CN108275882B

CN108275882B - Ultraviolet light excited multicolor light emitting glass and preparation method thereof

Info

Publication number: CN108275882B
Application number: CN201810023833.8A
Authority: CN
Inventors: 步妍妍; 王祥夫; 颜晓红
Original assignee: Nanjing University Of Posts And Telecommunications Institute At Nantong Co ltd; Nanjing University of Posts and Telecommunications
Current assignee: Nanjing University Of Posts And Telecommunications Institute At Nantong Co ltd; Nanjing University of Posts and Telecommunications
Priority date: 2018-01-10
Filing date: 2018-01-10
Publication date: 2020-11-06
Anticipated expiration: 2038-01-10
Also published as: CN108275882A

Abstract

The invention belongs to the technical field of illumination and display, and particularly relates to ultraviolet light excited multicolor light emitting glass and a preparation method thereof; the matrix material of the glass comprises the following components in molar ratio: SiO 2₂：70％，SnO：1.14％，Na₂O：20％,CaO：x％,CaF₂: (10-x)%, wherein x% is the molar ratio of CaO, and (10-x)% is CaF₂The molar ratio of (A) to (B); x is 5, 3, 7, 2 or 8. Re with the mol ratio of 0.1 to 1.5 percent is also doped³⁺(ii) a Wherein Re³⁺Is a rare earth ion; the preparation method comprises the following steps: (a) selecting raw materials, (b) mixing ingredients, and (c) melting glass ceramics. The transparent glass ceramic prepared by the invention has high-efficiency ultraviolet-visible down-conversion luminescence property, can realize multicolor light emission, and is suitable for large-area industrial production.

Description

Ultraviolet light excited multicolor light emitting glass and preparation method thereof

Technical Field

The invention belongs to the technical field of illumination and display, and particularly relates to ultraviolet light excited multicolor light emitting glass and a preparation method thereof.

Background

In recent years, white light sources have attracted much attention because of their important application prospects in fields such as solid-state multicolor three-dimensional displays and bioluminescent probes. At present, energy-saving lamps and white light LED devices which are widely used are irradiated by short-wavelength light, and white light emission is obtained through mixed light conversion of a plurality of groups of phosphors. However, the method still has the problems of weak light intensity, poor color stability, complex process and the like. Therefore, it is necessary to find a new solid luminescent material that emits strong white light under near ultraviolet excitation and is resistant to ultraviolet radiation (stable structure and performance). The luminescent glass is an important fluorescent material, and has the advantages of simple preparation, low cost, good repeatability, good transparency, easy doping and the like. The rare earth ions have rich electronic energy levels and narrow emission lines, so that the rare earth ions are very suitable to be used as down-conversion emission centers. By doping rare earth ions, the optical glass has the characteristics of better fluorescence characteristic, pure luminous chromaticity, stable physicochemical property, high conversion efficiency and the like.

However, the rare earth ions have the problem of relatively narrow absorption cross section for ultraviolet light.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides ultraviolet light excited multicolor light emitting glass and a preparation method thereof, and Eu is selected and used in the invention³⁺、Tb³⁺Rare earth ions as luminescent center to prepare Eu³⁺、Tb³⁺A rare earth ion-doped transparent glass-ceramic having high light transmittance, high thermal stability (capable of withstanding high temperatures of 800 ℃) and high luminous intensity; and color tunability from green to white to red is achieved.

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

an ultraviolet light excited multicolor light emitting glass, the matrix material comprises the following components in molar ratio: SiO 2₂：70％，SnO：1.14％，Na₂O：20％,CaO：x％,CaF₂: (10-x)%, wherein x% is the molar ratio of CaO, and (10-x)% is CaF₂The molar ratio of (A) to (B); x is 5, 3, 7, 2 or 8.

Preferably, Re is also doped in a molar ratio of 0.1-1.5%³⁺(ii) a Wherein Re³⁺Is a rare earth ion.

Preferably, the Re³⁺Is Eu³⁺Or Tb³⁺。

A method for preparing ultraviolet light excited multicolor light emitting glass comprises the following steps:

(a) selecting glass ceramic raw materials;

(b) mixing glass ceramic batch; weighing the raw materials according to the proportion, and adding absolute ethyl alcohol for grinding treatment;

(c) melting glass ceramics; the glass ceramic is melted by adopting a corundum crucible, the melting temperature is 1550 ℃, the melting time is 1 hour, then the glass ceramic is rapidly cooled, and the ultraviolet light excited multicolor light emitting glass is obtained through annealing treatment.

Preferably, the milling treatment of step (b) is 0.5 hours.

Preferably, the annealing time of the step (c) is 4 hours, and the annealing temperature is 540 ℃.

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

1. the preparation method is simple and convenient, has low color temperature, and is suitable for industrial batch production.

2. Compared with fluorescent powder, the glass ceramic prepared by the invention has better thermal stability and chemical stability.

3. The glass related by the invention is a novel ultraviolet light conversion material with good stability and good chroma, Eu³⁺And Tb³⁺The doping of (a) makes the emission of the glass tunable from green through white to red.

4. The invention absorbs ultraviolet light in a wide band by doping rare earth ions; the invention utilizes low power (about 0.5 Mw/mm)²) The 266nm ultraviolet light is an excitation light source, and the thermal influence of the excitation source is reduced.

Drawings

FIG. 1 is an emission spectrum of a sample of examples 1-5 under 266nm excitation;

FIG. 2 is an emission spectrum of the samples of examples 6-12 at 266nm excitation;

FIG. 3 is an emission spectrum of the samples of examples 13-18 at 266nm excitation.

Detailed Description

The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The specific techniques or conditions are not indicated in the examples, and the techniques or conditions described in the literature in the art are performed in accordance with the instructions. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Examples 1 to 5

The substrate material is analytically pure SiO₂，SnO,Na₂O, CaO and CaF₂The matrix material ratio is as follows: 70SiO₂-1.14SnO-20Na₂O–xCaO-(10-x)CaF₂And x is 5, 3, 7, 2 and 8. The mass of each raw material is shown in table 1. The preparation method comprises the steps of weighing the raw materials according to the proportion, fully grinding the raw materials, putting the raw materials into a corundum crucible, heating the mixture for 1 hour at 1550 ℃, then rapidly cooling the mixture to form glass ceramics, and annealing the glass ceramics for 4 hours at 540 ℃ to increase the crystallinity of microcrystals to obtain the ultraviolet light excited multicolor light emitting glass.

Spectral measurements were performed on the samples obtained in examples 1 to 5, and the emission spectra were obtained as shown in FIG. 1 and the color coordinates are shown in Table 2.

TABLE 1 glass compositions (units: g) of examples 1-5

The experimental results are as follows: the samples of examples 1 to 5 were excited by a 266nm ultraviolet light source to obtain the emission spectra of fig. 1, and the emission spectra of fig. 1 were analyzed by CIE1931 color coordinate calculation software to obtain the color coordinates in table 2, and it can be seen from table 2 that CaO and CaF were changed under the excitation of the ultraviolet light source₂The ratio of (a) achieves white light emission of fluorescence intensity, the optimum color coordinates being (0.3201, 0.3105) corresponding to example 4.

TABLE 2 color coordinates of examples 1-5

Examples	CIEx	CIEy
			Example 1	0.3204	0.3546
Example 2	0.3201	0.3596
			Example 3	0.2994	0.3342
Example 4	0.3201	0.3150
			Example 5	0.3074	0.3425

Examples 6 to 12

The material is analytically pure SiO₂，SnO,Na₂O，CaO，CaF₂The rare earth ions select fluoride with the purity of 99.99 percent as a main raw material, and the mixture ratio of the matrix materials is as follows: 70SiO₂-1.14SnO-20Na₂O–2CaO-8CaF₂: doped ion Eu³⁺Weighing raw materials according to the molar ratio of y to 0, 0.1, 0.3, 0.5, 0.8, 1 and 1.5 percent; the mass of each raw material is shown in table 3; fully grinding for 0.5 hour; putting the glass into a corundum crucible, heating the glass at 1550 ℃ for 1 hour, then quickly cooling the glass into glass ceramic, and annealing the glass at 540 ℃ for 4 hours to increase the crystallinity of the microcrystal so as to obtain the ultraviolet light excited multicolor light emitting glass.

Spectral measurements were performed on the samples of examples 6-12 to obtain emission spectra as shown in FIG. 2 and color coordinates as shown in Table 4.

TABLE 3 glass compositions (units: g) of examples 6-12

The experimental results are as follows: the samples of examples 6 to 12 were excited by a 266nm ultraviolet light source to obtain the emission spectra of FIG. 2, and the emission spectra of FIG. 2 were analyzed by CIE1931 color coordinate calculation software to obtain the color coordinates in Table 4, from which it can be seen in Table 4 that the rare earth ion Eu was changed under the excitation of the ultraviolet light source³⁺The concentration of (a) achieves white light emission with adjustable fluorescence intensity, the optimum color coordinates being (0.3234, 0.3475) corresponding to example 7.

TABLE 4 color coordinates of examples 6-12

Examples	CIEx	CIEy
			Example 6	0.3191	0.3484
Example 7	0.3234	0.3475
			Example 8	0.3583	0.3707
Example 9	0.3578	0.3561
			Example 10	0.4050	0.3764
Example 11	0.3973	0.3617
			Example 12	0.4407	0.3779

Examples 13 to 18

The material is analytically pure SiO₂，SnO,Na₂O, CaO and CaF₂The rare earth ions select fluoride with the purity of 99.99 percent as a main raw material, and the mixture ratio of the matrix materials is as follows: 70SiO₂-1.14SnO-20Na₂O–2CaO-8CaF₂: doping ion Tb³⁺The raw materials were weighed so that the molar ratio y was 0.1, 0.3, 0.5, 0.8, 1, 1.5%. Mixing the raw materials and fully grinding for 0.5 hour; putting the glass into a corundum crucible, heating the glass at 1550 ℃ for 1 hour, then quickly cooling the glass into glass ceramic, and annealing the glass at 540 ℃ for 4 hours to increase the crystallinity of the microcrystal so as to obtain the ultraviolet light excited multicolor light emitting glass. The mass of each raw material is shown in table 5. Spectral measurements were performed on the samples of examples 13-18 to obtain emission spectra as shown in FIG. 3 and color coordinates as shown in Table 6.

TABLE 5 glass compositions (units: g) of examples 13-18

The experimental results are as follows: 266nm ultraviolet light source is used for exciting the samples of the embodiments 13 to 18 to obtain the emission spectrum of the figure 3, CIE1931 color coordinate calculation software is used for analyzing the emission spectrum of the figure 3 to obtain the color coordinates in the table 6, and the change of the rare earth ion Tb under the excitation of the ultraviolet light source can be seen from the table 6³⁺(teeo) concentration realizationWith white light emission with tunable fluorescence intensity, the optimal color coordinates (0.3046, 0.3420) correspond to example 13.

TABLE 6 color coordinates of examples 13-18

Examples	CIEx	CIEy
			Example 13	0.3046	0.3420
Example 14	0.3184	0.3711
			Example 15	0.3055	0.3888
Example 16	0.3055	0.4106
			Example 17	0.3174	0.4379
Example 18	0.3081	0.4645

The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.

Claims

1. The ultraviolet excited multicolor light emitting glass ceramic is characterized in that a matrix material consists of the following raw materials in molar ratio: SiO 2₂：SnO：Na₂O：CaO：CaF₂70: 1.14: 20: x: (10-x), wherein x is the molar ratio of CaO, and (10-x) is CaF₂The molar ratio of (A) to (B); x is 5, 3, 7, 2 or 8; and also doping Re of 0.1-1.5% of the total molar weight of the matrix material³⁺(ii) a Wherein Re³⁺Is a rare earth ion.

2. The UV-excited, polychromatic light-emitting glass-ceramic according to claim 1, wherein Re³ ⁺Is Eu³⁺Or Tb³⁺。

3. The method of making an ultraviolet light excited multicolor light emitting glass-ceramic according to claim 1, comprising the steps of:

(a) selecting raw materials;

(b) mixing glass ceramic batch; weighing the raw materials according to the proportion, adding absolute ethyl alcohol, and grinding for 0.5 hour;

(c) melting glass ceramics; the glass ceramic is melted by adopting a corundum crucible, the melting temperature is 1550 ℃, the melting time is 1 hour, then the glass ceramic is rapidly cooled into glass ceramic, and the glass ceramic is annealed at 540 ℃ for 4 hours to obtain the ultraviolet light excited multicolor light emitting glass ceramic.