CN115725294B - 0D antimony doped indium-based inorganic luminescent material and preparation method and application thereof - Google Patents
0D antimony doped indium-based inorganic luminescent material and preparation method and application thereof Download PDFInfo
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- CN115725294B CN115725294B CN202211361601.6A CN202211361601A CN115725294B CN 115725294 B CN115725294 B CN 115725294B CN 202211361601 A CN202211361601 A CN 202211361601A CN 115725294 B CN115725294 B CN 115725294B
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Abstract
The invention discloses a 0D antimony doped indium-based inorganic luminescent material, a preparation method and application thereof, wherein the luminescent material has a chemical formula of (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is cation at A position and metal In at B position 3+ Ion and Sb 3+ Ions. Under the excitation of light of 250-380 nm, the luminescent material shows strong yellow-white light emission near 560nm, and the quantum efficiency reaches 93%; the material has high thermal quenching resistance, and the emission intensity can still be kept 64% at normal temperature at 420K. The preparation method of the inorganic luminescent material has the advantages of simple synthesis method, low cost and easy mass synthesis. The inorganic luminescent material can be applied to novel luminescent devices or photoelectric detection devices with different light colors, temperature detection, illumination and display devices.
Description
Technical Field
The invention belongs to the field of illumination and display, and particularly relates to a 0D antimony doped indium-based inorganic luminescent material, and a preparation method and application thereof.
Background
In recent years, in the search for more stable, environmentally friendly lead-based halide perovskite substitutes, zero-dimensional (0D) metal halides have been the focus of increasing attention because of their unique soft lattice and strong interactions between electrons and lattices under excitation, resulting in efficient broadband self-trapping exciton emission. Compared with 0D organic-inorganic hybrid metal halides, all-inorganic 0D metal halides are applied to the field of solid-state lighting, display and the like luminescence because of higher stability than organic-inorganic hybrid like products which are generally subject to organic chain degradation.
Reasonable doping and compositional control are important means to design luminescent metal halides to achieve efficient and tunable emission. In recent years, ns 2 Metal ions such as Pb 2+ 、Sn 2+ 、Sb 3+ Particular interest has been raised as an effective dopant in 0D metal halides.
Disclosure of Invention
The invention aims to solve the technical problems that the 0D organic-inorganic hybrid metal halide in the prior art is not high in stability and is not widely applied to the field of solid-state lighting, display and other luminescence.
In order to solve the technical problems, the invention provides the following technical scheme:
A0D antimony doped indium-based phosphor having the formula (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is cation at A position and metal In at B position 3+ Ion and Sb 3+ Ions.
Preferably, the luminescent material is a luminescent material that is in (NH 4 ) 2 InCl 5 ·H 2 Adding SbCl into O 3 Content x=sbcl 3 /(InCl 3 +SbCl 3 ) Obtained when =50%, different concentrations of SbCl are achieved by varying the value of x 3 Doping (x=5%, 10%,20%,30%,40%,50%,60%,70%,80%, 100%). On Sb 3+ When the feeding ratio is x=50%, the yellow-white light emission intensity of the luminescent material is highest.
Preferably, the luminescent material is excited by using 250-380 nm light, and the emission spectrum range of the luminescent material doped with antimony with different contents is 560-715 nm, so that broadband weak orange red light to yellow white light emission is realized.
Preferably, the luminescent material (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 Belonging to the orthorhombic system, the space group is Pnma (a=12.387, b=24.990, c= 7.784).
Preferably, the luminescent material still has very good thermal quenching resistance at 420K.
Preferably, (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 The emission intensity was maintained at 64% at room temperature at 420K.
Preferably, the luminescent material exhibits broadband yellow-white light emission around 560nm with a quantum efficiency of 93% when excited with 340nm light.
The preparation method of the 0D antimony doped indium-based inorganic luminescent material adopts a solution method and comprises the following steps:
s1, sequentially weighing NH according to the stoichiometric ratio 4 Cl, indium-containing compound and antimony-containing compound as raw materials, NH 4 Adding Cl and an indium-containing compound into a reaction container, adding HCl serving as a solvent into the reaction container, heating and stirring until the raw materials are completely dissolved, and obtaining a solution A;
s2, adding an antimony-containing compound into the solution A, then adding HCl as a solvent, heating to 70-95 ℃ and stirring to obtain a clear solution B;
s3, placing the clarified solution B into a baking oven, setting a baking oven program to slowly cool, and cooling for 2-4 days to obtain (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 And (3) filtering and drying the obtained reaction liquid and the crystals in sequence to obtain dried crystals.
Preferably, in step S3, the initial temperature of the oven is the temperature at which the solution is stirred to the full dissolution in step S2.
The application of the 0D antimony doped indium-based inorganic luminescent material is that the luminescent material is applied to luminescent devices or photoelectric detection devices with different light colors, temperature detection, illumination and display devices.
The technical scheme provided by the invention has the beneficial effects that at least:
the invention provides a 0D antimony doped indium-based phosphor, said material (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 The emission peak is around 560nm, atThe ultraviolet lamp emits high-intensity yellow white light under excitation, the half-peak width is 200nm at normal temperature, and the full spectrum white light can be realized by mixing the ultraviolet lamp with blue fluorescent powder due to large half-peak width and strong yellow white light emission. Can pass through In 3+ 、Sb 3+ The change of the relative content of the crystal structure is realized so as to realize the regulation and control of light color; has high luminous efficiency and excellent thermal quenching resistance; the price of the luminescent material is extremely low; the physical and chemical properties are stable.
The invention provides a preparation method of a 0D antimony doped indium-based inorganic luminescent material, which is simple and easy to popularize on a large scale. The invention adopts the lead-free (NH) with 0D structure 4 ) 2 InCl 5 ·H 2 O crystals were used as starting points for the study by the reaction of the metal in (NH 4 ) 2 InCl 5 ·H 2 Doping Sb in O 3+ Realizes the transformation of the crystal structure and designs a luminescent material. With SbCl 3 /(InCl 3 +SbCl 3 ) The emission spectrum of the luminescent materials doped with antimony with different contents can be finely regulated and controlled within the range of 560 nm-715 nm, so that the broadband weak orange red light emission to yellow white light emission is realized. The luminescent material has a structure of (NH) when x=50% 4 ) 3 In 0.95 Sb 0.05 Cl 6 The yellow-white light emission intensity is highest. In addition, the excellent air stability and thermal stability paves the way for the further application of the fluorescent marker in white light emitting diodes and high-resolution fluorescent marker anti-counterfeiting technology.
The invention provides application of a 0D antimony doped indium-based inorganic luminescent material, which can be used for manufacturing luminescent devices, and can be applied to luminescent devices or photoelectric detection devices with different light colors, temperature detection, illumination and display devices.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a 0D antimony doped indium-based phosphor (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 Is a crystal structure diagram of (a).
FIG. 2 is a powder X-ray diffraction (XRD) pattern and single crystal XRD pattern and (NH) of a sample prepared in example 1 of the present invention 4 ) 2 InCl 5 ·H 2 O single crystal XRD pattern comparison.
Figure 3 shows the XRD patterns of powders at different feed mole ratios during the preparation of example 1 according to the invention.
FIG. 4 shows emission spectra of the preparation of example 1 according to the invention at different feed mole ratios.
FIG. 5 is a graph showing the temperature change spectrum of the sample prepared in example 1 of the present invention from room temperature to 480K.
Detailed Description
The technical solutions and the technical problems to be solved in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present patent.
Example 1
The present embodiment provides a catalyst having a chemical composition formula (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 The preparation method of the luminescent material comprises the following steps:
according to the chemical composition formula (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 0.225g NH was weighed out according to the molar stoichiometric amounts 4 Cl and 0.165g InCl 3 Adding high-purity powder raw material into a reaction vessel glass bottle, adding 2.0ml of HCl, heating at 90 ℃ and stirring for 20min to obtain a clear solution, and weighing and mixing with InCl 3 SbCl of the same molar ratio 3 Adding 0.5-1.0 ml of HCl, continuously stirring until the HCl is completely dissolved, putting a glass bottle into a baking oven, controlling the cooling rate to be 0.01 ℃/min, and slowly cooling to room temperature to obtain the compound (NH) with the chemical composition formula of (A) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Crystals, and corresponding powder can be obtained after grinding.
The powder XRD pattern of the luminescent material of example 1 produced according to the invention is shown uppermost in fig. 2, fitted in the middle (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 Crystalline powder XRD pattern, lowest (NH 4 ) 2 InCl 5 ·H 2 The single crystal XRD patterns of O indicate that the single crystal prepared in example 1 is identical to the powder phase, and the pure phase is determined as the product, which is obtained by single crystal analysis (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 The crystal structure is shown in fig. 1.
The luminescent material of example 1 (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Not the theoretical chemical formula, but the chemical formula determined from the resolution of the crystal structure obtained by XRD diffractometry. The material is prepared by mixing the materials in a feeding ratio of x=SbCl 3 /(InCl 3 +SbCl 3 ) Prepared when=50%. The feed ratio was 50% but only 5% of the Sb actually entered the crystal.
Powder XRD and emission spectra at different feed mole ratios are shown in fig. 3 and 4. The SbCl is described in the foregoing 3 /(InCl 3 +SbCl 3 ) The ratio of (2) is denoted as x, and from fig. 3, x is 0,5%,10%,20%,30%,40%,50%,60%,70%,80%,100% in order from bottom to top. At the lowest part (NH) 4 ) 2 InCl 5 ·H 2 O diffraction line, uppermost (NH 4 ) 3 SbCl 6 Is a diffraction line of (2). FIG. 3 illustrates at x<At 30%, the synthesized compound was reacted with (NH) 4 ) 2 InCl 5 ·H 2 O has consistent structure and emits weak orange-red light under an ultraviolet lamp. When x=30%, a different form of the matrix (NH 4 ) 2 InCl 5 ·H 2 O, which emits yellow white light under an ultraviolet lamp. Alternatively, it is considered that a hetero-phase, which is the new compound that emits yellow-white light, appears in the original matrix. With the increase of the subsequent Sb content, the impurity phase becomes a main body, and the original matrix phase disappears.When x=50%, the yellow-white light emission is strongest, and the chemical formula is (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 。
The temperature-changing spectrum of the luminescent material of the embodiment 1 prepared by the invention is shown in fig. 5, the emission peak is about 560nm at normal temperature, and the emission peak gradually red shifts along with the temperature rise, which is caused by the expansion of the lattice when the temperature rises. The emission intensity of the material can still keep 64% of the emission intensity at normal temperature under the high temperature of 420K, which proves that the luminescent material has good thermal quenching resistance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A0D antimony doped indium-based phosphor is characterized in that the phosphor has a chemical formula (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is cation at A position and metal In at B position 3+ Ion and Sb 3+ Ions.
2. The luminescent material according to claim 1, wherein the luminescent material is based on Sb 3+ The feed ratio is Sb 3+ /(In 3+ +Sb 3+ ) Obtained when=50%, the luminescent material has the highest yellow-white light emission intensity.
3. Luminescent material according to claim 2, characterized in that in the luminescent material (NH 4 ) 3 In 0.95 Sb 0.05 Cl 6 Belongs to an orthorhombic system, and the space group is Pnma.
4. A luminescent material as claimed in claim 3, characterized in that the luminescent material still has very good thermal quenching resistance at 420K.
5. A luminescent material as claimed in claim 3, wherein the luminescent material maintains 64% of the emission intensity at room temperature at 420K.
6. The luminescent material according to claim 4, wherein the luminescent material exhibits broadband yellow-white light emission around 560nm with a quantum efficiency of 93% when excited with 340nm light.
7. The method for preparing a 0D antimony doped indium-based phosphor according to any one of claims 1 to 6, wherein the method employs a solution method, comprising the steps of:
s1, sequentially weighing NH according to the stoichiometric ratio 4 Cl, indium-containing compound and antimony-containing compound as raw materials, NH 4 Adding Cl and an indium-containing compound into a reaction container, adding HCl serving as a solvent into the reaction container, heating and stirring until the raw materials are completely dissolved, and obtaining a solution A;
s2, adding an antimony-containing compound into the solution A, then adding HCl as a solvent, heating to 70-95 ℃ and stirring to obtain a clear solution B;
s3, placing the clarified solution B into a baking oven, setting a baking oven program to slowly cool, and cooling for 2-4 days to obtain (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 And (3) filtering and drying the obtained reaction liquid and the crystals in sequence to obtain dried crystals.
8. The method of claim 7, wherein in step S3, the oven initial temperature is the temperature at which step S2 is stirred to full dissolution.
9. Use of a 0D antimony doped indium-based phosphor according to any of claims 1 to 6, wherein the phosphor is applied in light emitting devices or photo-detector devices, temperature detector devices of different light colors.
10. Use of a 0D antimony doped indium-based phosphor according to claim 9, wherein the light emitting device is an illumination and display device.
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