CN115725294A - 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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Abstract
The invention discloses a 0D antimony doped indium-based inorganic luminescent material, a preparation method and application thereof, wherein the chemical formula of the luminescent material is (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is a cation at the A site, and a metal In at the B site 3+ Ions and Sb 3+ Ions. Under the excitation of 250-380 nm light, 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 keep 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 process of searching for more stable and environmentally-friendly lead-based halide perovskite substitutes, zero-dimensional (0D) metal halides are becoming the focus of attention due to their unique soft lattices and strong interactions between electrons and lattices under excitation. Compared to 0D organic-inorganic hybrid metal halides, all-inorganic 0D metal halides are applied in the field of light emission such as solid state lighting, display, etc. because they have higher stability than organic-inorganic hybrid homogeneous products that are generally subject to organic chain degradation.
Reasonable doping and composition control are important means for designing luminescent metal halides to achieve efficient and tunable emission. In recent years, ns 2 Metal ions such as Pb 2+ 、Sn 2+ 、Sb 3+ Of particular interest as effective dopants are 0D metal halides.
Disclosure of Invention
The invention aims to solve the technical problems that the stability of 0D organic-inorganic hybrid metal halide in the prior art is not high, and the application in the light-emitting fields of solid-state illumination, display and the like is not wide.
In order to solve the technical problems, the invention provides the following technical scheme:
A0D antimony-doped indium-based inorganic luminescent material with a chemical formula of (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is a cation at the A site, and a metal In at the B site 3+ Ions and Sb 3+ Ions.
Preferably, the luminescent material is in (NH) 4 ) 2 InCl 5 ·H 2 Adding SbCl into O 3 Content x = SbCl 3 /(InCl 3 +SbCl 3 ) Is obtained when the content is not less than 50 percentAchieving different concentrations of SbCl by changing the value of x 3 Doping (x =5%,10%,20%,30%,40%,50%,60%,70%,80%, 100%). In Sb 3+ When the feeding ratio is x =50%, the yellow-white light emission intensity of the luminescent material is the highest.
Preferably, the luminescent material is excited by light of 250-380 nm, the emission spectrum range of the luminescent material doped with different contents of antimony is 560-715 nm, and 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 64% of the emission intensity at room temperature was maintained at 420K.
Preferably, the luminescent material is excited by 340nm light, and shows broadband yellow-white light emission around 560nm, and the quantum efficiency is 93%.
A method for preparing 0D antimony doped indium-based inorganic luminescent material, which adopts a solution method and comprises the following steps:
s1, sequentially weighing NH according to the stoichiometric ratio of chemical mol 4 Cl, an indium-containing compound and an 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, and heating and stirring until the raw materials are completely dissolved to obtain a solution A;
s2, adding an antimony-containing compound into the solution A, then adding HCl serving as a solvent, heating to 70-95 ℃, and stirring to obtain a clear solution B;
s3, placing the clear solution B into an oven, setting an oven program to slowly cool for 2-4 days to obtain (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Crystal, filtering and drying the obtained reaction liquid and the crystal in sequence to obtainTo dry crystals.
Preferably, in step S3, the initial temperature of the oven is the temperature at which the stirring in step S2 is completed to dissolve.
The application of 0D antimony doped indium-based inorganic luminescent material in 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 present invention provides a 0D antimony doped indium-based phosphor, the material (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 The emission peak is near 560nm, yellow white light with high intensity is emitted under the excitation of an ultraviolet lamp, the half-peak width is 200nm at normal temperature, and the large half-peak width and strong yellow white light emission enable the yellow white light to be mixed with blue fluorescent powder to realize full-spectrum white light. Can pass In 3+ 、Sb 3+ The change of the relative content of the crystal structure realizes the change of the crystal structure so as to realize the regulation and control of light color; has high luminous efficiency and excellent heat quenching resistance; the luminescent material has extremely low price; stable physical and chemical properties.
The invention provides a preparation method of a 0D antimony doped indium-based inorganic luminescent material, which is simple and easy for large-scale popularization. The invention relates to lead-free (NH) with a 0D structure 4 ) 2 InCl 5 ·H 2 O crystals were the starting point for the study by reacting at (NH) 4 ) 2 InCl 5 ·H 2 Doping of Sb in O 3+ The transformation of the crystal structure is realized, and a luminescent material is designed. With SbCl 3 /(InCl 3 +SbCl 3 ) The ratio x of the antimony to the red light is different, the emission spectrum of the luminescent material doped with different antimony contents can be finely regulated and controlled within the range of 560nm to 715nm, and broadband weak orange red light to yellow white light emission is realized. When the luminescent material is x =50%, the structure of the luminescent material is (NH) 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 are that the material is applied to white light emitting diodes and high-resolution fluorescenceFurther application in the optical identification anti-counterfeiting technology paves the way.
The invention provides an application of a 0D antimony doped indium-based inorganic luminescent material, which can be used for manufacturing luminescent devices, luminescent devices with different light colors or photoelectric detection devices, temperature detection, illumination and display devices.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a 0D antimony doped indium-based phosphor (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Crystal structure of (2).
FIG. 2 is a powder X-ray diffraction (XRD) pattern and a single crystal XRD pattern and (NH) of a sample prepared in example 1 of the present invention 4 ) 2 InCl 5 ·H 2 And (4) comparing XRD patterns of O single crystals.
FIG. 3 is a powder XRD pattern at different feed mole ratios during the preparation of example 1 of the present invention.
FIG. 4 shows the emission spectra of the preparation of example 1 according to the invention at different molar ratios of the feed.
FIG. 5 is a graph of the temperature change spectrum from room temperature to 480K for the sample prepared in example 1 of the present invention.
Detailed Description
The following describes technical solutions and technical problems to be solved in the embodiments of the present invention with reference to the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the patent of the invention, and not all embodiments.
Example 1
This example provides a chemical composition formula of (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Preparation method of luminescent materialThe method comprises the following steps:
according to the chemical composition formula (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 0.225g of NH is weighed out in each case according to the stoichiometric molar ratio 4 Cl and 0.165g InCl 3 Adding high-purity powder raw materials into a glass bottle of a reaction vessel, adding 2.0ml of HCl, heating and stirring at 90 ℃ for 20min to obtain a clear solution, and then weighing the clear solution and InCl 3 SbCl in the same molar ratio 3 Adding 0.5-1.0 ml of HCl, continuously stirring until the HCl is completely dissolved, putting the glass bottle into an oven, controlling the cooling rate to be 0.01 ℃/min, slowly cooling to room temperature to obtain the chemical composition formula (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 Grinding the crystals to obtain the corresponding powder.
In FIG. 2, the top shows the powder XRD pattern of the luminescent material of example 1 prepared by the present invention, and the middle is fitted (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 XRD pattern of crystal powder with (NH) at the bottom 4 ) 2 InCl 5 ·H 2 The XRD pattern of O on single crystal showed that the single crystal prepared in example 1 was the same as the powder phase, and that the product was determined to be pure phase and was (NH) resolved from the single crystal 4 ) 3 In 0.95 Sb 0.05 Cl 6 The crystal structure is shown in figure 1.
Example 1 luminescent Material (NH) prepared according to the invention 4 ) 3 In 0.95 Sb 0.05 Cl 6 Not a theoretical chemical formula, but a chemical formula determined by solving the crystal structure obtained by XRD diffraction. The material is prepared by the following steps of feeding ratio x = SbCl 3 /(InCl 3 +SbCl 3 ) And (d) = 50%. Indicating a 50% charge, but the actual incorporation of Sb into the crystals was only 5%.
Powder XRD and emission spectra at other different feed molar ratios are shown in fig. 3 and 4. The introduction of SbCl is described 3 /(InCl 3 +SbCl 3 ) The ratio of (A) is marked as x, and as can be seen from FIG. 3, x is 0,5%,10%,20%,30%,40%,50%,60%,70%,80%,100% in sequence from bottom to top. The lowest part is (NH) 4 ) 2 InCl 5 ·H 2 Diffraction line of O, uppermost is (NH) 4 ) 3 SbCl 6 The diffraction line of (2). FIG. 3 illustrates at x<At 30%, the synthesized compound is reacted with (NH) 4 ) 2 InCl 5 ·H 2 The structure of O is consistent, and the light emission is weak orange red under an ultraviolet lamp. When x =30%, a different (NH) from the matrix is generated 4 ) 2 InCl 5 ·H 2 O, which emits yellowish white light under an ultraviolet lamp. Alternatively, it is believed that a heterogeneous phase, which is the new yellow-white emitting compound, appears in the original matrix. With subsequent increase in Sb content, this impurity phase becomes a host and the original matrix phase disappears. The yellow-white light emission is strongest when x =50%, and its chemical formula is (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 。
The temperature-variable spectrum of the luminescent material of example 1 prepared by the present invention is shown in fig. 5, and at room temperature, the emission peak is around 560nm, and the emission peak gradually red-shifts with the temperature increase, which is caused by the lattice expansion due to the temperature increase. The emission intensity of the material can still keep 64% of that of the material at the normal temperature at the high temperature of 420K, which shows that the luminescent material has good thermal quenching resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A0D antimony doped indium-based inorganic luminescent material is characterized in that the chemical formula of the luminescent material is (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 ，NH 4 + Is a cation at the A site, and a metal In at the B site 3+ Ions and Sb 3+ Ions.
2. The luminescent material according to claim 1, wherein the luminescent material is excited by light of 250-380 nm, and the emission spectrum range of the luminescent material doped with different amounts of antimony is 560-715 nm, so that broadband weak orange-red to yellow-white light emission is realized.
3. The luminescent material according to claim 2, wherein the luminescent material is Sb 3+ The material feeding ratio is Sb 3+ /(In 3+ +Sb 3+ ) The emission intensity of yellow and white light of the luminescent material is the highest when the luminous material is obtained when the luminous material is 50 percent.
4. The luminescent material according to claim 3, wherein (NH) in the luminescent material 4 ) 3 In 0.95 Sb 0.05 Cl 6 Belongs to an orthorhombic system, and the space group is Pnma.
5. A luminescent material as claimed in claim 4, characterized in that it has a very good thermal quenching resistance at 420K.
6. The luminescent material according to claim 4, wherein the luminescent material maintains 64% of emission intensity at 420K at normal temperature.
7. A luminescent material as claimed in claim 5, which, when excited with light of 340nm, exhibits broad-band yellow-white light emission around 560nm with a quantum efficiency of 93%.
8. A method of making a 0D antimony doped indium-based phosphor according to any one of claims 1 to 7, wherein the method uses a solution process comprising the steps of:
s1, sequentially weighing NH according to stoichiometric molar ratio 4 Cl, an indium-containing compound and an antimony-containing compound as raw materials, and NH 4 Adding Cl and an indium-containing compound into a reaction container, adding HCl serving as a solvent into the reaction container, and heating and stirring until the raw materials are completely dissolved to obtain a solution A;
s2, adding an antimony-containing compound into the solution A, then adding HCl serving as a solvent, heating to 70-95 ℃, and stirring to obtain a clear solution B;
s3, placing the clear solution B into an oven, setting an oven program to slowly cool for 2-4 days to obtain (NH) 4 ) 3 In 0.95 Sb 0.05 Cl 6 And (3) crystals, and filtering and drying the obtained reaction liquid and the crystals in sequence to obtain dried crystals.
9. The method of claim 8, wherein in step S3, the initial oven temperature is the temperature at which the mixture is stirred to be completely dissolved in step S2.
10. Use of the 0D antimony doped indium based phosphor according to any of claims 1 to 7 in light emitting or photodetection devices of different light colors, temperature detection, illumination and display devices.
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