CN113264687A - Topology chemical reduction Eu3+/Eu2+Co-doped UV-LED white light microcrystalline glass and preparation method thereof - Google Patents
Topology chemical reduction Eu3+/Eu2+Co-doped UV-LED white light microcrystalline glass and preparation method thereof Download PDFInfo
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- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 abstract 1
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Images
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
Abstract
The invention discloses a topology chemical reduction Eu3+/Eu2+The co-doped UV-LED white light microcrystalline glass and the preparation method thereof are prepared from the following components in percentage by mol: 40-60% SiO210-25% of Al2O310-20% of Na2CO38-15% of YF36 to 15 percent of NaF and 0.1 to 0.5 percent of Eu2O3And 0.02-0.1% of reducing agent, the reducing agent is nitride or carbide, and all the raw material components are mixed and ground according to a set proportionGrinding, melting and annealing to obtain the white light microcrystalline glass. The method directly performs high-temperature solid-phase melting reaction in the air, and partially reduces Eu in situ by using nitride or carbide reducing agent3+Thereby realizing Eu3+With Eu2+The co-doping of the glass generates white light under the ultraviolet excitation of 395nm, and the white light microcrystalline glass is obtained.
Description
Technical Field
The invention belongs to the technical field of inorganic non-metallic luminescent materials, and particularly relates to topologically chemically reduced Eu capable of being synthesized under the air condition3+/Eu2+Co-doped UV-LED white light microcrystalline glass and co-doped UV-LED white light microcrystalline glassA preparation method.
Background
White light LEDs have gradually replaced conventional light sources such as incandescent lamps and tungsten lamps as a new type of energy-saving light source, and have advantages in reliability, environmental protection, energy saving, and safety, and thus have been widely noticed.
In many published studies, Eu is generally carried out by a high temperature solid phase method under a reducing atmosphere3+Reduction to Eu2 +. The reducing atmosphere usually contains H2，N2、H2Mixed gas, carbon monoxide, argon gas mixture, etc., though Eu can be reduced in reducing atmosphere3+The method has high requirements on high-temperature sintering equipment and carrier gas accessories, and because most of reducing gases are flammable and explosive gases and some are toxic gases, the method has certain potential safety hazard. In addition, since only a small amount of the surface sample is in direct contact with the reducing gas during the aeration process, there is a limit to the thickness of the powder sample so that it cannot be prepared in large quantities. The self-reduction method for obtaining Eu is proposed for the first time by the iron clanging team in 19932+The process of (1). Although the method has simple sintering process, no flammable and explosive gas and mass production, four limitations (1) are provided for self-reduction without oxidizing ions in the doped matrix; (2) doped Re3+Must replace the divalent alkaline earth metal cations in the matrix; (3) the substrate can provide a proper crystal environment for the divalent rare earth ions, and the substituted alkaline earth metal ions and the divalent rare earth ions have similar ionic radii; (4) to prevent re-oxidation of the divalent rare earth ions, the mixture matrix must contain a suitable crystal structure.
At present, there are three main measures for generating white light, the first is to use a blue chip to excite red and green fluorescent materials, which have high color rendering property but poor color stability. The second is that the ultraviolet chip excites the three primary colors (red, green and blue) fluorescent material, which has better color rendering property and color stability but complex packaging process. The third is the principle of single-matrix direct white fluorescent material or the white light generated by three primary colors of light.The single-substrate direct white light material has simple packaging process and good color rendering property and color stability. Researches find that the single-matrix direct white light material has the advantages of good color rendering property, strong color reducibility, low cost, simple process, long service life and the like, is a material with development potential, and is concerned with. At present, the most used and mature process is that InGaN blue light chip excites YAG Ce3+The yellow phosphor produces white light. Single matrix direct white light materials other than YAG: ce3+Besides yellow fluorescent materials, rare earth luminescent materials are the most representative, and the most studied is the luminescence research of Eu-doped system.
Eu3+Commonly used as red phosphor material, Eu2+Is often used as a blue fluorescent material. Eu (Eu)3+Ions dominate the f-f transition corresponding to narrow-band emission, but it is difficult to cover the full spectrum. Eu (Eu)2+The ions mainly emit in a broadband mode by taking d-f transition as a main emission mode, and the intensity is high. Since Eu is used2 +Can be changed with the matrix material, so that Eu2+Can fall in any region from blue-violet light to red light in the visible region. Existing Eu3+/Eu2+In the co-doped fluorescent material, Eu is in most of the matrix2+Is obtained by subjecting Eu to reduction atmosphere3+Ion-implemented, and also in small part, by obtaining Eu through self-reduction effect of specific matrix material2+Ions.
Disclosure of Invention
Aiming at the existing Eu3+Reduced Eu2+The invention aims to provide a topology chemical reduction Eu, which has the problems of complexity and safety in the process3+/Eu2+The co-doped UV-LED white light microcrystalline glass is prepared by directly performing high-temperature solid-phase melting reaction in air and using nitride or carbide reducing agent (such as BN, AlN, Si)3N4SiC), partial in-situ reduction of Eu3+Thereby realizing Eu3+With Eu2+The co-doping of the glass generates white light under the ultraviolet excitation of 395nm, and the white light microcrystalline glass is obtained.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
topochemical reduction Eu3+/Eu2+The co-doped UV-LED white light microcrystalline glass is prepared from the following components in percentage by mole:
the reducing agent is nitride or carbide.
Preferably, the reducing agent is BN, AlN or Si3N4Or SiC; further preferably, the reducing agent is Si3N4. Further preferred in the present invention is Si3N4As reducing agent, Si3N4Decomposition at elevated temperature to produce N2Can effectively reduce Eu in glass matrix3+And can prevent Eu obtained after reduction2+Reoxidation in air and Si at high temperature3N4Compared with other nitrides, the nitrogen element can be introduced more under the same condition, and the melting point is lower.
The invention also provides the topology chemical reduction Eu3+/Eu2+The preparation method of the co-doped UV-LED white light microcrystalline glass comprises the steps of mixing and grinding the raw material components according to a set proportion, and melting and annealing to prepare the white light microcrystalline glass;
wherein the melting process is carried out in the air, and the temperature of the melting process is 1300-1450 ℃.
Preferably, the melting time is 40-50 min.
Preferably, the annealing process is carried out in air, and the temperature of the annealing process is 300-350 ℃ and the time is 2-5 h.
Preferably, the annealing is followed by further heat treatment, the heat treatment process is carried out under air, and the temperature of the heat treatment process is 540-.
The invention directly carries out high-temperature solid-phase melting reaction in the air by using nitride or carbide reducing agents (such as BN, AlN and Si)3N4SiC), partially reduced Eu3+Thereby realizing Eu3+With Eu2+And further adopting heat treatment to separate out NaYF4Contribute to Eu2+Thereby emitting blue light with Eu3+The red light is better complementary, and white light is generated under 395nm ultraviolet excitation, so that the white light glass ceramics is obtained.
Compared with the prior art, the invention has the following advantages:
1. the high-temperature solid-phase melting reaction is carried out in the air atmosphere in the whole process, the process is simple and easy to implement, and the safety coefficient is high.
2. The invention uses a nitride or carbide reducing agent (e.g. BN, AlN, Si)3N4SiC) partial in-situ reduction of Eu3+Thereby realizing Eu3+With Eu2+To achieve white light.
3. The NaYF exists in the heat treatment process after annealing4Contributes to Eu2+Thereby emitting blue light with Eu3+The red light of (a) preferably complements to form white light.
Drawings
FIG. 1 is a graph showing the emission spectra of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 under 365nm excitation;
FIG. 2 is a graph showing the emission spectra of the samples obtained in examples 1 to 3 and comparative examples 1 to 3 under 395nm excitation;
FIG. 3 is an XRD pattern of a sample prepared in example 1-2;
FIG. 4 is an absorption spectrum chart of samples obtained in examples 1 to 3 and comparative examples 1 to 3;
FIG. 5 is a CIE color coordinate diagram of samples prepared in examples 1-3 and comparative examples 1-3.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The white light LED glass sample of the embodiment comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3-0.05Si3N4
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
XRD of the sample obtained in this example was measured by an X-ray polycrystalline powder diffractometer, and the results are shown in FIG. 3.
The absorption spectrum of the sample prepared in this example was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The ultraviolet-visible spectrum of the sample prepared in this example is measured by a fluorescence spectrometer, and the results are shown in fig. 1 and 2, and the CIE color coordinates (0.437, 0.3314) are plotted, and the results are shown in fig. 5.
Example 2
The white light LED glass sample of the embodiment comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3-0.05Si3N4
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) placing the cooled glass sample into a muffle furnace at 560 ℃ for heat treatment for 4 h;
(5) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
XRD of the sample obtained in this example was measured by an X-ray polycrystalline powder diffractometer, and the results are shown in FIG. 3.
The absorption spectrum of the sample prepared in this pair was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The uv-vis spectra of the samples prepared in this example were obtained by fluorescence spectroscopy, and the results are shown in fig. 1 and 2, and CIE color coordinates (0.3165, 0.3203) are plotted, and the results are shown in fig. 5.
Example 3
The white light LED glass sample of the embodiment comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3-0.1Si3N4
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
The absorption spectrum of the sample prepared in this pair was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The uv-vis spectra of the samples prepared in this example were obtained by fluorescence spectroscopy, and the results are shown in fig. 1 and 2, and CIE color coordinates (0.2708, 0.3232) are plotted, and the results are shown in fig. 5.
Comparative example 1
The white light LED glass sample of the comparative example comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
The absorption spectrum of the sample prepared in this pair was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The uv-vis spectra of the sample prepared in this comparative example were obtained by fluorescence spectroscopy, and the results are shown in fig. 1 and 2, and CIE color coordinates (0.5872, 0.3605) were plotted, and the results are shown in fig. 5.
Comparative example 2
The white light LED glass sample of the comparative example comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3-0.5Si3N4
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
The absorption spectrum of the sample prepared in this pair was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The uv-vis spectra of the sample prepared in this comparative example were obtained by fluorescence spectroscopy, and the results are shown in fig. 1 and 2, and CIE color coordinates (0.2852, 0.3715) were plotted, and the results are shown in fig. 5.
Comparative example 3
The white light LED glass sample of the comparative example comprises the following components in percentage by mole:
40SiO2-25Al2O3-18Na2CO3-10YF3-7NaF-0.5Eu2O3-0.2Si3N4
(1) respectively weighing the required raw materials according to the mol percentage;
(2) grinding the raw materials in an agate mortar respectively, uniformly mixing, putting into a corundum crucible, calcining at 1400 ℃ for 45min to completely melt the powder mixture, and melting at high temperature without atmosphere protection only in air;
(3) pouring the material in the molten state onto a pre-heated copper plate in a muffle furnace, performing stress relief annealing treatment for 3 hours at 350 ℃, and then cooling to room temperature along with the furnace;
(4) and taking out the sample from the muffle furnace, grinding the sample into wafer glass with the radius of 30mm and the thickness of 3mm, and polishing the wafer glass by using the diamond micro powder solution until the surface of the block glass is mirror smooth.
The absorption spectrum of the sample prepared in this pair was measured by an ultraviolet-visible spectrophotometer, and the result is shown in fig. 4.
The uv-vis spectra of the sample prepared in this comparative example were obtained by fluorescence spectroscopy and are shown in fig. 1 and 2, and the CIE color coordinates (0.278, 0.3417) are plotted and are shown in fig. 5.
As shown in FIG. 1, the blue light emission is stronger in examples 1, 2, 3 and comparative examples 2, 3 under 365nm excitation light source, showing that Eu is2+The red emission of comparative example 1 is stronger. Thus, depending on the three primary colors of light, examples 1, 2 and 3 and comparative examples 2 and 3 are more blue-green under 365nm excitation, and Eu is partially contained in examples 1, 2 and 33+Reduced Eu in comparative example 23+Is completely reduced.
As shown in FIG. 2, examples 1, 2 and 3 and comparative examples 2 and 3 all showed blue light emission and Eu under 395nm excitation light source2+The red light emission of the embodiments 1, 2 and 3 is enhanced, the red light loss under 365nm excitation is compensated, and the embodiments are closer to white light under 395nm excitation according to the three primary colors of light.
As shown in FIG. 3, the non-heat treated sample (example 1) showed a distinct amorphous diffraction peak, and the heat treated sample (example 2) precipitated NaYF4 crystal to promote the blue light emission of example 2, i.e. to favor Eu2+Energy level transition of (2).
As shown in FIG. 4, the absorption cut-off edges of examples 1, 2 and 3 and comparative examples 2 and 3 showed a significant red shift, and the absorption peak before 395nm disappeared. The absorption at 395nm and 460nm in examples 1, 2 and 3 is derived from Eu3+Showing Eu in examples 1, 2 and 33+Only partially reduced, two absorptions in comparative example 2The peak is completely disappeared, indicating that Eu3+Is completely reduced to Eu2+。
As shown in fig. 5, examples 1, 2, and 3 and comparative examples 1, 2, and 3 have CIE color coordinates (0.3165, 0.3203), and example 2 is closest to white light.
Claims (8)
1. Topology chemical reduction Eu3+/Eu2+The co-doped UV-LED white light microcrystalline glass is characterized by being prepared from the following components in percentage by mole:
the reducing agent is nitride or carbide.
2. Topologically chemically reduced Eu according to claim 13+/Eu2+The co-doped UV-LED white light microcrystalline glass is characterized in that: the reducing agent is BN, AlN or Si3N4Or SiC.
3. Topologically chemically reduced Eu according to claim 23+/Eu2+The co-doped UV-LED white light microcrystalline glass is characterized in that: the reducing agent is Si3N4。
4. Topologically chemically reduced Eu according to any one of claims 1 to 33+/Eu2+The preparation method of the co-doped UV-LED white light microcrystalline glass is characterized by comprising the following steps: mixing and grinding the raw material components according to a set proportion, and melting and annealing to prepare the white light glass ceramics;
wherein the melting process is carried out in the air, and the temperature of the melting process is 1300-1450 ℃.
5. The method of claim 4, wherein: the melting time is 40-50 min.
6. The method of claim 4, wherein: the annealing process is carried out in the air, the temperature of the annealing process is 300-350 ℃, and the time is 2-5 h.
7. The method of claim 4, wherein: and further carrying out heat treatment after the annealing.
8. The method of claim 7, wherein: the heat treatment process is carried out in air, and the temperature of the heat treatment process is 540-560 ℃, and the time is 2-5 h.
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