A rare earth doped multicolor fluorescent emission borate glass and preparation method thereof

Abstract

The present application provides a rare-earth doped multi-color fluorescence-emitting borate glass and a preparation method thereof. The chemical general formula of the multi-color fluorescence-emitting borate glass is Sr 2.99 B 14 O 24 : 0.01RE 3+ , where RE is any one of the four rare-earth elements Ce, Tb, Sm, and Eu. The multi-color fluorescence-emitting borate glass of the present application is an inorganic light conversion material, which can simultaneously play the roles of a luminescent converter and a packaging material of a phosphor and an organic resin in packaging, and overcomes the disadvantages of the phosphor requiring the use of an organic packaging resin. The multi-color fluorescence-emitting borate glass of the present application doped with different rare-earth ions in the same matrix obtains a glass that emits trichromatic fluorescence. It produces good monochromatic light, has stable structure and stable luminescence under blue light or near-ultraviolet light excitation, and the emission range is 460-620 nm. It can emit blue, green, orange, and red light respectively under the irradiation of blue light or near-ultraviolet light, and can well match the blue-violet light chip for manufacturing WLEDs, showing outstanding advantages in the application of WLEDs.

Description

Technical Field

[0001] The present application belongs to the technical field of inorganic luminescent materials, and more specifically, relates to a rare earth doped multicolor fluorescent emitting borate glass and a preparation method thereof. Background Art

[0002] With the development of modern lighting industry technology, automobile headlights have experienced the changes of acetylene lamps, halogen lamps, xenon lamps, LED lamps and the current fifth generation of laser (LD) headlights. LD lighting not only has all the advantages of LED such as good stability, environmental protection and energy saving, but also has the advantages of strong penetration, longer lighting distance and higher luminous efficiency. It is considered to be the most promising automobile headlight at present. There are three ways to obtain white light LD: (1) three primary color lasers are mixed into white light; (2) blue laser excites yellow phosphor; (3) near-ultraviolet laser excites multi-color phosphor. The first method LD chip is relatively expensive, and laser leakage is prone to cause safety accidents. The second method has a poor color rendering index due to the lack of red emission. The third method only uses one LD chip, which is safer and more economical, and the tunable fluorescence emission of multi-color phosphor can effectively make up for the problem of insufficient monochromatic fluorescence emission. However, the commercial phosphors used in LEDs are often mixed with organic resins for packaging. When used in LD lighting systems, they are prone to rapid aging and carbonization under high-power laser irradiation, which will lead to a series of problems such as fluorescence color deviation and shortened LD device service life. With the emergence of more and more high-power LD chips, the application environment has also put forward higher standards for LD white light lighting fluorescent materials. Summary of the invention

[0003] The purpose of the present application is to provide a rare earth doped multicolor fluorescent emitting borate glass and a preparation method thereof, so as to solve the technical problems of color deviation and short equipment service life caused by the need to use organic encapsulation resin for commercial luminescent powder in existing lighting technology, which is of great significance to the development of new low-carbon energy-saving and environmentally friendly lighting technology.

[0004] To achieve the above-mentioned object, in a first aspect of the present application, a rare earth doped multicolor fluorescent emitting borate glass is provided, wherein the chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01RE 3+ , where RE is any one of the four rare earth elements Ce, Tb, Sm, and Eu.

[0005] Furthermore, the chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01Ce 3+The multicolor fluorescent emitting borate glass is composed of SrCO 3 : 30-35%, H 3 BO 3 : 65-70%, CeO 2 : 0.3-0.4% of raw materials.

[0006] Furthermore, the chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 : 0.01Tb 3+ The multicolor fluorescent emitting borate glass is composed of SrCO 3 : 30-35%, H 3 BO 3 : 65-70%, Tb 4 O 7 : 0.3-0.4% of raw materials.

[0007] Furthermore, the chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01Sm 3+ The multicolor fluorescent emitting borate glass is composed of SrCO 3 : 30-35%, H 3 BO 3 : 65-70%, Sm 2 O 3 : 0.3-0.4% of raw materials.

[0008] Furthermore, the chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01Eu 3+ The multicolor fluorescent emitting borate glass is composed of SrCO 3 : 30-35%, H 3 BO 3 : 65-70%,Eu 2 O 3 : 0.3-0.4% of raw materials.

[0009] In a second aspect of the present application, a method for preparing rare earth doped multicolor fluorescent emitting borate glass is provided, comprising the following steps:

[0010] According to the chemical formula Sr 2.99 B 14 O 24 :0.01RE 3+Weigh the raw material SrCO in the molar ratio 3 , H 3 BO 3 and rare earth oxides, adding the weighed raw materials into anhydrous ethanol and grinding them to mix them uniformly;

[0011] After the anhydrous ethanol is completely volatilized, the mixed raw materials are heated to 900-1200° C. in an air atmosphere or a reducing atmosphere and then kept warm for 4-5 hours. After naturally cooling to room temperature, the glass sample is ground and polished to obtain the multicolor fluorescent emitting borate glass.

[0012] Furthermore, the heating rate of the heating is 5-10°C / min.

[0013] Furthermore, the H 3 BO 3 The amount of H is excessive to compensate for the loss of boric acid due to volatilization at high temperature. 3 BO 3 Add 10% more of the weighed mass.

[0014] Further, the mixed raw material is prepared under a reducing atmosphere. 2.99 B 14 O 24 :0.01Ce 3+ and Sr 2.99 B 14 O 24 : 0.01Tb 3+ Glowing glass.

[0015] Further, the mixed raw material is prepared under air atmosphere. 2.99 B 14 O 24 :0.01Sm 3+ and Sr 2.99 B 14 O 24 :0.01Eu 3+ Glowing glass.

[0016] Furthermore, the analytical purity of each raw material used was 99.99%.

[0017] Furthermore, the room temperature is 20±5°C.

[0018] Compared with the prior art, this application has the following technical effects:

[0019] The present invention relates to a rare earth doped multicolor fluorescent emitting borate glass Sr 2.99 B 14 O 24 :0.01RE 3+It is an inorganic light conversion material. The rare earth doped multicolor fluorescent emitting borate glass of the present application not only has excellent optical properties such as heat resistance and high transmittance, but also can play the role of luminescent converter and packaging material in the package of phosphor and organic resin at the same time, overcoming the disadvantage that phosphor needs to use organic packaging resin. The multicolor fluorescent emitting borate glass Sr 2.99 B 14 O 24 :0.01RE 3+ By doping different kinds of rare earth ions in the same matrix, we obtain glass that emits three primary colors of fluorescence. It produces good monochromatic light under the excitation of blue light or near-ultraviolet light, has a stable structure and luminescence, and an emission range of 460-620nm. It can emit blue, green, orange and red light respectively under the irradiation of blue light or near-ultraviolet light, and can be well matched with the blue-violet light chips for manufacturing WLEDs (white light emitting diodes), and has outstanding advantages in the application of WLEDs.

[0020] The method for preparing a rare earth-doped multicolor fluorescent emitting borate glass of the present application improves the luminous efficiency and chemical stability of four types of luminescent glasses by adjusting the type, content and calcination temperature of raw materials, and has the advantages of simple preparation process, low cost, green energy saving, clean and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0022] Figure 1 X-ray diffraction (XRD) patterns of the multicolor fluorescent emitting borate glasses provided in Examples 1-4 of the present application;

[0023] Figure 2 The luminescence spectrum of the multicolor fluorescent borate glass provided in Example 1 of the present application (λ em =463nm,λ ex =375nm);

[0024] Figure 3 The luminescence spectrum of the multicolor fluorescent borate glass provided in Example 2 of the present application (λ em =543nm,λ ex =369nm);

[0025] Figure 4 The luminescence spectrum of the multicolor fluorescent borate glass provided in Example 3 of the present application (λ em=599nm,λ ex =401nm);

[0026] Figure 5 The luminescence spectrum of the multicolor fluorescent borate glass provided in Example 4 of the present application (λ em =613nm,λ ex =394nm). DETAILED DESCRIPTION

[0027] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0028] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0029] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass described in the embodiment description of the present application can be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0030] Example 1

[0031] A rare earth ion Ce 3+ Blue fluorescence emitting borate glass doped with Sr 2.99 B 14 O 24 :0.01Ce 3+ , whose mass percentage is SrCO 3 : 31.41%, H 3 BO 3 : 68.21%, CeO 2 : 0.37%.

[0032] The preparation steps of the above-mentioned blue fluorescent emitting borate glass are as follows:

[0033] (1) Weighing: Use an electronic balance to weigh the raw material: SrCO 3 :1.3156g、H 3 BO 3 :2.8568g、CeO 2: 0.0157g;

[0034] (2) Grinding: Put the raw materials into an agate bowl, add an appropriate amount of anhydrous ethanol and grind them to make them uniformly mixed; after the mixture is uniform and the anhydrous ethanol is completely evaporated, pour them into an alumina crucible;

[0035] (3) Calcination: Finally, the crucible was placed in a KF1700 box-type muffle furnace, the heating rate was set to 5°C / min, and the temperature was raised to 900°C and then kept at this temperature for 4 hours. After cooling to room temperature, the sample was taken out and polished to obtain a blue fluorescent borate glass.

[0036] The XRD spectrum of the blue fluorescent borate glass obtained in Example 1 of the present application is as follows: Figure 1 As shown, a broad peak is observed at 29°, which is a typical XRD characteristic peak of glass. Although there is no obvious sharp diffraction peak in the spectrum, there is still a broad peak at the characteristic diffraction peak, which indicates that the blue fluorescent borate glass of Example 1 is successfully obtained.

[0037] The blue fluorescent borate glass obtained in Example 1 of the present application was subjected to fluorescence testing, and its excitation and emission spectra were as follows: Figure 2 As shown. Under the excitation of 375nm wavelength, the luminescent glass emits blue light.

[0038] Example 2

[0039] A rare earth ion Tb 3+ Green fluorescence emitting borate glass doped with Sr 2.99 B 14 O 24 : 0.01Tb 3+ , whose mass percentage is SrCO 3 : 31.41%, H 3 BO 3 : 68.19%, Tb 4 O 7 : 0.40%.

[0040] The green fluorescent emitting borate glass is prepared as follows:

[0041] (1) Weighing: Use an electronic balance to weigh the raw material: SrCO 3 :1.3156g、H 3 BO 3 :2.8568g、Tb 4 O 7 : 0.0169g;

[0042] (2) Grinding: Put the raw materials into an agate bowl, add an appropriate amount of anhydrous ethanol and grind them to make them uniformly mixed; after the mixture is uniform and the anhydrous ethanol is completely evaporated, pour them into an alumina crucible;

[0043] (3) Calcination: Finally, the crucible was placed in a KF1700 box-type muffle furnace, the heating rate was set to 5°C / min, and the temperature was raised to 900°C and then kept at this temperature for 4 hours. After cooling to room temperature, the sample was taken out and polished to obtain green fluorescent borate glass.

[0044] The XRD spectrum of the green fluorescent borate glass obtained in Example 1 of the present application is as follows: Figure 1 As shown, a broad peak is observed at 29°, which is a typical XRD characteristic peak of glass. Although there is no obvious sharp diffraction peak in the spectrum, there is still a broad peak at the characteristic diffraction peak, which indicates that the green fluorescent emitting borate glass of Example 1 is successfully obtained.

[0045] The green fluorescent borate glass obtained in Example 2 of the present application was subjected to fluorescence testing, and its excitation and emission spectra were as follows: Figure 3 As shown. Under the excitation of 369nm wavelength, the luminescent glass emits green light.

[0046] Example 3

[0047] A rare earth ion Sm 3+ Orange fluorescence emitting borate glass doped with Sr 2.99 B 14 O 24 :0.01Sm 3+ , whose mass percentage is SrCO 3 : 31.41%, H 3 BO 3 : 68.21%, Sm 2 O 3 : 0.37%.

[0048] The preparation steps of the above orange fluorescent emitting borate glass are as follows:

[0049] (1) Weighing: Use an electronic balance to weigh the raw material: SrCO 3 :1.3156g、H 3 BO 3 :2.8568g、Sm 2 O 3 : 0.0157g;

[0050] (2) Grinding: Put the raw materials into an agate bowl, add an appropriate amount of anhydrous ethanol and grind them to make them uniformly mixed; after the mixture is uniform and the anhydrous ethanol is completely evaporated, pour them into an alumina crucible;

[0051] (3) Calcination: Finally, the crucible was placed in a KF1700 box-type muffle furnace, the heating rate was set to 5°C / min, and the temperature was raised to 900°C and then kept at this temperature for 4 hours. After cooling to room temperature, the sample was taken out and polished to obtain an orange fluorescent borate glass.

[0052] The XRD spectrum of the orange fluorescent borate glass obtained in Example 1 of the present application is as follows: Figure 1 As shown, a broad peak is observed at 29°, which is a typical XRD characteristic peak of glass. Although there is no obvious sharp diffraction peak in the spectrum, there is still a broad peak at the characteristic diffraction peak, which indicates that the orange fluorescent borate glass of Example 1 is successfully obtained.

[0053] The orange fluorescent borate glass obtained in Example 3 of the present application was subjected to fluorescence testing, and its excitation and emission spectra were as follows: Figure 4 As shown. Under the excitation of 401nm wavelength, the luminescent glass emits orange light.

[0054] Example 4

[0055] A rare earth ion Eu 3+ Red fluorescence emitting borate glass doped with Sr 2.99 B 14 O 24 :0.01Eu 3+ , whose mass percentage is SrCO 3 : 31.41%, H 3 BO 3 : 68.21%,Eu 2 O 3 : 0.38%.

[0056] The preparation steps of the red fluorescent emitting borate glass are as follows:

[0057] (1) Weighing: Use an electronic balance to weigh the raw material: SrCO 3 :1.3156g、H 3 BO 3 :2.8568g、Eu 2 O 3 : 0.0158g;

[0058] (2) Grinding: Put the raw materials into an agate bowl, add an appropriate amount of anhydrous ethanol and grind them to make them uniformly mixed; after the mixture is uniform and the anhydrous ethanol is completely evaporated, pour them into an alumina crucible;

[0059] (3) Calcination: Finally, the crucible was placed in a KF1700 box-type muffle furnace, the heating rate was set to 5°C / min, and the temperature was raised to 900°C and then kept at this temperature for 4 hours. After cooling to room temperature, the sample was taken out and polished to obtain red fluorescent emitting borate glass.

[0060] The XRD spectrum of the red fluorescent borate glass obtained in Example 1 of the present application is as follows: Figure 1 As shown, a broad peak is observed at 29°, which is a typical XRD characteristic peak of glass. Although there is no obvious sharp diffraction peak in the spectrum, there is still a broad peak at the characteristic diffraction peak, which indicates that the red fluorescent borate glass of Example 1 is successfully obtained.

[0061] The red fluorescent borate glass obtained in Example 4 of the present application was subjected to fluorescence testing, and its excitation and emission spectra were as follows: Figure 5 As shown. Under the excitation of 394nm wavelength, the luminescent glass emits red light.

[0062] A rare earth doped multicolor fluorescent emitting borate glass Sr 2.99 B 14 O 24 :0.01RE 3+ It is an inorganic light conversion material. The rare earth doped multicolor fluorescent emitting borate glass of the embodiment of the present application not only has excellent optical properties such as heat resistance and high transmittance, but also can play the role of luminescent converter and packaging material in the package of phosphor and organic resin at the same time, overcoming the disadvantage that phosphor needs to use organic packaging resin. The multicolor fluorescent emitting borate glass Sr in the embodiment of the present application not only has excellent optical properties such as heat resistance and high transmittance, but also can play the role of luminescent converter and packaging material in the package of phosphor and organic resin at the same time, overcoming the disadvantage that phosphor needs to use organic packaging resin. 2.99 B 14 O 24 :0.01RE 3+ By doping different kinds of rare earth ions in the same matrix, we obtain glass that emits three primary colors of fluorescence. It produces good monochromatic light under the excitation of blue light or near-ultraviolet light, has a stable structure and luminescence, and an emission range of 460-620nm. It can emit blue, green, orange and red light respectively under the irradiation of blue light or near-ultraviolet light, and can match well with the blue-violet light chips used to manufacture WLEDs, and has outstanding advantages in the application of WLEDs.

[0063] A method for preparing a rare earth-doped multicolor fluorescent emitting borate glass in an embodiment of the present application improves the luminous efficiency and chemical stability of four types of luminescent glasses by adjusting the type, content and calcination temperature of raw materials, and has the advantages of simple preparation process, low cost, green energy saving, clean and environmentally friendly.

[0064] The above embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the present application. It should be pointed out that, for a person of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. A rare earth doped multicolor fluorescent emitting borate glass, characterized in that: The general chemical formula of the multicolor fluorescent borate glass is Sr 2.99 B 14 O 24 :0.01RE 3+ , wherein RE is any one of the four rare earth elements Ce, Tb, Sm, and Eu; in terms of mass percentage, the multicolor fluorescent emitting borate glass is composed of raw materials of SrCO3: 30-35%, H3BO3: 65-70%, and rare earth oxide: 0.3-0.4%, with a total mass of 100%; The multicolor fluorescent emitting borate glass is prepared by the following steps: According to the chemical formula Sr 2.99 B 14 O 24 :0.01RE 3+ Weigh the raw materials SrCO3, H3BO3 and rare earth oxide, add the weighed raw materials into anhydrous ethanol and grind them to mix them evenly; After the anhydrous ethanol is completely volatilized, the mixed raw materials are heated to 900°C at a heating rate of 5°C / min in an air atmosphere or a reducing atmosphere, and then kept warm for 4 hours. After naturally cooling to room temperature, the glass sample is polished to obtain the multicolor fluorescent emitting borate glass.

2. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01 Ce 3+ The multicolor fluorescent emitting borate glass is composed of raw materials with a mass percentage of SrCO3: 30-35%, H3BO3: 65-70%, and CeO2: 0.3-0.4%.

3. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01 Tb 3+ The multicolor fluorescent emitting borate glass is composed of raw materials with a mass percentage of SrCO3: 30-35%, H3BO3: 65-70%, and Tb4O7: 0.3-0.4%.

4. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01 Sm 3+ The multicolor fluorescent emitting borate glass is composed of raw materials with a mass percentage of SrCO3: 30-35%, H3BO3: 65-70%, and Sm2O3: 0.3-0.4%.

5. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The chemical formula of the multicolor fluorescent emitting borate glass is Sr 2.99 B 14 O 24 :0.01Eu 3+ The multicolor fluorescent emitting borate glass is composed of raw materials with a mass percentage of SrCO3: 30-35%, H3BO3: 65-70%, and Eu2O3: 0.3-0.4%.

6. A rare earth doped multicolor fluorescent emitting borate glass according to any one of claims 1 to 5, characterized in that: The amount of H3BO3 weighed is excessive.

7. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The mixed raw material is prepared under a reducing atmosphere. 2.99 B 14 O 24 :0.01Ce 3+ and Sr 2.99 B 14 O 24 : 0.01Tb 3+ Luminous glass.

8. The rare earth doped multicolor fluorescent emitting borate glass according to claim 1, characterized in that: The mixed raw materials are prepared under air atmosphere. 2.99 B 14 O 24 :0.01Sm 3+ and Sr 2.99 B 14 O 24 :0.01Eu 3+ Luminous glass.

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