CN107805779A - A kind of Laser vaporization prepares CsPbBr3The method of film - Google Patents

A kind of Laser vaporization prepares CsPbBr3The method of film Download PDF

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Publication number
CN107805779A
CN107805779A CN201710933312.1A CN201710933312A CN107805779A CN 107805779 A CN107805779 A CN 107805779A CN 201710933312 A CN201710933312 A CN 201710933312A CN 107805779 A CN107805779 A CN 107805779A
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cspbbr
film
laser
prepare
target
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CN107805779B (en
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徐庆宇
张昊
马眉扬
王宏
董帅
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Southeast University
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Disclosure sets forth a kind of Laser vaporization to prepare CsPbBr3The method of film.Concretely comprise the following steps：First pass through DMF, DMSO, cyclohexanol, PbBr2, CsBr materials enough CsPbBr are prepared with solution heating means3Monocrystalline is simultaneously pressed into target, then using pld (pulsed laser deposition) technology of preparing：Laser energy and base reservoir temperature are adjusted, film thickness is controlled by laser pulse number, vacuum moulding machine prepares CsPbBr3Film.The present invention prepares CsPbBr using pulsed laser deposition technique3Film, the convenient preparation of uniform large-area film can be achieved, be easy to effectively control film thickness and save material, be advantageous to industrialized production and application of the material in solar cell.

Description

A kind of Laser vaporization prepares CsPbBr3The method of film
Technical field
The present invention is CsPbBr3A kind of preparation method of film, it is especially a kind of to be prepared using pulse laser sediment method Inorganic perovskite CsPbBr3The method of film, belongs to technical field of film preparation.
Background technology
Inorganic perovskite crystal formation (ABX3) light absorbent, in ABX3In structure, A is metal cesium ion (Cs+), B is metal Lead ion (Pb2+), X is halogen family bromide ion (Br-).This material widely applies to solar cell and fluorescent material.At present In general CsPbBr3Method for manufacturing thin film is mainly solution spin-coating method and chemical vapour deposition technique etc., but these preparation methods without Method is convenient to be accurately controlled thickness, and preparation process largely wastes raw material, and is unsuitable for the preparation of large area film mostly With applied to industrial production and practical application.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of Laser vaporization to prepare inorganic perovskite CsPbBr3Film Method.The present invention prepares CsPbBr using pulsed laser deposition technique3Film, the convenient system of uniform large-area film can be achieved It is standby, be easy to effectively control film thickness and save material, be advantageous to the industrialized production of inorganic perovskite solar cell with Using.
Technical scheme：A kind of Laser vaporization of the present invention prepares inorganic perovskite CsPbBr3The method of film include with Lower step：
1.) CsPbBr is prepared3Target：Using solution heating standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr systems It is standby go out enough CsPbBr3Monocrystal, CsPbBr is made after being suppressed with tablet press machine3Target；
2.) by clean substrate and the CsPbBr prepared3Target is put into pulsed laser deposition cavity jointly, is taken out true Sky, heating substrate adjust the energy of incident cavity laser to 100 DEG C -250 DEG C, then set laser pulse number and start to sink Product；
3.) after deposition terminates, substrate takes out after keeping heating-up temperature vacuum annealing in cavity, obtains CsPbBr3Film.
Wherein：
The solution heating standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr prepare enough CsPbBr3It is single Crystalline flour end, wherein DMSO, CsBr, PbBr2, cyclohexanol, DMF addition be： DMSO:CsBr:PbBr2:Cyclohexanol:DMF= (20-35):(0.5-1.5):(1-3):(5-8):(12-20)。
The energy of the incident cavity laser of regulation, refers to the energy adjustment of incident cavity laser to 50mJ-400mJ, CsPbBr3The thickness of film is accurately controlled by laser energy and umber of pulse.
Described vacuumizes, and refers to be evacuated to pressure for 1 × 10-2Below Pa.
Described silicon, refer to silicon to temperature range be 100 DEG C -250 DEG C.
The described vacuum annealing time is 5-30 minutes.
Beneficial effect：
(1) CsPbBr is prepared with solwution method3Monocrystal is simultaneously pressed into target, easily prepared, and purity is high.
(2) pld (pulsed laser deposition) technology of preparing is utilized, the waste of raw material can be significantly reduced and prepared Even CsPbBr3Film.
(3) pld (pulsed laser deposition) technology of preparing is utilized, can be controlled by changing laser energy and umber of pulse CsPbBr3Film thickness, it is more precisely convenient.
(4) this technique can be applied to the industrialized production and practical application of the organic perovskite solar cell of large area.
Brief description of the drawings
Fig. 1 is CsPbBr prepared by Laser vaporization3The SEM sectional views of film.
Fig. 2 is CsPbBr prepared by Laser vaporization3The SEM plans of film.
Fig. 3 is CsPbBr prepared by Laser vaporization3The XRD of film.
Fig. 4 is CsPbBr prepared by Laser vaporization3The PL figures of film.
Embodiment
Embodiment one：
By PbBr2With CsBr according to mol ratio 2:1 is put into 70 DEG C of heating magnetic agitation dissolvings in 60ml DMSO solution.Again DMF and hexamethylene mixed alkoxide solution are poured into, after being warming up to 110 DEG C with 1 DEG C/min speed and be incubated 10 hours, taken out red heavy Shallow lake solid is put into 100 DEG C of DMF solution and cleaned, and then takes out and is put into 60 DEG C of drying in baking oven.Again by enough powder after drying End collects to be put into mould is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparing CsPbBr3Target is together put into cavity, and intracavitary vacuum is evacuated into 7 × 10-3Pa, heating substrate adjust incident chamber to 110 DEG C The laser energy of body is 100mJ, and selection laser frequency is 1500 for 5Hz and umber of pulse.After 1500 pulsed depositions terminate, substrate Continue the 10min that anneals, then take out, CsPbBr3(film morphology is shown in Fig. 1 and Fig. 2 SEM photograph, and XRD is shown in for film preparation completion Fig. 3, fluorescence spectrum are shown in Fig. 4).
Embodiment two：
By PbBr2With CsBr according to mol ratio 2.1:0.9 to be put into 65ml DMSO solution 70 DEG C of heating magnetic agitations molten Solution.DMF and hexamethylene mixed alkoxide solution are poured into again, with 1 DEG C/min speed be warming up to 110 DEG C and be incubated 10 hours after, take out Red precipitate solid is put into 100 DEG C of DMF solution and cleaned, and then takes out and is put into 60 DEG C of drying in baking oven.Again by after drying Enough powder are collected to be put into mould is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparing Good CsPbBr3Target is together put into cavity, and intracavitary vacuum is evacuated into 1 × 10-3Pa, heating substrate to 150 DEG C, and adjust into The laser energy for penetrating cavity is 160mJ, and selection laser frequency is 1000 for 5Hz and umber of pulse.After 1000 pulsed depositions terminate, Substrate continues the 20min that anneals, and then takes out, CsPbBr3Film preparation is completed.
Embodiment three：
By PbBr2With CsBr according to mol ratio 1.6:1.3 to be put into 55ml DMSO solution 70 DEG C of heating magnetic agitations molten Solution.DMF and hexamethylene mixed alkoxide solution are poured into again, with 1 DEG C/min speed be warming up to 110 DEG C and be incubated 10 hours after, take out Red precipitate solid is put into 100 DEG C of DMF solution and cleaned, and then takes out and is put into 60 DEG C of drying in baking oven.Again by after drying Enough powder are collected to be put into mould is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparing Good CsPbBr3Target is together put into cavity, and intracavitary vacuum is evacuated into 6 × 10-4Pa, heating substrate to 230 DEG C, and adjust into The laser energy for penetrating cavity is 230mJ, and selection laser frequency is 2000 for 5Hz and umber of pulse.After 2000 pulsed depositions terminate, Substrate continues the 30min that anneals, and then takes out, CsPbBr3Film preparation is completed.
The invention provides a kind of effectively and uniformly inorganic perovskite CsPbBr3Film passes through laser splash preparation method Thinking and implementation, concrete application approach is a lot, and described above is only the preferred embodiment of the present invention, it is noted that right For those skilled in the art, under the premise without departing from the principles of the invention, some improvement can also be made, Such as similar inorganic perovskite material C sPbX is grown by pulse laser deposition process3(X=Cl, I) film, different Grown film etc., these improvement also should be regarded as protection scope of the present invention.

Claims (6)

1. a kind of Laser vaporization prepares CsPbBr3The method of film, it is characterised in that this method comprises the following steps：
1.) CsPbBr is prepared3Target：Using solution heating standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr prepares Enough CsPbBr3Monocrystal, CsPbBr is made after being suppressed with tablet press machine3Target；
2.) by clean substrate and the CsPbBr prepared3Target is put into pulsed laser deposition cavity jointly, is vacuumized, heating Substrate, while the energy of incident cavity laser is adjusted, then set laser pulse number and start to deposit；
3.) after deposition terminates, substrate takes out after keeping heating-up temperature vacuum annealing in cavity, obtains CsPbBr3Film.
2. prepare CsPbBr according to the Laser vaporization described in claim 13The method of film, it is characterised in that the solution heating Standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr prepare enough CsPbBr3Monocrystal, tabletting is utilized at room temperature Machine height is pressed into target, wherein DMSO, CsBr, PbBr2, cyclohexanol, DMF addition be：
DMSO:CsBr:PbBr2:Cyclohexanol:DMF=(20-35):(0.5-1.5):(1-3):(5-8):(12-20).
3. prepare CsPbBr according to the Laser vaporization described in claim 13The method of film, it is characterised in that the regulation is incident The energy of cavity laser, refer to the energy adjustment of incident cavity laser to 50mJ-400mJ, CsPbBr3The thickness of film passes through Laser energy and umber of pulse are accurately controlled.
4. prepare CsPbBr according to the Laser vaporization described in claim 13The method of film, it is characterised in that described vacuumizes, Refer to be evacuated to pressure for 1 × 10-2Below Pa.
5. prepare CsPbBr according to the Laser vaporization described in claim 13The method of film, it is characterised in that described substrate adds Heat, it is 100 DEG C -250 DEG C to refer to temperature range.
6. prepare CsPbBr according to the Laser vaporization described in claim 13The method of film, it is characterised in that described vacuum is moved back The fiery time is 5-30 minutes.
CN201710933312.1A 2017-10-10 2017-10-10 A kind of Laser vaporization preparation CsPbBr3The method of film Active CN107805779B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109097741A (en) * 2018-08-31 2018-12-28 鲁东大学 A kind of CsPbBr3The preparation method of film
CN110565054A (en) * 2019-09-12 2019-12-13 东南大学 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
CN111647848A (en) * 2020-05-27 2020-09-11 山东大学 Preparation of large-area CsPbBr by magnetron sputtering3Method and application of photoelectric film
CN116705893A (en) * 2023-08-02 2023-09-05 济南大学 MSM type photoelectric detector and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160254472A1 (en) * 2015-02-26 2016-09-01 Nanyang Technological University Perovskite thin films having large crystalline grains
CN105925938A (en) * 2016-07-08 2016-09-07 合肥工业大学 Laser pulse deposition preparation method for Cs2SnI6 thin film
CN106745204A (en) * 2016-11-28 2017-05-31 湖北大学 A kind of environmental protection CsPbX3The synthetic method of perovskite quantum dot
CN107123706A (en) * 2017-04-07 2017-09-01 湖南大学 A kind of CVD builds CsPbBr3The method of nanometer sheet electroluminescent device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160254472A1 (en) * 2015-02-26 2016-09-01 Nanyang Technological University Perovskite thin films having large crystalline grains
CN105925938A (en) * 2016-07-08 2016-09-07 合肥工业大学 Laser pulse deposition preparation method for Cs2SnI6 thin film
CN106745204A (en) * 2016-11-28 2017-05-31 湖北大学 A kind of environmental protection CsPbX3The synthetic method of perovskite quantum dot
CN107123706A (en) * 2017-04-07 2017-09-01 湖南大学 A kind of CVD builds CsPbBr3The method of nanometer sheet electroluminescent device

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109097741A (en) * 2018-08-31 2018-12-28 鲁东大学 A kind of CsPbBr3The preparation method of film
CN110565054A (en) * 2019-09-12 2019-12-13 东南大学 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
CN110565054B (en) * 2019-09-12 2021-04-27 东南大学 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
CN111647848A (en) * 2020-05-27 2020-09-11 山东大学 Preparation of large-area CsPbBr by magnetron sputtering3Method and application of photoelectric film
CN116705893A (en) * 2023-08-02 2023-09-05 济南大学 MSM type photoelectric detector and preparation method thereof

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