CN113528127A - A kind of preparation method of manganese-doped copper-based halide perovskite powder - Google Patents
A kind of preparation method of manganese-doped copper-based halide perovskite powder Download PDFInfo
- Publication number
- CN113528127A CN113528127A CN202110946748.0A CN202110946748A CN113528127A CN 113528127 A CN113528127 A CN 113528127A CN 202110946748 A CN202110946748 A CN 202110946748A CN 113528127 A CN113528127 A CN 113528127A
- Authority
- CN
- China
- Prior art keywords
- manganese
- halide perovskite
- copper
- based halide
- preparation
- 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.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- 150000004820 halides Chemical class 0.000 title claims abstract description 57
- 239000000843 powder Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 10
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims abstract description 10
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- SWEHEIXLKOFPBQ-UHFFFAOYSA-N O.O.O.O.[Cl] Chemical compound O.O.O.O.[Cl] SWEHEIXLKOFPBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 150000004685 tetrahydrates Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
本发明公开了一种锰掺杂铜基卤化物钙钛矿粉末及其制备方法，该锰掺杂铜基卤化物钙钛矿为Mn:Cs3Cu2I5，所述制备方法为：(1)将碘化铯与碘化亚铜混合后充分研磨，得到铜基卤化物钙钛矿粉末；(2)将步骤(1)制得的铜基卤化物钙钛矿粉末与四水合氯化锰混合后充分研磨，得到锰掺杂的铜基卤化物钙钛矿粉末。本发明操作简单，可以大批量生产，且制得的锰掺杂铜基卤化物钙钛矿粉末发光可调。
The invention discloses a manganese-doped copper-based halide perovskite powder and a preparation method thereof. The manganese-doped copper-based halide perovskite is Mn:Cs 3 Cu 2 I 5 , and the preparation method is: ( 1) fully grinding the cesium iodide and cuprous iodide to obtain copper-based halide perovskite powder; (2) mixing the copper-based halide perovskite powder obtained in step (1) with tetrahydrate chlorination The manganese is mixed and thoroughly ground to obtain manganese-doped copper-based halide perovskite powder. The invention has simple operation, can be mass-produced, and the prepared manganese-doped copper-based halide perovskite powder has adjustable light emission.
Description
Technical Field
The invention relates to a manganese-doped copper-based halide perovskite and a preparation method thereof, belonging to the field of photoelectric functional materials.
Background
In recent years, halide perovskites are considered to be good candidate materials for next-generation light-emitting devices due to the advantages of simple preparation method, low cost, easy regulation and control of light emission and the like. The traditional lead-based halide perovskites have certain limitations in practical application due to poor stability and toxicity of lead elements. Copper-based halide perovskites are believed to be expected to address both of these issues while maintaining a high fluorescence quantum yield of lead-based halide perovskites. There are two main approaches to fluorescence modulation of halide perovskites: (1) the energy gap is adjusted by changing the halogen composition, so that the intrinsic fluorescence peak position is changed; (2) impurity level is introduced by doping to realize impurity fluorescence. Both of these methods have certain difficulties in copper-based halide perovskites: halogen exchange can greatly reduce the fluorescence quantum yield, and the fluorescence regulation range is far smaller than that of lead-based halide perovskite. Cation doping is realized at a high temperature of 450 ℃, the process is complex and the cost is increased. Therefore, a new doping method needs to be provided, which can realize the doping of cations and reduce the reaction temperature, so as to realize the low-cost regulation and control of the luminescence of the copper-based halide perovskite.
Disclosure of Invention
The invention aims to provide manganese-doped copper-based halide perovskite powder and a preparation method thereof, which can reduce the temperature required by doping and realize the fluorescence regulation and control of the copper-based halide perovskite by manganese doping.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for preparing the Mn-doped Cu-base halide perovskite powder (Mn: Cs)3Cu2I5The preparation method comprises the following steps:
(1) preparation of copper-based halide perovskite Cs3Cu2I5: mixing cesium iodide powder and cuprous iodide powder, and then fully grinding to obtain copper-based halide perovskite powder;
(2) preparation of manganese-doped copper-based halide perovskite Mn: Cs3Cu2I5: and (2) mixing the copper-based halide perovskite powder prepared in the step (1) with manganese chloride tetrahydrate, and then fully grinding to obtain manganese-doped copper-based halide perovskite powder.
In the step (1), the stoichiometric ratio of cesium iodide powder to cuprous iodide powder is 3: 2.
In the step (2), the dosage of the manganese chloride tetrahydrate is 0-15% in terms of Mn/Cu molar ratio, but 0% is not included.
In the steps (1) and (2), the grinding time is more than 20 minutes.
In the steps (1) and (2), the grinding is one of the following three grinding modes: (a) grinding by adding raw materials only, (b) grinding by adding raw materials and silicon dioxide powder, (c) grinding by adding raw materials and 10-50 ml of buffer solution.
The buffer solution is one of n-hexane, toluene and octadecene; if octadecene is added as buffer for grinding, it is necessary to wash for 2-3 times with n-hexane and then dry, and if n-hexane or toluene is added as buffer for grinding, it is dried directly.
Has the advantages that: compared with the prior art, the manganese-doped copper-based halide perovskite and the preparation method thereof provided by the invention have the following advantages:
(1) the method has the advantages of simple operation, high material utilization rate, small dependence on equipment and short preparation period;
(2) the copper-based halide perovskite powder with higher fluorescence quantum yield can be produced in large batch;
(3) the doping of manganese can introduce an impurity fluorescence peak with a peak value at 540 nm;
(4) the relative intensity of the intrinsic fluorescence peak and the impurity fluorescence can be adjusted by changing the feed ratio of manganese.
Drawings
FIG. 1 is a graph showing the results of fluorescence spectrum characterization of copper-based halide perovskite powders of different manganese doping concentrations prepared in examples 1 to 5;
FIG. 2 is a CIE coordinate diagram corresponding to the fluorescence spectra of copper-based halide perovskite powders with different manganese doping concentrations prepared in examples 1-5 and an application example of the copper-based halide perovskite powders as color conversion layers for light emitting diodes;
FIG. 3 is a graph showing the X-ray diffraction spectrum characterization results of copper-based halide perovskites of different manganese doping concentrations prepared in examples 1-5;
FIG. 4 is an X-ray photoelectron spectroscopy characterization of manganese-doped copper-based halide perovskites prepared in example 2 at a Mn/Cu molar ratio of 7.5% doping concentration;
FIG. 5 is a scanning electron microscopy characterization of manganese-doped copper-based halide perovskites prepared in example 2 at a Mn/Cu molar ratio of 7.5% doping concentration;
FIG. 6 is a schematic diagram of a manganese doped copper-based halide perovskite energy level structure;
FIG. 7 is a schematic process flow diagram of the preparation method of the present invention.
Detailed Description
The invention is explained in more detail below with reference to exemplary embodiments and the accompanying drawings.
Example 1
Preparation of undoped copper-based halide perovskite powder: 77.94 mg cesium iodide was mixed with 38.09 mg cuprous iodide and directly ground for 25 minutes to obtain copper-based halide perovskite powder.
Example 2
(1) Preparation of copper-based halide perovskite powder: mixing 77.94 mg of cesium iodide and 38.09 mg of cuprous iodide, and directly grinding for 25 minutes to obtain copper-based halide perovskite powder;
(2) preparing manganese-doped copper-based halide perovskite powder: and (3) adding 3 mg of manganese chloride tetrahydrate (the molar ratio of Mn to Cu is 7.5%) into the prepared copper-based lead-free perovskite powder, mixing, adding 30ml of n-hexane, grinding for 30 minutes, filtering and drying the suspension to obtain the manganese-doped copper-based lead-free perovskite powder.
Example 3
(1) Preparation of copper-based halide perovskite powder: mixing 779.4 mg of cesium iodide and 380.9 mg of cuprous iodide, and directly grinding for 25 minutes to obtain copper-based lead-free perovskite powder;
(2) preparing manganese-doped copper-based halide perovskite powder: and taking the prepared copper-based lead-free perovskite powder, adding 19.8 mg of manganese chloride tetrahydrate (the molar ratio of Mn/Cu is 5%), mixing, adding 30ml of n-hexane, grinding for 30 minutes, filtering and drying the suspension to obtain the manganese-doped copper-based lead-free perovskite powder.
Example 4
(1) Preparation of copper-based halide perovskite powder: mixing 1558.8 mg of cesium iodide and 761.8 mg of cuprous iodide, directly adding 20mL of toluene, grinding for 30 minutes, filtering and drying the suspension to obtain copper-based lead-free perovskite powder;
(2) preparing manganese-doped copper-based halide perovskite powder: and (3) adding 79.2 mg of tetrahydrated manganese chloride (the molar ratio of Mn to Cu is 10%) into the prepared copper-based lead-free perovskite powder, mixing, adding 20mL of toluene, grinding for 30 minutes, filtering and drying the suspension to obtain the manganese-doped copper-based lead-free perovskite powder.
Example 5
(1) Preparation of copper-based halide perovskite powder: mixing 3897 mg of cesium iodide and 1904.5 mg of cuprous iodide, directly adding 10mL of octadecene, grinding for 30 minutes, cleaning the suspension with n-hexane for 2 times, filtering, and drying to obtain copper-based lead-free perovskite powder;
(2) preparing manganese-doped copper-based halide perovskite powder: and adding 296.7 mg of manganese chloride tetrahydrate (the molar ratio of Mn to Cu is 15%) into the prepared copper-based lead-free perovskite powder, mixing, adding 10mL of octadecene, grinding for 30 minutes, cleaning the suspension with n-hexane for 2 times, filtering and drying to obtain the manganese-doped copper-based lead-free perovskite powder.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110946748.0A CN113528127A (en) | 2021-08-18 | 2021-08-18 | A kind of preparation method of manganese-doped copper-based halide perovskite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110946748.0A CN113528127A (en) | 2021-08-18 | 2021-08-18 | A kind of preparation method of manganese-doped copper-based halide perovskite powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113528127A true CN113528127A (en) | 2021-10-22 |
Family
ID=78122563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110946748.0A Pending CN113528127A (en) | 2021-08-18 | 2021-08-18 | A kind of preparation method of manganese-doped copper-based halide perovskite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113528127A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124994A (en) * | 2022-05-25 | 2022-09-30 | 福建江夏学院 | Synthesis method and product of a novel cesium ammonium copper iodide perovskite material with enhanced fluorescence |
| KR20240006396A (en) * | 2022-07-06 | 2024-01-15 | 서울과학기술대학교 산학협력단 | Method of fabricating blue-emitting nanoparticles |
| CN118495577A (en) * | 2024-07-17 | 2024-08-16 | 中国科学技术大学 | Copper-based halide powder, scintillator film, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880618A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A Synthesis Method of Mn-Doped Cs2AgInCl6 with High Fluorescence Efficiency |
| CN113265251A (en) * | 2021-05-28 | 2021-08-17 | 吉林师范大学 | A kind of preparation method of metal bromide post-treated manganese-doped perovskite nanocrystal and perovskite nanocrystal |
-
2021
- 2021-08-18 CN CN202110946748.0A patent/CN113528127A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880618A (en) * | 2019-03-14 | 2019-06-14 | 吉林大学 | A Synthesis Method of Mn-Doped Cs2AgInCl6 with High Fluorescence Efficiency |
| CN113265251A (en) * | 2021-05-28 | 2021-08-17 | 吉林师范大学 | A kind of preparation method of metal bromide post-treated manganese-doped perovskite nanocrystal and perovskite nanocrystal |
Non-Patent Citations (1)
| Title |
|---|
| JUNFENG QU ET AL.: "Lead-free p-type Mn:Cs3Cu2I5 perovskite with tunable dual-color emission through room-temperature grinding method", 《 J MATER SCI》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124994A (en) * | 2022-05-25 | 2022-09-30 | 福建江夏学院 | Synthesis method and product of a novel cesium ammonium copper iodide perovskite material with enhanced fluorescence |
| KR20240006396A (en) * | 2022-07-06 | 2024-01-15 | 서울과학기술대학교 산학협력단 | Method of fabricating blue-emitting nanoparticles |
| KR102696629B1 (en) | 2022-07-06 | 2024-08-20 | 서울과학기술대학교 산학협력단 | Method of fabricating blue-emitting nanoparticles |
| CN118495577A (en) * | 2024-07-17 | 2024-08-16 | 中国科学技术大学 | Copper-based halide powder, scintillator film, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113528127A (en) | A kind of preparation method of manganese-doped copper-based halide perovskite powder | |
| CN109777403B (en) | High fluorescence efficiency Cs2AgxNa1-xInCl6Preparation method of double-layer perovskite | |
| CN109880618B (en) | A Synthesis Method of Mn-Doped Cs2AgInCl6 with High Fluorescence Efficiency | |
| CN111081816A (en) | Perovskite nanocrystalline with alkali metal ion passivated surface defect and preparation and application thereof | |
| JP2020161442A (en) | Perovskite quantum dot light emitting device and manufacturing method thereof | |
| CN107384387B (en) | Manganese-doped CsPbBr3Perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application thereof | |
| KR102615700B1 (en) | Method of manufacturing phosphor | |
| CN106701070A (en) | Blue, yellow and orange light calcium titanium mining quantum dot and molecular sieve composite luminescent material and preparing method and application thereof | |
| Zhao et al. | Inorganic halide perovskites for lighting and visible light communication | |
| CN112521938B (en) | Organic-inorganic hybrid halide luminescent material and preparation method and application thereof | |
| CN115028184B (en) | Er 3+ Doped rare earth-based double perovskite single crystal and preparation method and application thereof | |
| CN110776907A (en) | A method for improving the stability of red fluorescent organic-inorganic hybrid perovskite-structured MAPbI3 quantum dots | |
| CN107118769A (en) | A kind of additive Mn perovskite quantum dot and molecular sieve composite luminescent material and preparation method and application | |
| WO2019099657A1 (en) | Doped perovskite structures for light-emitting devices and other applications | |
| CN109957400B (en) | A kind of preparation method of Mn4+ ion-activated fluoride phosphor | |
| CN111635758A (en) | A kind of preparation method of silica-wrapped fluorescent carbon quantum dot composite microspheres | |
| CN109266325B (en) | Preparation method of blue light emitting perovskite quantum dot based on surface modifier | |
| CN107201227A (en) | A kind of method that Microwave-assisted firing synthesizes CsSnX3 perovskite quantum dots | |
| CN114032100A (en) | A Sb3+ ion-activated and color-tunable perovskite-type chloride luminescent material | |
| KR102626917B1 (en) | Nanocrystal, preparing method thereof, and optoelectronic device | |
| CN115838593A (en) | Method for preparing halogen-doped double perovskite fluorescent powder under mild reaction conditions | |
| CN113667473A (en) | Zero-dimensional organic-inorganic hybrid metal halide luminescent material, preparation method and application thereof | |
| CN115651652B (en) | All-inorganic quaternary metal halide with waterproof function and preparation method thereof | |
| CN116814254B (en) | A rare earth-free and lead-free halide double perovskite-based two-component phosphor and its preparation method and application | |
| CN114806564B (en) | Trivalent chromium ion doped fluoroantimonate near infrared fluorescent material, preparation method and LED light source thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211022 |