阅读说明：本技术 一种氮化物红光玻璃及其应用 (Nitride red-light glass and application thereof ) 是由 向卫东 张玉洁 于 2020-03-31 设计创作，主要内容包括：本发明公开了一种氮化物红光玻璃及其应用。所述氮化物红光玻璃由玻璃基体和CaAlSiN<Sub>3</Sub>:Eu<Sup>2+</Sup>荧光粉组成；所述氮化物红光玻璃通过如下步骤制备：(1)将SiO<Sub>2</Sub>、B<Sub>2</Sub>O<Sub>3</Sub>、CaO、Na<Sub>2</Sub>O粉体原料按照组分配比称量,放入坩埚中混合均匀后加热熔融,淬冷获得前驱玻璃；(2)将前驱玻璃研磨成粉,加入一定量的CaAlSiN<Sub>3</Sub>:Eu<Sup>3+</Sup>荧光粉,研磨、置于涂抹了纳米Al<Sub>2</Sub>O<Sub>3</Sub>层的坩埚中,放入高温熔融炉加热至750℃-850℃并保温15-25min使之熔融成型,使之随炉冷却获得氮化物红光玻璃。本发明提供了所述氮化物红光玻璃在制备白光LED器件中的应用,能提高白光LED器件的显色指数和光效。本发明的还提供了所述氮化物红光玻璃在制备LD器件中的应用,能提高激光饱和阈值和流明通量。(The invention discloses nitride red light glass and application thereof. The nitride red light glass consists of a glass substrate and CaAlSiN 3 :Eu 2+ Fluorescent powder composition; the nitride red glass is prepared by the following steps: (1) mixing SiO 2 、B 2 O 3 、CaO、Na 2 Weighing O powder raw materials according to the component proportion, putting the raw materials into a crucible, uniformly mixing, heating, melting and quenching to obtain precursor glass; (2) grinding the precursor glass into powder, adding a certain amount of CaAlSiN 3 :Eu 3+ Grinding and placing the fluorescent powder coated with nano Al 2 O 3 Crucible of layerPutting the crucible into a high-temperature melting furnace, heating to 750-850 ℃, preserving heat for 15-25min, melting and forming, and cooling along with the furnace to obtain the nitride red-light glass. The invention provides application of the nitride red light glass in preparation of a white light LED device, which can improve the color rendering index and the luminous efficiency of the white light LED device. The invention also provides application of the nitride red light glass in preparing an LD device, and the laser saturation threshold and the lumen flux can be improved.)

1. The nitride red-light glass consists of glass substrate and CaAlSiN₃:Eu²⁺Fluorescent powder composition; the method is characterized in that: the composition of the glass substrate is as follows: 40-50 wt% SiO₂，20-30wt％B₂O₃，1-15wt％CaO，1-20wt％Na₂O, the sum of the mass fractions of all the components is 100 percent; the microstructure of the nitride red-light glass is characterized by CaAlSiN₃:Eu²⁺Fluorescent powder is embedded in the glass substrate, and CaAlSiN is contained in the nitride red light glass₃:Eu²⁺The mass percentage content of the fluorescent powder is 5-50 Wt%;

the nitride red glass is prepared by the following steps:

(1) mixing raw materials: mixing SiO₂、B₂O₃、CaO、Na₂Weighing O powder raw materials according to the component proportion, putting the raw materials into a crucible, uniformly mixing, heating to 1300 ℃ and 1500 ℃, preserving heat for 5-20min, and carrying out melt quenching to obtain precursor glass;

(2) preparation: grinding the precursor glass obtained in the step (1) into powder, and adding a certain amount of CaAlSiN₃:Eu³⁺Grinding and placing the fluorescent powder coated with nano Al₂O₃And putting the crucible in the layer into a high-temperature melting furnace, heating to 750-850 ℃, preserving heat for 15-25min, melting and forming, and cooling along with the furnace to obtain the nitride red-light glass.

2. The nitride red glass of claim 1, wherein: the glass substrate comprises the following components: 45-50 wt% SiO₂，23-27wt％B₂O₃，7-12wt％CaO，14-18wt％Na₂O。

3. The nitride red glass of claim 1, wherein: the glass matrix consists of 16 parts of B₂O₃30 parts of SiO₂10 parts of Na₂O and 6 parts of CaO.

4. The nitride red glass of any one of claims 1 to 3, wherein: CaAlSiN in nitride red light glass₃:Eu²⁺The mass percentage content of the fluorescent powderIs 10 wt%.

5. The nitride red glass of any one of claims 1 to 3, wherein: in the step (1), the melting temperature is 1350 ℃ and the heat preservation time is 10 min.

6. The nitride red glass of any one of claims 1 to 3, wherein: in the step (2), the melting temperature is 750-850 ℃, and the melting time is 15-35 minutes.

7. The nitride red glass of any one of claims 1 to 3, wherein: in the step (2), the melting temperature is 800 ℃ and the melting time is 25 min.

8. The nitride red glass of claim 1, used for preparing a white LED device excited by a blue LED chip.

9. Use of the nitride red glass of claim 1 in the preparation of a blue LD chip-excited LD device.

Technical Field

The invention relates to nitride red light glass and application thereof in preparation of LED and LD devices, belonging to the field of solid luminescent materials.

Background

White light LEDs are widely used as a new generation of green illumination light source due to their advantages of energy saving, environmental protection, long lifetime, etc. Such as: white LEDs have become an important component in human daily life in the fields of indoor lighting, outdoor lighting, display backlights, spot lights, automotive headlamps, landscape lamps, and the like. At present, commercial white light LEDs are mainly realized by combining and packaging a blue light LED chip and yellow fluorescent powder together, and the method has the advantages of simple preparation process, simple driving circuit, low cost, high packaging light efficiency, high reliability and the like. And the formed white light spectrum only has two colors of blue light and yellow light and lacks a red light part, so that the white light LED obtained by the method has a low color rendering index and is not suitable for indoor illumination. Meanwhile, the fluorescent powder is required to be dispersed in the silica gel or the epoxy resin, the encapsulated epoxy resin/silica gel has poor thermal conductivity and chemical stability and low glass transition temperature, but some problems can occur when the high-power white light LED is used, the high-power white light LED emits light and generates a large amount of heat to dissociate the methyl functional groups of the silica gel, and the epoxy resin/silica gel is easy to age and yellow due to the defects generated by bond fracture, so that the color cast of the LED is caused, the luminous efficiency is reduced, and the service life of a white light LED device is seriously shortened. Therefore, it is necessary to develop a novel fluorescent conversion material with high luminous efficiency, high color rendering index, good thermal stability and stable physical and chemical properties to meet the development requirement of high-power LEDs.

In order to solve the above problems, researchers have conducted intensive research and have proposed various phosphor encapsulation technologies. One is to use transparent glass as the carrier of the phosphor, i.e. by screen printing, suspension coating, dip coating, electrophoretic deposition of the phosphor, etc. on top of the carrier. Secondly, preparing a fluorescent film by utilizing a screen printing technology; thirdly, low melting point glass is used as a substrate for encapsulating the fluorescent powder, which is called Pi G (Phosphor-in-glass) for short. Yang Peng et al (Journal of alloys and company 693(2017)279e284) reportedThe fan-shaped sheet and the concentric ring-shaped PIG prepared by the screen printing are applied to the white light LED, but the preparation process flow is more complicated. Kim et al (J.Am.Ceram.Soc.100(2017)5186) in Korea reported B₂O₃-R₂O-ZnO-SiO₂-P₂O₅Red light emitting CaAlSiN codoped in low melting point (R ═ K, Na) glass₃:Eu²⁺YAG fluorescent powder emitting yellow light is prepared by a method of firstly carrying out static pressure forming and then sintering, the process is complex, the prepared sample has poor transparency, the luminescence property needs to be further improved, and the fluorescent powder has more pores and poor heat dissipation. The third method is to encapsulate the fluorescent powder in the low-melting-point glass substrate, so that the substrate is stable, good in heat dissipation, high in strength and high in luminous efficiency, and has unique advantages when being applied to high-power LEDs. There are two methods for preparing PiG: glass crystallization and low-temperature co-sintering, wherein the low-temperature co-sintering is the mainstream preparation method at present due to simple process and low cost.

However, when the low-temperature co-sintering is adopted to prepare the PiG at present, the doped phosphor is generally oxide phosphor, and the reports of preparing the PiG by co-sintering (oxy) nitride phosphor and glass powder are very few, which is probably due to the fact that the nitride phosphor is CaAlSiN₃:Eu²⁺、Ca₂Si₅N₈:Eu²⁺And the like are easy to react with the glass matrix in the preparation process, so that the fluorescent powder is degraded. However, among red phosphors currently used, nitride red phosphors have the best thermal stability, quantum efficiency, and chemical stability. Therefore, in order to obtain a high-power warm white LED, it is necessary to prepare a red nitride phosphor and a low-melting glass composite material. The nitride red-light glass is a composite material of glass and fluorescent powder, integrates the advantages of the glass and the fluorescent powder material, and has the advantages of simple preparation method, high thermal stability and chemical and physical stability, good weather resistance and long service life. Compared with silica gel, the silica gel has better heat conductivity, and is expected to replace the conventional fluorescent powder and a blue LED chip to form a white LED device.

The patent CN103183473A Ce: YAG microcrystalline glass for white light LED and preparation method thereof disclose that the microcrystalline glass contains Ce: YAGA preparation method of microcrystalline low-melting-point glass ceramics. However, the material only contains the Ce: YAG microcrystal emitting yellow light and lacks red light components, so that the color rendering index of a white light LED device packaged with a blue light LED chip is not high. CN110117160A patent "A glass ceramics, its preparation method and application" discloses that Ce, YAG and CaAlSiN are inlaid in oxide glass matrix₃:Eu²⁺The microcrystalline glass of the two kinds of fluorescent powder is prepared by adopting a two-step melt quenching method, the performance of a prepared sample is improved compared with that of the traditional microcrystalline glass, but the performance of the prepared sample is improved because the microcrystalline glass is doped with CaAlSiN₃:Eu²⁺The concentration of (2) is low, and the color rendering index of the LED is not greatly improved. This is because CaAlSiN₃:Eu²⁺The concentration of the fluorescent powder is too high, and a large amount of bubbles can be generated during melting with a glass matrix and cannot be digested, so that the microcrystalline glass cannot be formed or loose and irregular shapes can be generated.

In short, some patents for the existing low-melting-point fluorescent microcrystalline glass for white LEDs exist, but the luminescent performance of the existing low-melting-point fluorescent microcrystalline glass for white LEDs still needs to be improved due to unreasonable material component design and the like.

Blue Laser Diodes (LDs) have many advantages over blue Light Emitting Diodes (LEDs) in high brightness lighting applications. Surprisingly, there is no inevitable "efficiency drop" in blue LD, even at up to 25kW cm^-2Can also maintain high efficiency at the input laser power density of (2), and the peak efficiency of the LED is only 3Wcm^-2. In view of this, ultra-high brightness white light can be produced by using LDs in place of LEDs in combination with fluorescent converters, which have become an emerging technology suitable for various high brightness applications, including projectors, displays, automotive headlights and general lighting. The thermal performance of the fluorescence converter is a major technical parameter of laser illumination, considering the effects of high-throughput laser irradiation and thermal attack. To solve the problem of low heat resistance and thermal conductivity (0.1-0.4 Wm)^-1K^-1) The organic binder of (2), high-density phosphor ceramic (5-15 Wm)^-1K^-1) And Phosphor In Glass (PiG) (0.8-2 Wm)^-1K^-1) Phosphor dispersed in glass matrix may be suitable for high power laser excitation. At present, when the PiG is prepared by low-temperature co-sintering, the doped fluorescent powder is generally oxide fluorescent powder, and the reports of preparing the PiG by co-sintering (oxy) nitride fluorescent powder and glass powder are less, probably because the nitride fluorescent powder CaAlSiN₃:Eu^{2 +}、Ca₂Si₅N₈:Eu²⁺And the like are easy to react with the glass matrix in the preparation process, so that the fluorescent powder is degraded. However, among red phosphors currently used, nitride red phosphors have the best thermal stability, quantum efficiency, and chemical stability. Therefore, in order to obtain a phosphor suitable for applying a high power LD, it is necessary to prepare a composite material of a red nitride phosphor and a low melting point glass. The nitride red light glass (R-PiG)) is a composite material of glass and fluorescent powder, integrates the advantages of the glass and the fluorescent powder material, and has the advantages of simple preparation method, high thermal stability and chemical and physical stability, good weather resistance and long service life. Compared with silica gel, the silica gel has better heat conductivity, and is expected to replace the conventional fluorescent powder and a blue LED chip to form an LD device.

In 2016, Li et al successfully synthesized translucent CaAlSiN by using the Rapid sintering technique (SPS)₃:Eu²⁺A ceramic. Its external quantum efficiency can be up to 60%, and its thermal stability is 15% higher than that of powder. When the incident power density is from 20Wcm^-2Increased to 150Wcm^-2Its constant high light efficiency is 42.2lmW^-1. In the same year, plum et al have a blue laser flux density of 0.75Wmm^-2Under the conditions of (1), translucent CaAlSiN was produced₃:Eu²⁺Ceramic with luminous efficiency of 10.6lmW^-1This indicates that CaAlSiN₃:Eu²⁺Ceramics are expected to become an emerging potential color converter in laser illumination and display technologies. Compared with fluorescent ceramics, the PiG attracts much attention, and the luminescence of the PiG can be easily controlled by combining various fluorescent powders and glass components. Furthermore, in order to maintain the high performance of the contained phosphor during the manufacturing process, PiG (r) was synthesized at low temperature<900 deg.C) is a better choice. On the other hand, at high temperatures (>The luminescence and microstructure of the phosphor ceramic are difficult to control at 1500 ℃. More recently, the development of new and more recently developed devicesZhu et al [ Journal of alloys and Compounds,702(2017)193-]By reaction between ZnO-B₂O₃-BaO-Al₂O₃CaAlSiN dispersed in glass system₃:Eu²⁺The fluorescent powder successfully prepares a series of low-concentration red light transparent glass, and the maximum external quantum efficiency is 43 percent. At 0.5Wmm^-2The maximum lumen flux can reach 39lm at the blue laser flux density. The article was mainly studied at low concentrations of red PiG, CaAlSiN₃:Eu²⁺The properties of the phosphor are challenging to realize if high concentrations of red PiG can be achieved. And the laser saturation threshold is lower, and a lifting space is provided.

To our knowledge, few reports have been made on the use of PiG materials as color converters in high power laser illumination, based on CaAlSiN₃:Eu²⁺Outstanding performance of phosphor, CaAlSiN₃:Eu²⁺The PiG material has the potential to become one of the red converters most suitable for high-power blue laser excitation. At present, few patents of the existing low-melting-point nitride fluorescent microcrystalline glass for the blue-light-excited LD are available.

The invention provides preparation and application of nitride red light glass based on a new component formula, and is expected to develop an excellent material which can be applied to a white light LED with a high color rendering index and an LD device with a high laser saturation threshold.

Disclosure of Invention

The invention aims to solve the technical problem of providing the nitride red light glass which has high luminous intensity, high brightness, low melting temperature, stable product color, good color reducibility, and excellent hydrothermal stability and chemical stability.

The second purpose of the invention is to provide the application of the nitride red glass in the preparation of a white light LED device so as to improve the color rendering index and the luminous efficiency of the white light LED device.

The third purpose of the invention is to provide the application of the nitride red glass in preparing an LD device, so as to improve the laser saturation threshold and the lumen flux.

The invention adopts the technical scheme for solving the problems that:

in a first aspect, the invention provides nitride red-light glass, which consists of a glass matrix and CaAlSiN₃:Eu²⁺Fluorescent powder composition; wherein the glass matrix comprises the following components: 40-50 wt% SiO₂，20-30wt％B₂O₃，1-15wt％CaO，1-20wt％Na₂O, the sum of the mass fractions of all the components is 100 percent; the microstructure of the nitride red-light glass is characterized by CaAlSiN₃:Eu²⁺Fluorescent powder is embedded in the glass substrate, and CaAlSiN is contained in the nitride red light glass₃:Eu²⁺The mass percentage content of the fluorescent powder is 5-50 Wt%;

the nitride red glass is prepared by the following steps:

(1) mixing raw materials: mixing SiO₂、B₂O₃、CaO、Na₂Weighing O powder raw materials according to the component proportion, putting the raw materials into a crucible, uniformly mixing, heating to 1300 ℃ and 1500 ℃, preserving heat for 5-20min, and carrying out melt quenching to obtain precursor glass;

(2) preparation: grinding the precursor glass obtained in the step (1) into powder, and adding a certain amount of CaAlSiN₃:Eu³⁺Grinding and placing the fluorescent powder coated with nano Al₂O₃And putting the crucible in the layer into a high-temperature melting furnace, heating to 750-850 ℃, preserving heat for 15-25min, melting and forming, and cooling along with the furnace to obtain the nitride red-light glass.

The preparation method of the nitride red-light glass selects SiO₂-B₂O₃-CaO-Na₂O glass substrate such that CaAlSiN₃:Eu²⁺After the phosphor is dispersed in the glass matrix to form the PiG, the performance of the PiG is hardly affected by the PiG. Preferably, the composition of the glass matrix is: 45-50 wt% SiO₂，23-27wt％B₂O₃，7-12wt％CaO，14-18wt％Na₂O; most preferably, the glass matrix consists of 16 parts of B₂O₃30 parts of SiO₂10 parts of Na₂O and 6 parts of CaO.

The preparation method of the nitride red-light glass enables the nitride red-light glass to be prepared along with CaAlSiN₃:Eu²⁺The increase of the content of the fluorescent powder increases the luminous intensity of the red glass. Most preferably, CaAlSiN in the nitride red glass₃:Eu²⁺The mass percentage content of the fluorescent powder is 10 wt%.

In the invention, nano Al is coated on₂O₃The crucible of the layer is obtained by easy demoulding of the prepared sample, and the nano Al₂O₃The layers act as spacers. Preferably, the crucible used is a corundum crucible.

Preferably, in step (1), the melting temperature is 1350 ℃ and the holding time is 10 min.

Preferably, in step (2), the melting temperature is 750-850 ℃, wherein the red glass fired at 800 ℃ is the most preferred.

Preferably, in the step (2), the melting time is 15 to 35 minutes, wherein 25min of the fired red glass is optimal.

The nitride red-light glass prepared by the invention can be plane, concave and convex in shape, can be cut, ground and polished, and does not influence the properties of the nitride red-light glass.

In a second aspect, the invention provides application of the nitride red light glass in preparing a white light LED device excited by a blue LED chip.

In a third aspect, the invention provides application of the nitride red light glass in preparing an LD device excited by a blue LD chip.

The invention has the advantages that:

(1) compared with the prior art, the invention uses B₂O₃-SiO₂-Na₂O-CaO is used as a matrix glass system, and CaAlSiN is added₃:Eu²⁺The fluorescent powder is prepared into the nitride red-light glass in the air without atmosphere protection through a high-temperature melting process. The nitride red-light glass prepared by the process has the advantages of high luminous intensity, high brightness, low melting temperature, stable product color, high color rendering index, good color reducibility, good hydrothermal stability and excellent chemical stability. In addition, the nitride red-light glass prepared by the preparation method has simple process and low cost, and is suitable for industrial production.

(2) The white light LED device prepared from the nitride red light glass has high color rendering index and high light efficiency.

(3) The white light LED device prepared from the nitride red light glass has high laser saturation threshold and lumen flux.

The invention is further described with reference to the drawings and the detailed description.

Drawings

FIG. 1: (a) different CaAlSiN formulations prepared for example 1₃:Eu²⁺A picture of a doped amount of R-PiG sample under normal light and ultraviolet light, (b) is a fluorescence (PL) pattern of R-PiG, and (c) is an X-ray diffraction (XRD) pattern of R-PiG;

FIG. 2 is CaAlSiN prepared in example 1₃:Eu²⁺An External Quantum Efficiency (EQE) plot for R-PiG;

FIG. 3 is a 10 wt% CaAlSiN alloy prepared in example 1₃:Eu²⁺HRTEM image of R-PiG;

FIG. 4: (a) and (b) 10 wt% CaAlSiN prepared in example 1, respectively₃:Eu²⁺R-PiG and CaAlSiN₃:Eu²⁺A water stability diagram of the phosphor;

FIG. 5 is a thermal stability diagram wherein: (a) and (c) CaAlSiN₃:Eu²⁺Thermal stability of the phosphor, (b) and (d) show that 10 wt% CaAlSiN prepared in example 1₃:Eu²⁺Thermal stability of R-PiG;

FIG. 6: (a) b prepared for example 1₂O₃-SiO₂-Na₂SEM image of O-CaO precursor glass, and (b) CaAlSiN₃:Eu²⁺SEM image of phosphor, (c) 10 wt% CaAlSiN prepared in example 1₃:Eu²⁺SEM picture of R-PiG;

FIG. 7 is 10 wt% CaAlSiN prepared in example 1₃:Eu²⁺An LED diagram of matching of R-PiG and LuAG fluorescent powder;

FIG. 8: (a) 10 wt% CaAlSiN prepared for example 1₃:Eu²⁺Transmission graphs of different thicknesses of R-PiG; (b) different CaAlSiN at 0.2mm thickness₃:Eu²⁺Penetration of doping amount of R-PiGA drawing;

FIG. 9 is a diagram of a reflection type blue laser driven measuring device of the present invention, the lower right photograph being a red laser image;

FIG. 10: (a) and (b) 10 wt% CaAlSiN as a function of incident laser power density₃:Eu²⁺The electroluminescence spectra of the R-PiG samples, (c) and (d) are plots of the luminous flux versus incident power for different R-PiG samples, and (e) and (f) are plots of the luminous flux versus incident laser power density for different R-PiG samples.

Detailed Description

The invention is described in detail below with reference to examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and many insubstantial modifications and variations of the invention can be made by an engineer skilled in the art based on the teachings of the invention.