阅读说明：本技术 一种激发波长依赖的多色长余辉发光材料及其制备方法和应用 (Excitation wavelength dependent multicolor long afterglow luminescent material and preparation method and application thereof ) 是由 王静 刘伯梅 于 2020-06-23 设计创作，主要内容包括：本发明涉及一种激发波长依赖的多色长余辉发光材料及其制备方法和应用。该多色长余辉发光材料的化学组成为Ca<Sub>1-y</Sub>Bi<Sub>y</Sub>Ga<Sub>x</Sub>O<Sub>4</Sub>,其中,1.95≤x≤2,0.001≤x≤0.01。本发明提供的材料在240–420nm激发下,表现出605–542nm连续可调的余辉发射,其“橙色–黄色–绿色”的余辉转变能够被肉眼轻易分辨,而且能够通过余辉发光色彩对紫外波段的激发光进行可视化显示与分辨；另外缺陷相的近红外长余辉发光材料具有更为优异的余辉性能。此外,该材料能够被太阳光激发产生余辉发射,具有太阳能转换潜力,有望作为一种智能发光材料运用于余辉显示、信息存储、传感器和催化储能等新型光电应用领域。(The invention relates to a multicolor long afterglow luminescent material with excitation wavelength dependence, a preparation method and application thereof. The chemical composition of the multicolor long afterglow luminescent material is Ca 1‑y Bi y Ga x O 4 Wherein x is more than or equal to 1.95 and less than or equal to 2, and x is more than or equal to 0.001 and less than or equal to 0.01. The material provided by the invention shows 605-542 nm continuously adjustable afterglow emission under the excitation of 240-420 nm, the orange-yellow-green afterglow conversion can be easily distinguished by naked eyes, and the excitation light of an ultraviolet band can be visually displayed and distinguished through the afterglow luminescent color; in addition, the near-infrared long afterglow luminescent material of the defect phase has more excellent afterglow performance. In addition, the material can be excited by sunlight to generate afterglow emission, has the potential of solar energy conversion, and is expected to be used as an intelligent luminescent material in the novel photoelectric application fields of afterglow display, information storage, sensors, catalytic energy storage and the like.)

1. The multicolor long-afterglow luminescent material with the excitation wavelength dependent is characterized in that the chemical composition of the multicolor long-afterglow luminescent material is Ca_1-yBi_yGa_xO₄Wherein x is more than or equal to 1.95 and less than or equal to 2, and x is more than or equal to 0.001 and less than or equal to 0.01.

2. The multi-color long-afterglow luminescent material of claim 1, wherein x is 1.95-1.99.

3. The multi-color long-afterglow luminescent material of claim 2, wherein x is 1.97; y is 0.005.

4. The method for preparing the multicolor long-afterglow luminescent material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:

s1: grinding and uniformly mixing a calcium-containing compound, a bismuth-containing compound and a gallium-containing compound to obtain a mixture;

s2: and calcining the mixture at high temperature in an oxygen-containing atmosphere to obtain the multicolor long-afterglow luminescent material.

5. The method according to claim 4, wherein the calcium-containing compound in S1 is calcium carbonate; the bismuth-containing compound is bismuth oxide; the gallium-containing compound is gallium oxide.

6. The preparation method according to claim 4, wherein the high-temperature calcination in S2 is carried out at a temperature of 1000-1200 ℃ for 6-18 h.

7. The method according to claim 4, wherein the step of calcining S2 is followed by cooling and grinding.

8. The method according to claim 4, wherein the temperature rise rate in S2 is 5-10 ℃/min.

9. The method according to claim 4, wherein the calcination is carried out at a high temperature in an air atmosphere in S2.

10. The use of the multi-color long-afterglow luminescent material of any one of claims 1 to 3 in the field of photoelectricity.

Technical Field

The invention belongs to the technical field of long-afterglow luminescent materials, and particularly relates to a multicolor long-afterglow luminescent material with excitation wavelength dependence, and a preparation method and application thereof.

Background

The dynamic fluorescence emission phenomenon endows the luminescent material with excellent photoelectric application performance, for example, when the multicolor coded up-conversion material is used as an information carrier, the luminescent material can be used for the storage of high-flux encrypted data, anti-counterfeiting and multiplexed biological detection; carbon quantum dots and small amounts of organic substances are becoming the research heat due to the adjustable fluorescence emission phenomenon that the excitation wavelength depends on.

On the other hand, luminescent materials with afterglow luminescent properties have important application values in the fields of display, information encryption, bio-imaging and the like, for example, through SrAl₂O₄:Eu²⁺The green long afterglow material is used as an anti-counterfeiting mark. In recent years, the demand for information storage and security is increased, but the application capability of the traditional long afterglow material in the field of information storage is limited, and the traditional long afterglow material has substitutability. Therefore, in recent years, long-afterglow materials with different properties are obtained by utilizing different stimulus response modes (such as temperature change, stress change, excitation source difference and the like), and the new materials show huge application potential. However, to our knowledge, in the field of inorganic materials, researchers have not found continuously tunable afterglow luminescence in a single host material system activated by a single luminescence center, and polychromatic afterglow display by means of composite materials, such as CaAl ₂O₄:Eu²⁺,Nd³⁺Composite CsPbX₃(X ═ Cl, Br, and I) quantum dots are capable of realizing multi-color afterglow Luminescence (Gong, z., et al., Full-Spectrum Persistent Using All-Inorganic Persistent quantum dots, angelwan patent Chemie (2019)58(21), 6943). In a word, the shortage of the multi-color long afterglow luminescent material greatly limits the application of the long afterglow luminescent material in the field of intelligent photoelectric devices.

Disclosure of Invention

The invention aims to overcome the shortage of the multicolor long afterglow luminescent material in the prior art and provide the multicolor long afterglow luminescent material with excitation wavelength dependence. The invention is prepared by doping Bi³⁺Activating ions to obtain the near-infrared long-afterglow luminescent material. The material shows 605-542 nm continuously adjustable afterglow emission under the excitation of 240-420 nm, the orange-yellow-green afterglow conversion can be easily distinguished by naked eyes (the afterglow naked eye visible time can reach about 30 minutes at most), and the excitation light of an ultraviolet band can be visually displayed and distinguished through afterglow luminescent colors; in addition, the material can be excited by sunlight to generate afterglow emission, has the potential of solar energy conversion, and is expected to be used as an intelligent luminescent material for afterglow display, information storage and transmission The sensor and the catalytic energy storage and the like.

The invention also aims to provide a preparation method of the near-infrared long-afterglow luminescent material.

The invention also aims to provide the application of the near-infrared long-afterglow luminescent material in the photoelectric field.

In order to achieve the purpose, the invention adopts the following technical scheme:

the excitation wavelength dependent multicolor long afterglow luminescent material has the chemical composition of Ca_1-yBi_yGa_xO₄Wherein x is more than or equal to 1.95 and less than or equal to 2, and x is more than or equal to 0.001 and less than or equal to 0.01.

The invention is prepared by doping Bi³⁺Activating ions to obtain the near-infrared long-afterglow luminescent material. The material shows 605-542 nm continuously adjustable afterglow emission under the excitation of 240-420 nm, the orange-yellow-green afterglow conversion can be easily distinguished by naked eyes (the afterglow naked eye visible time can reach about 30 minutes at most), and the excitation light of an ultraviolet band can be visually displayed and distinguished through afterglow luminescent colors; in addition, the near infrared long afterglow luminescent material of the defect phase (Ga vacancy) has more excellent afterglow performance.

In addition, the material can be excited by sunlight to generate afterglow emission, has the potential of solar energy conversion, and is expected to be used as an intelligent luminescent material in the novel photoelectric application fields of afterglow display, information storage, sensors, catalytic energy storage and the like.

Preferably, 1.95. ltoreq. x.ltoreq.1.99.

More preferably, x is 1.97.

Preferably, y is 0.005.

The preparation method of the multicolor long afterglow luminescent material comprises the following steps:

s1: grinding and uniformly mixing a calcium-containing compound, a bismuth-containing compound and a gallium-containing compound to obtain a mixture;

s2: and calcining the mixture at high temperature in an oxygen-containing atmosphere to obtain the multicolor long-afterglow luminescent material.

The preparation method provided by the invention has the advantages of simple process, easiness in realization, high repetition rate and capability of realizing mass production.

Calcium-containing compounds, bismuth-containing compounds and gallium-containing compounds conventional in the art may be used in the present invention.

Preferably, the calcium-containing compound in S1 is calcium carbonate; the bismuth-containing compound is bismuth oxide; the gallium-containing compound is gallium oxide.

Preferably, the high-temperature calcination in S2 is carried out at 1000-1200 ℃ for 6-18 h.

Preferably, the calcining step of S2 further comprises cooling and grinding.

Preferably, the temperature rise rate in S2 is 5-10 ℃/min.

More preferably, the temperature increase rate in S2 is 5 deg.C/min.

Preferably, the high-temperature calcination is performed in S2 under an air atmosphere.

The application of the multicolor long afterglow luminescent material in the photoelectric field is also within the protection scope of the invention.

Preferably, the multicolor long-afterglow luminescent material is applied to afterglow display, information storage, sensors or catalytic energy storage.

Compared with the prior art, the invention has the following beneficial effects:

the multicolor long afterglow luminescent material provided by the invention shows 605-542 nm continuously adjustable afterglow emission under the excitation of 240-420 nm, the orange-yellow-green afterglow conversion can be easily distinguished by naked eyes (the afterglow naked eye visible time can reach about 30 minutes at most), and the excitation light of an ultraviolet band can be visually displayed and distinguished through the afterglow luminescent color.

The multicolor long afterglow luminescent material provided by the invention can be excited by sunlight to generate afterglow emission, has the potential of solar energy conversion, and is expected to be used as an intelligent luminescent material in the novel photoelectric application fields of afterglow display, information storage, sensors, catalytic energy storage and the like.

The preparation method provided by the invention has the advantages of simple process, easiness in realization, high repetition rate and capability of realizing mass production.

Drawings

FIG. 1 is a comparison of XRD patterns of samples provided in examples 1-4 with standard diffraction cards;

FIG. 2 is a comparison of XRD patterns of samples provided in examples 5-6 with standard diffraction cards;

FIG. 3 is a two-dimensional excitation emission spectrum of the sample provided in examples 1-4;

FIG. 4 is a fluorescence emission spectrum of the samples provided in examples 3, 5-6 under excitation at 300 nm;

FIG. 5 is an afterglow decay curve after excitation by 300nm ultraviolet light of the samples provided in examples 1-4;

FIG. 6 is a photograph of afterglow at different decay times after irradiation of a sample provided in example 3 by an ultraviolet portable lamp;

FIG. 7 shows the afterglow emission spectra at 3 min and 15 min of the sample provided in example 3 after excitation with different excitation lights (240-420 nm);

FIG. 8 is a long afterglow decay curve obtained after the sample provided in example 3 is irradiated for 5 minutes at different excitation wavelengths (240-420 nm), wherein the corresponding monitoring wavelength is 605-542 nm.

FIG. 9 is the CIE chromaticity diagram of afterglow luminescence corresponding to the samples provided in example 3 after excitation by different excitation lights (240-420 nm);

fig. 10 is an afterglow photograph of the samples provided in examples 1 and 3 after being exposed to sunlight for 10 minutes.

Detailed Description

The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.