COPPER ION-DOPED POLYCHROMATIC FLUORESCENT GLASS AND PREPARATION METHOD AND USE THEREOF

Abstract

A copper ion-doped polychromatic fluorescent glass and a preparation method and use thereof are provided. The fluorescent glass has a chemical formula shown as the following: aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, wherein a, b, c, d, e, and f in the formula represent the molar coefficients of compounds, wherein a is 45 to 65, b is 10 to 30, c is 1 to 5, d is 5 to 20, e is 5 to 20, f is 0.1 to 5. The fluorescent can achieve blue, orange and near-infrared photoluminescence under the UV light with higher fluorescent quantum yield.

Claims

1. A copper ion-doped polychromatic fluorescent glass, wherein it has a chemical formula shown as the following:
aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, wherein a, b, c, d, e, and f in the formula represent the molar coefficients of compounds, wherein a is 45 to 65, b is 10 to 30, c is 1 to 5, d is 5 to 20, e is 5 to 20, f is 0.1 to 5.

2. The copper ion-doped polychromatic fluorescent glass according to claim 1, wherein in the fluorescent glass, d is 5 to 10, f is 0.1 to 0.5, or d is 8 to 15, f is 2 to 3, or d is 10 to 20, f is 0.3 to 1.

3. A preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 1, wherein the preparation method comprises the following steps: step S1, weighing P.sub.2O.sub.5, SiO.sub.2, ZnO, Cs.sub.2CO.sub.3, NaCl, CuCl and a reductant, and sufficiently grinding and mixing to form a mixture; step S2, under a reducing atmosphere, melting the mixture at 1000° C. to 1300° C. for 5 to 60 minutes; and step S3, pouring the melted mixture into a preheated mold, then annealing, cooling, cutting and polishing, thus obtaining the copper ion-doped polychromatic fluorescent glass.

4. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 3, wherein in step S2, temperature of the melting is 1050° C. to 1200° C.

5. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 3, wherein in step S2, the melting lasts for 10 to 30 minutes.

6. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 3, wherein in step S2, the reducing atmosphere is provided by carbon blocks.

7. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 3, wherein in step S3, temperature of the annealing is 320° C. to 450° C.

8. Use of the copper ion-doped polychromatic fluorescent glass according to claim 1 in luminescence conversion materials.

9. The use according to claim 8, wherein the use of the copper ion-doped polychromatic fluorescent glass in single host white-light illumination, near-infrared venography, infrared night-vision scope or food testing.

10. A LED device, comprising a photoconverter and a LED chip, wherein the photoconverter comprises the copper ion-doped polychromatic fluorescent glass according to claim 1.

11. A preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 2, wherein the preparation method comprises the following steps: step S1, weighing P.sub.2O.sub.5, SiO.sub.2, ZnO, Cs.sub.2CO.sub.3, NaCl, CuCl and a reductant, and sufficiently grinding and mixing to form a mixture; step S2, under a reducing atmosphere, melting the mixture at 1000° C. to 1300° C. for 5 to 60 minutes; and step S3, pouring the melted mixture into a preheated mold, then annealing, cooling, cutting and polishing, thus obtaining the copper ion-doped polychromatic fluorescent glass.

12. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 11, wherein in step S2, temperature of the melting is 1050° C. to 1200° C.

13. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 11, wherein in step S2, the melting lasts for 10 to 30 minutes.

14. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 11, wherein in step S2, the reducing atmosphere is provided by carbon blocks.

15. The preparation method for the copper ion-doped polychromatic fluorescent glass according to claim 11, wherein in step S3, temperature of the annealing is 320° C. to 450° C.

16. Use of the copper ion-doped polychromatic fluorescent glass according to claim 2 in luminescence conversion materials.

17. The use according to claim 16, wherein the use of the copper ion-doped polychromatic fluorescent glass in single host white-light illumination, near-infrared venography, infrared night-vision scope or food testing.

18. A LED device, comprising a photoconverter and a LED chip, wherein the photoconverter comprises the copper ion-doped polychromatic fluorescent glass according to claim 2.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0039] FIG. 1 is an emission spectrum of a fluorescent glass prepared in Example 12.

[0040] FIG. 2 is an emission spectra of a fluorescent glass prepared in Example 7.

[0041] FIG. 3 is an XRD graph of fluorescent glass prepared in Examples 1, 6 and 11.

DESCRIPTION OF EMBODIMENTS

[0042] The technical solutions of the examples of the present invention are clearly and entirely described in the following, but implementations of the present invention are not limited thereto.

[0043] Unless specified, reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

Example 1

[0044] A copper ion-doped polychromatic fluorescent glass was provided by the present example, having a chemical formula as follows: aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, and a preparation method thereof included the following steps: [0045] step S1, P.sub.2O.sub.5, SiO.sub.2, ZnO, Cs.sub.2CO.sub.3, NaCl, CuCl and a reductant were weighed, and sufficiently grinded and mixed for 0.5 hour; [0046] step S2, under a reducing atmosphere, melting was performed at 1100° C. for 30 minutes; and [0047] step S3, poured into a preheated mold, then annealed at 350° C. for 2 hours, after cooling, cutting and polishing, thus the copper ion-doped polychromatic fluorescent glass was obtained. Specific formulation is shown in Table 1.

Examples 2 to 10

[0048] A series of copper ion-doped polychromatic fluorescent glass was provided by the examples, having a chemical formula as follows: aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, and the preparation method was the same as that of Example 1. Specific formulation is shown in Table 1.

TABLE-US-00001 TABLE 1 Formulation of Examples 1 to 10 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 P.sub.2O.sub.5 55 55 55 55 55 55 55 55 55 55 SiO.sub.2 20 20 20 20 20 20 20 20 20 20 ZnO 3 3 3 3 3 3 3 3 3 3 NaCl 12 12 12 12 12 12 12 12 12 12 Cs.sub.2CO.sub.3 5 8 10 8 8 8 12 15 12 12 CuCl 0.2 0.2 0.2 0.1 0.5 2.5 2.5 2.5 2 3

Examples 11 to 17

[0049] A series of copper ion-doped polychromatic fluorescent glass was provided by the examples, having a chemical formula as follows: aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, and the preparation method was the same as that of Example 1. Specific formulation is shown in Table 2.

TABLE-US-00002 TABLE 2 Formulation of Examples 11 to 17 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 P.sub.2O.sub.5 55 55 55 55 55 45 65 SiO.sub.2 20 20 20 20 20 30 10 ZnO 3 3 3 3 3 1 5 NaCl 12 12 12 12 12 20 5 Cs.sub.2CO.sub.3 10 15 20 15 15 5 20 CuCl 0.6 0.6 0.6 0.3 1 5 0.1

Example 18

[0050] A copper ion-doped polychromatic fluorescent glass provided by Example 18 had the same components and preparation method as those of Example 1, only with the difference in the temperature for melting of step S2, i.e., the temperature for melting in Example 18 is 1100° C.

Example 19

[0051] A copper ion-doped polychromatic fluorescent glass provided by Example 19 had the same components and preparation method as those of Example 1, only with the difference in the temperature for melting of step S2, i.e., the temperature for melting in Example 19 is 1300° C.

Comparative Examples 1 to 4

[0052] A series of fluorescent glass was provided by Comparative Examples 1 to 4, having a chemical formula as follows: aP.sub.2O.sub.5-bSiO.sub.2-cZnO-dCs.sub.2CO.sub.3-eNaCl-fCuCl, and the preparation method of Comparative Examples 1 to 4 was the same as that of Example 1, only with the difference in formulation. Specific formulation is shown in Table 3.

TABLE-US-00003 TABLE 3 Formulation of Comparative Examples 1 to 4 (part) Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 P.sub.2O.sub.5 55 55 55 55 SiO.sub.2 20 20 20 20 ZnO 3 3 3 3 NaCl 12 12 12 12 Cs.sub.2CO.sub.3 10 10 3 25 CuCl 8 0.05 0.5 0.5

[0053] Test Results

[0054] The above examples and comparative examples were all subjected to the fluorescent quantum yield test. The test was performed by using the absolute quantum yield spectrometer C13534, from HAMAMATSU. The excitation wavelengths were 300 nm (blue), 320 nm (orange) and 365 nm (near-infrared). Emission intensity at the corresponding waveband (280 to 600 nm for blue, 300 to 800 nm for orange, 350 to 1300 nm for near-infrared) of the reference sample (a blank cuvette was selected in the test) was first tested, and emission intensity at the corresponding waveband of the samples were then tested. Results of the quantum yield were given directly by the spectrometer.

TABLE-US-00004 TABLE 3 Data of Examples and Comparative Examples Fluorescent quantum yield Example 1 64.7% (blue) Example 2 65.8% (blue) Example 3 34.8% (blue) Example 4 76.0% (blue) Example 5 68.0% (blue) Example 6 52.7% (orange) Example 7 56.0% (orange) Example 8 53.7% (orange) Example 9 54.8% (orange) Example 10 60.1% (orange) Example 11 27.0% (near infrared) Example 12 22.1% (near infrared) Example 13 27.4% (near infrared) Example 14 23.2% (near infrared) Example 15 24.5% (near infrared) Example 16 30.9% (orange) Example 17 18.8% (near infrared) Example 18 54.7% (blue) Example 19 44.7% (blue) Comparative  2.7% (orange) Example 1 Comparative 10.8% (blue) Example 2 Comparative 15.7% (blue) Example 3 Comparative  1.6% (near infrared) Example 4 — —

[0055] It can be seen from Examples 1 to 5 that when the fluorescent glass has the d being 5 to 10 and f being 0.1 to 0.5, the quantum yield of blue photoluminescence is higher. It can be seen from Examples 6 to 10 that when the fluorescent glass has the d being 8 to 15 and f being 2 to 3, the quantum yield of orange photoluminescence is the highest. It can be seen from Examples 11 to 15 that when the fluorescent glass has the d being 10 to 20 and f being 0.3 to 1, quantum yield of the near-infrared photoluminescence is the highest.

[0056] It can be seen from Comparative Examples 1 to 4 that the quantum yield is low when the components of fluorescent glass are not within the range, making it unable to be used.

[0057] It can be seen from FIG. 1 that the fluorescent glass can achieve near-infrared emission under the UV light, and application scenarios of the fluorescent glass are widely expanded, such as in the fields of near-infrared venography, infrared night-vision scope or food testing.

[0058] It can be seen from FIG. 2 that under the UV light, the fluorescent glass prepared by Example 7 can realize blue and orange emission simultaneously, and with the red shift of the excitation wavelength, ratio of the orange emission increase gradually with respect to the blue emission. Under the excitation of 310 to 350 nm waveband, it is expected to realize single host white-light illumination.

[0059] The microcrystal phase probably existing in the glass may cause an effect on the coordination environment for Cu+, thereby affecting its quantum yield. It can be seen from FIG. 3 that there's only one hump of the amorphous phase in the XRD graph, demonstrating that there's no microcrystal phase in the fluorescent glass.

[0060] Apparently, the above examples of the present invention are only an example to clearly illustrate the invention, not a limitation of the implementation of the present invention. For those of ordinary skill in the art, other variation or changes in different forms can be made on the basis of the above description. It is unnecessary and impossible to enumerate all the implementations here. Any modification, equivalent replacement and improvement made within the spirit and principles of the present invention shall be included in the protection scope of the claims of the invention.