NCS-doped manganese-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof
By using the NCS-doped manganese-based organic-inorganic hybrid metal halide preparation method, the emission spectrum of manganese-based organic-inorganic hybrid halides has been extended to the yellow light region, solving the problem of single spectrum in the existing technology, realizing low-cost large-scale production and application in light-emitting devices, solid-state lighting, and display fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- KUNMING UNIV OF SCI & TECH
- Filing Date
- 2026-03-25
- Publication Date
- 2026-05-26
AI Technical Summary
The emission spectra of existing manganese-based organic-inorganic hybrid halide materials are limited to a single green or red light, making it difficult to extend to a wider range and thus limiting their application diversity.
A method for preparing NCS-doped manganese-based organic-inorganic hybrid metal halide luminescent materials was adopted. The (C12H28N)2MnBr4:NCS-microcrystalline powder was prepared by reacting C12H28NX, MnBr2 or MnBr2·4H2O and ASCN in N,N-dimethylformamide, followed by evaporation, crystallization, washing and drying.
The emission band of manganese-based organic-inorganic hybrid metal halides has been successfully extended to the yellow light region, providing a low-cost, large-scale method for preparing fluorescent materials that can be applied to light-emitting devices, solid-state lighting, displays and other fields.
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Figure CN122079796A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing hybrid metal halide materials, and more particularly to manganese-based organic-inorganic hybrid metal halide luminescent materials and their preparation. Background Technology
[0002] In recent years, organic-inorganic metal halides have shown great potential in fields such as light-emitting diodes, information storage, chemical sensing, and anti-counterfeiting due to their tunable structures and excellent optoelectronic properties. Unlike traditional all-inorganic metal halides, organic-inorganic hybrid halides have molecular-scale tunability, a wide range of organic-inorganic components to choose from, and the ability to adjust the crystal structure size.
[0003] Manganese-based organic-inorganic hybrid halides have attracted much attention due to their unique dd-transition luminescence properties, tunable crystal field environment, and strong absorption in the ultraviolet-blue light region. Mn 2+ The luminescence originates from spin-forbidden transitions within its 3d orbitals, a process that affects Mn. 2+ The crystal field environment in which it exists is highly sensitive. Typically, manganese-based organic-inorganic hybrid halides exhibit only single Mn content. 2+ dd transition emitter band: tetracoordinated Mn 2+ While narrow-band green light is produced, octahedral coordination generates broadband red light due to significant crystal field splitting. Furthermore, the efficient dd transitions make it difficult for OIHMHs to produce self-trapped exciton emissions common in other zero-dimensional hybrid metal halides. Therefore, breaking through the limitation of single green or red light emission in OIHMHs and extending their emission spectrum to a wider range is of great significance for enriching their luminescent properties and expanding their application diversity, and is also a major challenge currently faced.
[0004] In recent years, pseudohalogenated thiocyanate (SCN) - / NCS - Anions, due to their halogen-like properties, have attracted widespread attention in the photoelectric research of metal halides. Thiocyanate ions possess a linear Lewis base structure; the lone pairs of electrons on their sulfur and nitrogen atoms can induce charge density rearrangement around the coordination metal center, leading to significant lattice distortion. This provides a basis for regulating the coordination environment-sensitive MnO2. 2+ The dd transition provides a novel and promising approach. Summary of the Invention
[0005] To address the above problems, the present invention provides an NCS. - Manganese-doped organic-inorganic hybrid metal halide luminescent materials, their preparation methods, and applications have been successfully extended to the yellow light region of the emission band of manganese-based organic-inorganic hybrid metal halides, providing a new strategy for the photoelectric modulation of organic-inorganic hybrid metal halides.
[0006] Another objective of this invention is to propose a yellow light-emitting fluorescent material that is simple to prepare, has extremely low cost, and is easy to promote on a large scale.
[0007] To achieve the above-mentioned technical effects, the present invention is implemented through the following preparation method: an NCS - Manganese-doped organic-inorganic hybrid metal halide luminescent materials, raw material: C 12 H 28 NX (X can be Cl) - ,Br - I - BF4 - One or more of the following), MnBr2 or MnBr2·4H2O), ASCN (A can be NH4) + Li + Na + K + One or more of them).
[0008] Its preparation method includes the following steps:
[0009] 1) Precursor solution: Prepare raw material C... 12 H 28 NX, MnBr2 (MnBr2·4H2O) and ASCN were dissolved in 2-6 mL of N,N-dimethylformamide at a molar ratio of 1.0-4.0:0.5-2.0:0.5-2.0. The solution was stirred at room temperature for 10-30 minutes to obtain a clear precursor solution, which was then filtered.
[0010] 2) Evaporation and crystallization: Place the filtered solution from step 1) in an environment of 60-90℃ for 1-3 days to obtain (C 12 H 28 N)2MnBr4:NCS - Microcrystalline powder.
[0011] 3) Washing and drying: Pour the microcrystalline powder obtained in step 2) into a centrifuge tube, add 3-6 mL of ethyl acetate, centrifuge and wash at 4000-8000 rpm for 3-5 minutes, repeat 2-4 times, and then dry in a vacuum oven for 12-24 hours to obtain dried (C) 12 H 28 N)2MnBr4:NCS - Microcrystalline powder.
[0012] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0013] Yellow light emission was achieved in manganese-based organic-inorganic hybrid metal halides.
[0014] This luminescent material is extremely inexpensive.
[0015] The solvent evaporation method is a simple, low-cost, and easily scalable method for preparing manganese-based organic-inorganic hybrid metal halides. This luminescent material can be used to manufacture light-emitting devices and for applications in solid-state lighting, displays, and other fields. Attached Figure Description
[0016] Figure 1 The crystal structure of the sample prepared for Example 1 of the invention.
[0017] Figure 2 The powder X-ray diffraction (XRD) pattern of the sample prepared in Example 1 of the present invention.
[0018] Figure 3 The photoluminescence emission / excitation spectrum (PL / PLE) of the sample prepared in Example 1 of the present invention is shown.
[0019] Figure 4 The powder X-ray diffraction (XRD) pattern of the sample prepared in Example 2 of the present invention.
[0020] Figure 5 The photoluminescence emission spectrum (PL) of the sample prepared in Example 2 of the present invention is shown.
[0021] Figure 6 The powder X-ray diffraction (XRD) pattern of the sample prepared in Example 3 of the present invention.
[0022] Figure 7 The photoluminescence emission spectrum (PL) of the sample prepared in Example 3 of the present invention is shown.
[0023] Figure 8 The powder X-ray diffraction (XRD) pattern of the sample prepared in Example 4 of the present invention.
[0024] Figure 9 The photoluminescence emission spectrum (PL) of the sample prepared in Example 4 of the present invention is shown. Detailed Implementation
[0025] Example 1
[0026] 2 mmol C 12 H 28 NBr, 1 mmol MnBr2, and 1 mmol NH4SCN were dissolved in 4 mL of N,N-dimethylformamide and magnetically stirred for 20 min. After filtration, the solution was evaporated on a heating plate at 80 °C for 2 days. The resulting powder was poured into a centrifuge tube, 4 mL of ethyl acetate was added, and the mixture was centrifuged at 6000 rpm for 5 minutes, washed 4 times, and dried in a vacuum oven for 24 hours to obtain (C 12 H 28N)2MnBr4:NCS - Microcrystalline powder. The yield based on Mn was 79.2%, and the photoluminescence quantum yield was 30.13%.
[0027] The NCS prepared in this embodiment - The crystal structure of manganese-doped organic-inorganic hybrid metal halide luminescent materials is as follows: Figure 1 As shown, this crystal structure belongs to the monoclinic crystal system with space group I2 / a. Its powder X-ray diffraction (XRD) is as follows: Figure 2 As shown.
[0028] The NCS prepared in this embodiment - Photoluminescence excitation and emission spectra (PLE / PL) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as... Figure 3 As shown, under 365 nm ultraviolet light excitation, this luminescent material emits broadband yellow light with an emission wavelength of 552 nm. The excitation spectrum indicates that the luminescence mechanism of this material is Mn 2+ A typical dd transition.
[0029] Example 2
[0030] 2 mmol C 12 H 28 NCl, 1 mmol MnBr2, and 1 mmol NaSCN were dissolved in 2 mL of N,N-dimethylformamide and magnetically stirred for 10 min. After filtration, the solution was evaporated on a heating plate at 60 °C for 1 day. The resulting powder was poured into centrifuge tubes, 3 mL of ethyl acetate was added, and the mixture was centrifuged at 4000 rpm for 3 min. After washing three times, the mixture was dried in a vacuum oven for 12 h to obtain (C 12 H 28 N)2MnBr4:NCS - Microcrystalline powder. The yield based on Mn was 77.6%, and the photoluminescence quantum yield was 28.19%.
[0031] The NCS prepared in this embodiment - Powder X-ray diffraction (XRD) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 4 As shown, the types of coordinating anions and thiocyanates of organic molecules do not affect the phase structure of the material.
[0032] The NCS prepared in this embodiment - Photoluminescence excitation spectrum (PL) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 5 As shown.
[0033] Example 3
[0034] 4 mmol C 12 H 28 Ni, 2 mmol MnBr2·4H2O, and 2 mmol NaSCN were dissolved in 6 mL of N,N-dimethylformamide and magnetically stirred for 30 min. After filtration, the solution was evaporated on a heating plate at 90 °C for 3 days. The resulting powder was poured into centrifuge tubes, 6 mL of ethyl acetate was added, and the mixture was centrifuged at 8000 rpm for 5 min, washed four times, and dried in a vacuum oven for 24 h to obtain (C 12 H 28 N)2MnBr4:NCS - Microcrystalline powder. Yield: 38.12%, photoluminescence quantum yield: 16.19%.
[0035] The NCS prepared in this embodiment - Powder X-ray diffraction (XRD) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 6 As shown.
[0036] The NCS prepared in this embodiment - Photoluminescence excitation spectrum (PL) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 7 As shown.
[0037] Example 4.
[0038] 1 mmol C 12 H 28 NBF4, 0.5 mmol MnBr2·4H2O, and 1 mmol KSCN were dissolved in 4 mL of N,N-dimethylformamide and magnetically stirred for 20 min. After filtration, the solution was evaporated on a heating plate at 80 °C for 2 days. The resulting powder was poured into centrifuge tubes, 4 mL of ethyl acetate was added, and the mixture was centrifuged at 6000 rpm for 5 min. After washing four times, the mixture was dried in a vacuum oven for 24 h to obtain (C 12 H 28 N)2MnBr4:NCS - Microcrystalline powder. Yield: 36.46%, photoluminescence quantum yield: 12.19%.
[0039] The NCS prepared in this embodiment - Powder X-ray diffraction (XRD) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 8 As shown.
[0040] The NCS prepared in this embodiment - Photoluminescence excitation spectrum (PL) of manganese-doped organic-inorganic hybrid metal halide luminescent materials, such as Figure 9 As shown.
Claims
1. An NCS - A manganese-doped organic-inorganic hybrid metal halide luminescent material, characterized in that... The general structural formula of the luminescent material is (C 12 H 28 N)2MnBr4:NCS - C 12 H 28 N + It is a tetrapropylammonium bromide cation, NCS - It is a thiocyanate anion.
2. The NCS as described in claim 1 - A manganese-doped organic-inorganic hybrid metal halide luminescent material, characterized in that... The luminescent material, (C) 12 H 28 N)2MnBr4:NCS - It belongs to the monoclinic crystal system and has the space group I2 / a.
3. The NCS as described in claim 2 - A manganese-doped organic-inorganic hybrid metal halide luminescent material, characterized in that... The luminescent material, (C) 12 H 28 N)2MnBr4:NCS - Yellow light emission exists under light excitation at 350~400nm and 420~480nm, with the emission peak located at 552nm.
4. The NCS as described in any one of claims 1 to 3 - A manganese-doped organic-inorganic hybrid metal halide luminescent material, characterized in that... The method for preparing the luminescent material includes the following steps: 1) Precursor solution: Prepare raw material C... 12 H 28 NX (X can be Cl) - ,Br - I - BF4 - One or more of the following), MnBr2 (MnBr2·4H2O), ASCN (A can be NH4) + Li + Na + K + One or more of the ingredients are dissolved in an organic solvent, stirred at room temperature to obtain a transparent precursor solution, and then filtered. 2) Evaporation and crystallization: The solvent in the filtered solution from step 1) is evaporated at an environment of 60~90℃ to obtain (C 12 H 28 N)2MnBr4:NCS-microcrystalline powder. 3) Washing and drying: Pour the microcrystalline powder obtained in step 2) into a centrifuge tube, add ethyl acetate, wash 2-4 times in a centrifuge, and then dry in a vacuum oven to obtain dried (C) 12 H 28 N)2MnBr4:NCS - Microcrystalline powder.
5. The NCS as described in claim 4 - A method for preparing manganese-doped organic-inorganic hybrid metal halide luminescent materials, characterized in that... Step 1) C 12 H 28 The molar ratio of NX, MnBr2 (MnBr2·4H2O) and ASCN is 1.0~4.0:0.5~2.0:1.0~2.0; the organic solvent is 2~6 mL of N,N-dimethylformamide; and the stirring time is 10~30 minutes.
6. The NCS as described in claim 5 - A method for preparing manganese-doped organic-inorganic hybrid metal halide luminescent materials, characterized in that... In step 2), the solvent evaporation time is 1 to 3 days.
7. The NCS as described in claim 6 - A method for preparing manganese-doped organic-inorganic hybrid metal halide luminescent materials, characterized in that... The unsuitable solvent in step 3) refers to 3-6 mL of ethyl acetate, centrifuged at 4000-8000 rpm for 3-5 minutes, and dried for 12-24 hours.
8. The NCS as described in claim 7 - A manganese-doped organic-inorganic hybrid metal halide luminescent material, characterized in that... The luminescent material (C) 12 H 28 N)2MnBr4:NCS - Applied to solid-state lighting, displays and other fields.