CN107805779B - A kind of Laser vaporization preparation CsPbBr3The method of film - Google Patents

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

Info

Publication number
CN107805779B
CN107805779B CN201710933312.1A CN201710933312A CN107805779B CN 107805779 B CN107805779 B CN 107805779B CN 201710933312 A CN201710933312 A CN 201710933312A CN 107805779 B CN107805779 B CN 107805779B
Authority
CN
China
Prior art keywords
cspbbr
film
laser
pbbr
csbr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710933312.1A
Other languages
Chinese (zh)
Other versions
CN107805779A (en
Inventor
徐庆宇
张昊
马眉扬
王宏
董帅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southeast University
Original Assignee
Southeast University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southeast University filed Critical Southeast University
Priority to CN201710933312.1A priority Critical patent/CN107805779B/en
Publication of CN107805779A publication Critical patent/CN107805779A/en
Application granted granted Critical
Publication of CN107805779B publication Critical patent/CN107805779B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 vaporizations to prepare CsPbBr3The method of film.Specific steps are as follows: first pass through DMF, DMSO, cyclohexanol, PbBr2, CsBr material enough CsPbBr are prepared with solution heating means3Monocrystalline is simultaneously pressed into target, then uses pld (pulsed laser deposition) technology of preparing: adjustment laser energy and base reservoir temperature, controls film thickness by laser pulse number, vacuum deposition prepares CsPbBr3Film.The present invention prepares CsPbBr using pulsed laser deposition technique3Film, it can be achieved that uniform large-area film convenient preparation, be easy to effectively control film thickness and save material, be conducive to the material in the industrialized production and application of solar battery.

Description

A kind of Laser vaporization preparation 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 technique
Inorganic perovskite crystal form (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 battery and fluorescent material.At present 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 film thickness, and preparation process largely wastes raw material, and is unsuitable for the preparation of large area film mostly To be applied to industrial production and practical application.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of Laser vaporizations to prepare inorganic perovskite CsPbBr3Film Method.The present invention prepares CsPbBr using pulsed laser deposition technique3Film, it can be achieved that uniform large-area film convenient system It is standby, be easy to effectively control film thickness and save material, be conducive to the industrialized production of inorganic perovskite solar battery with Using.
Technical solution: a kind of Laser vaporization of the invention prepares inorganic perovskite CsPbBr3The method of film include with Lower step:
1.) CsPbBr is prepared3Target: standard measure mixing DMF, DMSO, cyclohexanol, PbBr are heated using solution2, CsBr system For CsPbBr enough out3CsPbBr is made after being suppressed with tablet press machine in monocrystal3Target；
2.) by clean substrate and the CsPbBr prepared3Target is put into jointly in pulse laser deposition chamber, is taken out true Sky heats substrate to 100 DEG C -250 DEG C, while adjusting the energy of incident cavity laser, then sets laser pulse number and starts to sink Product；
3.) after depositing, substrate takes out after keeping heating temperature vacuum annealing in the cavity, obtains CsPbBr3Film.
Wherein:
The solution heats standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr prepare enough CsPbBr3It is single Crystalline flour is last, wherein DMSO, CsBr, PbBr2, cyclohexanol, DMF additional amount are as follows: DMSO:CsBr:PbBr2: cyclohexanol: DMF= (20-35):(0.5-1.5):(1-3):(5-8):(12-20)。
The energy for adjusting incident cavity laser, 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 that being evacuated to pressure is 1 × 10-2Pa or less.
The silicon, refer to silicon to temperature range be 100 DEG C -250 DEG C.
The vacuum annealing time is 5-30 minutes.
The utility model has the advantages that
(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 is 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 accurate convenient.
(4) this technique can be applied to the industrialized production and practical application of the organic perovskite solar battery of large area.
Detailed description of the invention
Fig. 1 is the CsPbBr of Laser vaporization preparation3The SEM sectional view of film.
Fig. 2 is the CsPbBr of Laser vaporization preparation3The SEM plan view of film.
Fig. 3 is the CsPbBr of Laser vaporization preparation3The XRD diagram of film.
Fig. 4 is the CsPbBr of Laser vaporization preparation3The PL of film schemes.
Specific embodiment
Embodiment one:
By PbBr270 DEG C of heating magnetic agitations in the DMSO solution of 60ml are put into according to molar ratio 2:1 with CsBr to dissolve.Again DMF and hexamethylene mixed alkoxide solution are poured into, after being warming up to 110 DEG C with the rate of 1 DEG C/min and kept the temperature 10 hours, it is red heavy to take out Shallow lake solid is put into 100 DEG C of DMF solution and cleans, and then takes out and is put into 60 DEG C of drying in baking oven.Again by enough powder after drying End, which collects to be put into mold, is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparing CsPbBr3Target is put into cavity together, and intracavitary vacuum is evacuated to 7 × 10-3Pa heats substrate to 110 DEG C, and adjusts incident chamber The laser energy of body is 100mJ, and selecting laser frequency for 5Hz and umber of pulse is 1500.After 1500 pulsed depositions, substrate Continue the 10min that anneals, then takes out, CsPbBr3(film morphology is shown in that the SEM photograph of Fig. 1 and Fig. 2, XRD are shown in for film preparation completion Fig. 3, fluorescence spectrum are shown in Fig. 4).
Embodiment two:
By PbBr2It is molten that according to molar ratio 2.1:0.9 70 DEG C of heating magnetic agitations in the DMSO solution of 65ml are put into CsBr Solution.DMF and hexamethylene mixed alkoxide solution are poured into again, after being warming up to 110 DEG C with the rate of 1 DEG C/min and keep the temperature 10 hours, taken out Red precipitate solid is put into 100 DEG C of DMF solution and cleans, and then takes out and is put into 60 DEG C of drying in baking oven.It again will be after drying Enough powder collections, which are put into mold, is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparation Good CsPbBr3Target is put into cavity together, and intracavitary vacuum is evacuated to 1 × 10-3Pa, heat substrate to 150 DEG C, and adjust into The laser energy for penetrating cavity is 160mJ, and selecting laser frequency for 5Hz and umber of pulse is 1000.After 1000 pulsed depositions, Substrate continues the 20min that anneals, and then takes out, CsPbBr3Film preparation is completed.
Embodiment three:
By PbBr2It is molten that according to molar ratio 1.6:1.3 70 DEG C of heating magnetic agitations in the DMSO solution of 55ml are put into CsBr Solution.DMF and hexamethylene mixed alkoxide solution are poured into again, after being warming up to 110 DEG C with the rate of 1 DEG C/min and keep the temperature 10 hours, taken out Red precipitate solid is put into 100 DEG C of DMF solution and cleans, and then takes out and is put into 60 DEG C of drying in baking oven.It again will be after drying Enough powder collections, which are put into mold, is made CsPbBr with tablet press machine progress tabletting3Target.By clean glass substrate with preparation Good CsPbBr3Target is put into cavity together, and intracavitary vacuum is evacuated to 6 × 10-4Pa, heat substrate to 230 DEG C, and adjust into The laser energy for penetrating cavity is 230mJ, and selecting laser frequency for 5Hz and umber of pulse is 2000.After 2000 pulsed depositions, Substrate continues the 30min that anneals, and then takes out, CsPbBr3Film preparation is completed.
The present invention provides a kind of effectively and uniformly inorganic perovskite CsPbBr3Film passes through laser splash preparation method Thinking and implementation method, there are many concrete application approach, the above is only a preferred embodiment of the present invention, it is noted that right For those skilled in the art, without departing from the principle of the present invention, it can also make several improvements, Such as similar inorganic perovskite material C sPbX is grown by pulse laser deposition process3(X=Cl, I) film, different Growing film etc. on substrate, these improvement also should be regarded as protection scope of the present invention.

Claims (5)

1. a kind of Laser vaporization prepares CsPbBr3The method of film, it is characterised in that method includes the following steps:
1.) CsPbBr is prepared3Target: standard measure mixing DMF, DMSO, cyclohexanol, PbBr are heated using solution2, CsBr prepares Enough CsPbBr3CsPbBr is made after being suppressed with tablet press machine in monocrystal3Target；
2.) by clean substrate and the CsPbBr for preparing3Target is put into jointly in pulse laser deposition chamber, is vacuumized, heating Substrate, while the energy of incident cavity laser is adjusted, it then sets laser pulse number and starts to deposit；
3.) after depositing, substrate takes out after keeping heating temperature vacuum annealing in the cavity, obtains CsPbBr3Film；
The solution heats standard measure mixing DMF, DMSO, cyclohexanol, PbBr2, CsBr prepare enough CsPbBr3Monocrystalline powder Target is made using tablet press machine at room temperature, wherein DMSO, CsBr, PbBr in end2, cyclohexanol, DMF additional amount are as follows:
DMSO:CsBr:PbBr2: cyclohexanol: DMF=(20-35): (0.5-1.5): (1-3): (5-8): (12-20).
2. preparing CsPbBr according to Laser vaporization described in claim 13The method of film, it is characterised in that the adjusting is incident The energy of cavity laser refers 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.
3. preparing CsPbBr according to Laser vaporization described in claim 13The method of film, it is characterised in that described vacuumizes, Refer to that being evacuated to pressure is 1 × 10-2Pa or less.
4. preparing CsPbBr according to Laser vaporization described in claim 13The method of film, it is characterised in that the substrate adds Heat refers to that temperature range is 100 DEG C -250 DEG C.
5. preparing CsPbBr according to Laser vaporization described in claim 13The method of film, it is characterised in that the 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710933312.1A CN107805779B (en) 2017-10-10 2017-10-10 A kind of Laser vaporization preparation CsPbBr3The method of film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710933312.1A CN107805779B (en) 2017-10-10 2017-10-10 A kind of Laser vaporization preparation CsPbBr3The method of film

Publications (2)

Publication Number Publication Date
CN107805779A CN107805779A (en) 2018-03-16
CN107805779B true CN107805779B (en) 2019-07-12

Family

ID=61584850

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710933312.1A Active CN107805779B (en) 2017-10-10 2017-10-10 A kind of Laser vaporization preparation CsPbBr3The method of film

Country Status (1)

Country Link
CN (1) CN107805779B (en)

Families Citing this family (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
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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9997707B2 (en) * 2015-02-26 2018-06-12 Nanyang Technological University Perovskite thin films having large crystalline grains
CN105925938B (en) * 2016-07-08 2018-05-01 合肥工业大学 A kind of Cs2SnI6The pulsed laser deposition preparation method of film
CN106745204B (en) * 2016-11-28 2018-10-12 湖北大学 A kind of environmentally protective CsPbX3The synthetic method of perovskite quantum dot
CN107123706B (en) * 2017-04-07 2019-05-03 湖南大学 A kind of CVD building CsPbBr3The method of nanometer sheet electroluminescent device

Also Published As

Publication number Publication date
CN107805779A (en) 2018-03-16

Similar Documents

Publication Publication Date Title
CN107805779B (en) A kind of Laser vaporization preparation CsPbBr3The method of film
CN102912308B (en) Process for manufacturing vanadium dioxide thin film with low phase-transition temperature
CN105779956A (en) Method for preparing organic perovskite methyl amino lead iodide film by two-step method
CN101740358A (en) Method for preparing P type poly-silicon thin film on glass substrate
CN105925938B (en) A kind of Cs2SnI6The pulsed laser deposition preparation method of film
CN202989351U (en) Ingot furnace thermal field structure based on multiple heaters
CN105256280A (en) Method for regulating and controlling phase transition temperature of vanadium dioxide through fast heat treatment
CN111020487A (en) Method for preparing film of quasi-one-dimensional structure material with controllable orientation
CN105777800A (en) Method for preparing organic perovskite methyl amino lead iodide film through lead oxide film
CN102776556B (en) Polycrystalline silicon ingot and preparation method thereof as well as polycrystalline silicon wafer
CN105331950B (en) A kind of preparation method of two-dimentional perovskite thin film
CN104153001A (en) Method for preparing CdZnTe epitaxial film on GaAs single crystal substrate
CN1312734C (en) Method for preparing beta-FeSi2 semiconductor film by femtosecond pulsed laser
CN104264213A (en) EFG (edge-defined film-fed growth) device of large-size doped sapphire crystals and growth process thereof
CN102312293B (en) Method for growing large size Ta2O5 single crystal by using floating zone method
CN102586880A (en) Preparation method of oriented ZeTe nanocrystals
CN104975291B (en) Prepare the device of bismuth ferrite thin film, method and the method for preparing solar cell
CN114873639B (en) Ba (Bay) 3 Zr 2 S 7 Film, preparation method and application thereof
CN105177511B (en) A kind of negative thermal expansion material Sc2Mo3O12The preparation method of film
CN100368601C (en) Autoclave synthesis method of sulfur group compound
CN110565054B (en) Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
CN110349836A (en) A kind of preparation method of certain forbidden bandwidth selenizing germanous film
CN105132875B (en) A kind of method that diffusion method prepares high concentration gradient AZO monocrystalline conductive films
CN104505462A (en) Organic metal halide film and preparation method and application thereof
CN103693691A (en) Method of preparing vanadium dioxide by double-temperature area reduction process

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant