CN110565054B - Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film - Google Patents

Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film Download PDF

Info

Publication number
CN110565054B
CN110565054B CN201910863625.3A CN201910863625A CN110565054B CN 110565054 B CN110565054 B CN 110565054B CN 201910863625 A CN201910863625 A CN 201910863625A CN 110565054 B CN110565054 B CN 110565054B
Authority
CN
China
Prior art keywords
film
pbi
csi
cspbbr
pbbr
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
CN201910863625.3A
Other languages
Chinese (zh)
Other versions
CN110565054A (en
Inventor
徐庆宇
张昊
靳选
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 CN201910863625.3A priority Critical patent/CN110565054B/en
Publication of CN110565054A publication Critical patent/CN110565054A/en
Application granted granted Critical
Publication of CN110565054B publication Critical patent/CN110565054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation

Abstract

The invention discloses a method for preparing CsPbBr by laser two-step sputteringxI3‑xA method of fluorescent thin film. The method mainly utilizes the pulse laser deposition technology to deposit CsX and PbY on the substrate in sequence2Two layers of (X, Y ═ I, Br) are used for generating CsPbBr by using the principle of thermal diffusionxI3‑x(x is 0 < x < 3) fluorescent film. The method comprises the following specific steps: CsBr and PbBr are firstly added2、CsI、PbI2Pressing the powder into CsBr and PbBr2、CsI、PbI2And (3) preparing a target material by adopting a pulsed laser deposition film preparation technology: heating the substrate at 200 deg.C, and depositing CsX and PbY with specific pulse number by pulse laser2(X, Y ═ I, Br) two layers, CsPbBr was prepared by the thermal diffusion principlexI3‑xA fluorescent film. The invention utilizes the pulsed laser deposition technology and prepares CsPbBr by matching with the target materialxI3‑xThe fluorescent film replaces the traditional quantum dot solution method, the preparation method is simpler and more convenient, the cost is low, the preparation period is effectively reduced, the environment is protected, the safety is realized, the variety of the preparation materials is wider, and the industrial production and the commercial application of the fluorescent film are facilitated.

Description

Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
Technical Field
The invention relates to inorganic perovskite CsPbBrxI3-xA method for preparing a fluorescent film, in particular to a method for preparing inorganic perovskite CsPbBr by using a pulse laser deposition method and combining with a thermal diffusion reaction principlexI3-x(x is 0 < x < ═ 3) and belongs to the field of technology.
Background
Such inorganic perovskite crystalline forms (ABX)3) Material, ABX thereof3In the structure, A is metal cesium ion (Cs)+) B is a metal cation (Pb)2+、Sn2+Etc.), X is a halide bromide (Br)-、I-、Cl-Etc.). The material is widely applied to manufacturing light absorption layers and fluorescent materials of solar cells. CsPbBr commonly used at presentxI3-xThe preparation method of the fluorescent film (x is 0 < x ≦ 3) mainly comprises the steps of quantum dot solution spin coating and the like, but the preparation methods need to prepare the quantum dot solution firstly and then prepare the fluorescent film by a spin coating method, so that the steps are complex, the materials are wasted, the preparation period is long, and the preparation method is not beneficial to industrial production and practical application.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a method for preparing inorganic perovskite CsPbBr by two steps of laser sputteringxI3-x(x is 0 < x < 3) fluorescent film. The invention prepares the inorganic perovskite CsPbBr by using a pulse laser deposition method and combining with the thermal diffusion reaction principlexI3-xThe fluorescent film is realized by replacing a quantum dot solution method, the preparation method is simpler and more convenient, the cost is low, the environment is protected, the safety is realized, the preparation period is effectively reduced, the variety of preparation materials is wider, and the industrial production and the commercial application of the fluorescent film are facilitated.
The technical scheme is as follows: the invention relates to a method for preparing CsPbBr by laser two-step sputteringxI3-xA method of making a fluorescent film, comprising the steps of:
1.) preparing a target material: respectively reacting CsBr and PbBr2、CsI、PbI2Pressing into CsBr and PbBr by tablet press2、CsI、PbI2A target material;
2.) putting the clean substrate and two selected targets together into a deposition cavity of the pulsed laser deposition equipment by using the pulsed laser deposition equipment, wherein one target is CsBr or CsI target, and the other target is PbBr2Or PbI2A target material; vacuum pumping is carried out to 10-3Heating the substrate to 150-300 ℃ at the same time when the Pa magnitude is higher than the magnitude of Pa;
3.) in a pulsed laser deposition device, firstly depositing CsBr or CsI thin film and then depositing PbBr2Or PbI2Depositing double-layer films with different thicknesses by using different laser pulse numbers according to different proportions of Br and I in the final film, wherein the maximum thickness of each layer of film can reach 200nm,
4.) stopping heating immediately after the laser deposition is finished, and taking out the cavity in time after the temperature is reduced to the room temperature.
Wherein:
the substrate used in the step 2) is silica glass, acrylic glass, a mica sheet, a transparent polymer, a high-molecular substrate or a transparent plastic substrate.
And 3) controlling the thickness of each component by using a pulsed laser deposition device and controlling the final composition of the film by using laser energy and pulse number. The deposition process has a fixed sequence of firstly depositing CsX and then depositing PbY2(X,Y＝I,Br)。
The size of the target is larger than 1 cm, and the purity is more than 99%.
The thickness ratio of the bilayer films is determined by x, CsBr and PbI2The film thickness ratio is 1.28x/(3-x), CsI and PbBr2The film thickness ratio is 2.09(3-x)/x, the deposition process is maintained at 150-300 ℃ to directly generate the required CsPbBr by thermal diffusionxI3-xA fluorescent film; x is 0 < x < 3, CsPbI3Sample passage through CsI and PbI2And (4) preparing a target material.
Has the advantages that:
(1) the preparation technology of the Pulse Laser Deposition (PLD) film is used for replacing a quantum dot solution method, so that the complicated preparation process of the quantum dot can be omitted, the preparation process is simpler, the cost is effectively reduced, and the preparation period is shortened.
(2) The whole preparation process does not use any solution and any by-product, and the preparation process is more environment-friendly and safer.
(3) By selecting and matching different targets, the inorganic perovskite CsPbBr with continuously adjustable components can be preparedxI3-x(x is 0 < x < 3) fluorescent film.
Drawings
FIG. 1 laser two-step sputtering preparation of CsPbBrxI3-x(x is in the range of 0 < x < 3) schematic representation of fluorescent films.
FIG. 2 laser two-step sputtering preparation of CsPbBrxI3-x(x is in the range of 0 < x < 3) SEM plan view of the fluorescent film.
FIG. 3 laserStep sputtering preparation of CsPbBrxI3-x(x is in the range of 0 < x < 3) XRD pattern of the fluorescent film.
FIG. 4 laser two-step sputtering preparation of CsPbBrxI3-x(x is in the range of 0 < x < 3) PL profile of the fluorescent film.
Detailed Description
1.) preparing a target material: respectively reacting CsBr and PbBr2、CsI、PbI2Pressing into CsBr and PbBr by tablet press2、CsI、PbI2A target material;
2.) clean substrate with two selected targets (one CsBr or CsI target and the other PbBr target)2Or PbI2Target material) are put into a Pulsed Laser Deposition (PLD) cavity together and vacuumized to 10-3Heating the substrate to 150-300 ℃ at the same time when the Pa magnitude is higher than the magnitude of Pa;
3.) using a pulsed laser deposition device to deposit CsBr or CsI film first and then PbBr2Or PbI2Film according to CsPbBr finalxI3-x(x is in the range of 0 < x < 3) the ratio of Br to I in the fluorescent film determines the film thickness, CsBr and PbI2The film thickness ratio is 1.28x/(3-x), CsI and PbBr2The film thickness ratio was 2.09 (3-x)/x. The required CsPbBr is generated by thermal diffusion in the deposition process at 150-300 DEG CxI3-x(x is 0 < x < 3) fluorescent film;
4.) stopping heating immediately after the laser deposition is finished, and taking out the cavity in time after the temperature is reduced to the room temperature.
Wherein:
step 2) using thermal diffusion principle using dual targets CsX and PbY2(X, Y ═ I, Br) was prepared by two-step deposition. The substrate used for sputtering is glass, mica, a transparent polymer substrate, a transparent plastic substrate and other soft and hard transparent substrates.
And 3) the film preparation process is pulse laser deposition. The film thickness of each component is determined by the laser energy and the number of pulses, and ultimately the composition of the film. The deposition process has a fixed sequence of firstly depositing CsX and then depositing PbY2(X,Y＝I,Br)。
Embodiment 1:
reacting CsBr and PbBr2Pressing into CsBr and PbBr by tablet press2Placing the target material and clean substrate together into a Pulsed Laser Deposition (PLD) chamber, and vacuumizing to 10%-3Pa magnitude while heating the substrate to 300 degrees celsius. Adjusting the energy of the incident cavity laser to 120mJ, adjusting the pulse frequency to 5Hz, depositing CsBr and then PbBr2Setting CsBr and PbBr2Respectively 25 pulses and 15 pulses, stopping heating immediately after laser deposition is finished, and timely taking out the prepared CsPbBr after the cavity is deflated3A fluorescent film.
Embodiment 2:
mixing CsI and PbBr2Pressing into CsI and PbBr by tablet press2Placing the target material and clean substrate together into a Pulsed Laser Deposition (PLD) chamber, and vacuumizing to 10%-3Pa magnitude while heating the substrate to 200 degrees celsius. Adjusting the energy of the incident cavity laser to 120mJ, adjusting the pulse frequency to 5Hz, depositing CsI and then PbBr2Setting CsI and PbBr 220 pulses and 14 pulses respectively, stopping heating immediately after laser deposition is finished, and taking out the prepared CsPbIBr in time after the cavity is deflated2A fluorescent film.
Embodiment 3:
mixing CsBr and PbI2Pressing into CsBr and PbI powder with tablet press2Placing the target material and clean substrate together into a Pulsed Laser Deposition (PLD) chamber, and vacuumizing to 10%-3Pa magnitude while heating the substrate to 200 degrees celsius. Adjusting the energy of the incident cavity laser to 120mJ, adjusting the pulse frequency to 5Hz, depositing CsBr and then PbI2Setting CsBr and PbI 220 pulses and 13 pulses respectively, stopping heating immediately after laser deposition is finished, and taking out the prepared CsPbBrI in time after the cavity is deflated2A fluorescent film.
Embodiment 4:
mixing CsI and PbI2Pressing into CsI and PbI powder by tablet press2Placing the target material and clean substrate together into a Pulsed Laser Deposition (PLD) chamber, and vacuumizing to 10%-3Pa order while heating the substrateTo 150 degrees celsius. Adjusting the energy of the incident cavity laser to 120mJ, adjusting the pulse frequency to 5Hz, depositing CsI and then PbI2Setting CsI and PbI2Respectively 9 pulses and 7 pulses, stopping heating immediately after laser deposition is finished, and taking out the prepared CsPbI in time after the cavity is deflated3A fluorescent film.
The invention provides a method for preparing inorganic perovskite CsPbBr by a pulse laser sputtering methodxI3-x(x ranges from 0 to 3) the concept and implementation method of the fluorescent thin film are low in cost, simple in process, and many specific application ways, and the above are only preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements can be made, such as the growth of inorganic perovskite CsPbBr by magnetron sputtering, Atomic Layer Deposition (ALD), Molecular Beam Epitaxy (MBE) instead of pulsed laser deposition, and the likexI3-x(x is 0 < x < 3) fluorescent film; or the opaque substrate such as silicon chip, silicon dioxide substrate, metal iron sheet and the like is used for replacing the transparent substrate; or preparing similar materials such as CsPbBrxCl3-x(x ranges from 0 < x < 3); and increasing or decreasing the thickness of the film by increasing or decreasing the total number of pulses, etc., should also be considered as the scope of the present invention.

Claims (3)

1. Laser two-step sputtering preparation CsPbBrxI3-xA method of making a fluorescent film, comprising the steps of:
1.) preparing a target material: respectively reacting CsBr and PbBr2、CsI、PbI2Pressing into CsBr and PbBr by tablet press2、CsI、PbI2A target material;
2.) putting the clean substrate and two selected targets together into a deposition cavity of the pulsed laser deposition equipment by using the pulsed laser deposition equipment, wherein one target is CsBr or CsI target, and the other target is PbBr2Or PbI2A target material; vacuum pumping is carried out to 10-3 Pa or above, while heating the substrate to 150-Degree of change;
3.) in a pulsed laser deposition device, firstly depositing CsBr or CsI thin film and then depositing PbBr2Or PbI2Depositing double-layer films with different thicknesses by using different laser pulse numbers according to different proportions of Br and I in the final film, wherein the maximum thickness of each layer of film can reach 200nm,
4.) stopping heating immediately after the laser deposition is finished, and taking out the cavity in time after the cavity is deflated after the temperature is reduced to the room temperature;
the substrate used in the step 2) is silica glass, acrylic glass, a mica sheet, a transparent polymer, a high-molecular substrate or a transparent plastic substrate;
step 3) controlling the thickness of each component by using pulsed laser deposition equipment and laser energy and pulse number, and controlling the final components of the film; the deposition process has a fixed sequence of firstly depositing CsX and then depositing PbY2 (X,Y= I, Br)。
2. The laser two-step sputtering method for preparing CsPbBr according to claim 1xI3-x The method of the fluorescent film is characterized in that the size of the target material is larger than 1 cm, and the purity is more than 99%.
3. The laser two-step sputtering method for preparing CsPbBr according to claim 1xI3-x Method for the production of a fluorescent thin film, characterized in that the thickness ratio of the two layers is determined by x, CsBr and PbI2The film thickness ratio is 1.28x/(3-x), CsI and PbBr2The film thickness ratio is 2.09(3-x)/x, the deposition process is maintained at 150-300 ℃ to directly generate the required CsPbBr by thermal diffusionxI3-xA fluorescent film; x is 0 < x < 3, CsPbI3Sample passage through CsI and PbI2And (4) preparing a target material.
CN201910863625.3A 2019-09-12 2019-09-12 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film Active CN110565054B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910863625.3A CN110565054B (en) 2019-09-12 2019-09-12 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910863625.3A CN110565054B (en) 2019-09-12 2019-09-12 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film

Publications (2)

Publication Number Publication Date
CN110565054A CN110565054A (en) 2019-12-13
CN110565054B true CN110565054B (en) 2021-04-27

Family

ID=68779505

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910863625.3A Active CN110565054B (en) 2019-09-12 2019-09-12 Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film

Country Status (1)

Country Link
CN (1) CN110565054B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111874941B (en) * 2020-07-10 2022-09-27 五邑大学 CsPbBr 3 Perovskite and preparation method and device thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779956A (en) * 2016-03-21 2016-07-20 东南大学 Method for preparing organic perovskite methyl amino lead iodide film by two-step method
CN107805779A (en) * 2017-10-10 2018-03-16 东南大学 A kind of Laser vaporization prepares CsPbBr3The method of film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779956A (en) * 2016-03-21 2016-07-20 东南大学 Method for preparing organic perovskite methyl amino lead iodide film by two-step method
CN107805779A (en) * 2017-10-10 2018-03-16 东南大学 A kind of Laser vaporization prepares CsPbBr3The method of film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Transformation of sintered CsPbBr3 Nanocrystals to Cubic CsPbI3 and Grandient CsPbBrxI3-x through Halide Exchange";Jacob B. Hoffman，et al.;《Journal of the American chemical society》;20160620;第138卷;第8603-8611页 *

Also Published As

Publication number Publication date
CN110565054A (en) 2019-12-13

Similar Documents

Publication Publication Date Title
Kondrotas et al. Growth mechanism of Sb2Se3 thin films for photovoltaic application by vapor transport deposition
CN102912308B (en) Process for manufacturing vanadium dioxide thin film with low phase-transition temperature
WO2019214037A1 (en) Curved coated panel, preparation method thereof, and solar module
JP2009510263A (en) Sputtering target, low resistance transparent conductive coating, method for forming such coating and composition for use in the conductive coating
WO2017045398A1 (en) Low-temperature deposition method for vanadium dioxide thin film
CN112456813B (en) Nickel oxide electrochromic film and preparation method and application thereof
CN107805779B (en) A kind of Laser vaporization preparation CsPbBr3The method of film
CN110565054B (en) Laser two-step sputtering preparation CsPbBrxI3-xMethod for fluorescent film
CN106835030A (en) Infrared high antireflection film structure of wide-angle multiband and preparation method thereof
CN109136859A (en) A method of preparing high transparency gallium oxide film
CN111020487A (en) Method for preparing film of quasi-one-dimensional structure material with controllable orientation
CN110699670B (en) Preparation method of vanadium dioxide film
CN101798680A (en) Magnetron sputtering preparation process for Mg2Si thin film made of environment-friendly semiconductor material
CN104451600B (en) Preparation method of bismuth oxide thin film material
CN109082631B (en) Ga2O3Transparent conductive film and preparation method thereof
CN107245689B (en) Chemical method for large-area preparation of methylamine lead halide photoelectric film
JP2008297500A (en) Thermochromic material and manufacturing method thereof
JP2015510043A (en) Sputtering target and associated sputtering method for forming an airtight barrier layer
KR102164629B1 (en) Composite transparent electrodes
JP2009040640A (en) Method for producing zinc oxide thin film
CN105603382B (en) A method of enhancing vanadium dioxide film phase transition performance
CN103774098A (en) Thin film with stannous oxide texture and preparation method thereof
CN105112870B (en) A kind of ferroelectricity vanadium oxide composite film and preparation method thereof
CN104716227A (en) Method for manufacturing CZTS thin film solar cell absorbing layer
CN203460510U (en) Temperable high-transparent double-silver low-emissivity coated glass

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