fill factor, curve factor is 0.68, and energy conversion efficiency is 13.21%.
Thus it is seen that after using dimethyl sulfoxide annealing, battery performance is largely increased, and illustrates by dimethyl sulfoxide The perovskite thin film superior performance that annealing is formed.

Claims (3)

1. the method promoting perovskite crystalline: first the method deposits a perovskite thin film in substrate, then that this is thin Film is placed in annealing crystallization 2 minutes~2 hours in the dimethyl sulfoxide atmosphere that temperature is 100 DEG C.
A kind of method promoting perovskite crystalline the most as claimed in claim 1, it is characterised in that use molten in described method Liquid spin coating or vapour deposition process prepare the perovskite thin film that thickness range is 50~600nm.
A kind of method promoting perovskite crystalline the most as claimed in claim 1, it is characterised in that described in described method The perovskite crystalline thin film that method for annealing obtains is applied in battery structure: nesa coating, hole transmission layer, perovskite are thin Film, electron transfer layer, metal electrode.
CN201610575139.8A 2016-07-21 2016-07-21 A method of promoting perovskite crystalline Expired - Fee Related CN106128954B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107068875A (en) * 2017-03-10 2017-08-18 武汉大学 A kind of method for optimizing perovskite crystal film morphology
CN108987577A (en) * 2017-06-02 2018-12-11 杭州纤纳光电科技有限公司 A kind of perovskite thin film equipment for after-treatment and application method and application
CN109904319A (en) * 2019-01-29 2019-06-18 安徽大学 The flat crystal of large scale perovskite, calcium titanium ore bed preparation method and solar battery
CN110311038A (en) * 2019-06-21 2019-10-08 南京邮电大学 A method of increasing perovskite solar battery perovskite film layer crystal particle size
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
CN113594396A (en) * 2021-07-08 2021-11-02 浙江大学 Solvent atmosphere controlled perovskite in-situ film forming method and product and application thereof

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Publication number Priority date Publication date Assignee Title
CN109860403B (en) * 2019-04-10 2022-07-19 西南石油大学 Post-processing method for obtaining large-grain high-quality perovskite film and application thereof

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CN104934304A (en) * 2015-06-04 2015-09-23 苏州大学 Method for obtaining black cubic crystal system perovskite film through inductive regulation and control of mixed solvent at normal temperature
CN105098080A (en) * 2015-08-17 2015-11-25 电子科技大学 Method for manufacturing organic and inorganic perovskite crystal film
CN105609635A (en) * 2016-03-17 2016-05-25 东华大学 Method for preparing high-crystallinity perovskite thin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934304A (en) * 2015-06-04 2015-09-23 苏州大学 Method for obtaining black cubic crystal system perovskite film through inductive regulation and control of mixed solvent at normal temperature
CN105098080A (en) * 2015-08-17 2015-11-25 电子科技大学 Method for manufacturing organic and inorganic perovskite crystal film
CN105609635A (en) * 2016-03-17 2016-05-25 东华大学 Method for preparing high-crystallinity perovskite thin film

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107068875A (en) * 2017-03-10 2017-08-18 武汉大学 A kind of method for optimizing perovskite crystal film morphology
CN107068875B (en) * 2017-03-10 2019-06-25 武汉大学 A method of optimization perovskite crystal film morphology
CN108987577A (en) * 2017-06-02 2018-12-11 杭州纤纳光电科技有限公司 A kind of perovskite thin film equipment for after-treatment and application method and application
CN108987577B (en) * 2017-06-02 2024-02-02 杭州纤纳光电科技有限公司 Perovskite film post-treatment equipment, use method and application
CN109904319A (en) * 2019-01-29 2019-06-18 安徽大学 The flat crystal of large scale perovskite, calcium titanium ore bed preparation method and solar battery
CN109904319B (en) * 2019-01-29 2022-11-18 安徽大学 Preparation method of large-size perovskite flat crystal and perovskite layer and solar cell
CN110311038A (en) * 2019-06-21 2019-10-08 南京邮电大学 A method of increasing perovskite solar battery perovskite film layer crystal particle size
CN110311038B (en) * 2019-06-21 2022-08-26 南京邮电大学 Method for increasing crystal grain size of perovskite film layer of perovskite solar cell
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
CN113594396A (en) * 2021-07-08 2021-11-02 浙江大学 Solvent atmosphere controlled perovskite in-situ film forming method and product and application thereof
CN113594396B (en) * 2021-07-08 2022-08-05 浙江大学 Solvent atmosphere controlled perovskite in-situ film forming method and product and application thereof

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