CN102060442A

CN102060442A - Preparation method of fluorescent microcrystalline glass for white light-emitting diode (LED)

Info

Publication number: CN102060442A
Application number: CN 201010551495
Authority: CN
Inventors: 邹军
Original assignee: ZHEJIANG EMITTING OPTOELECTRONIC TECHNOLOGY Co Ltd
Current assignee: ZHEJIANG EMITTING OPTOELECTRONIC TECHNOLOGY Co Ltd
Priority date: 2010-11-11
Filing date: 2010-11-11
Publication date: 2011-05-18

Abstract

The invention relates to a preparation method of fluorescent microcrystalline glass for a white light-emitting diode (LED). The fluorescent microcrystalline glass for the white LED is characterized by comprising the following components by mole percent: 20-50% of SiO2, 10-40% of CaO, 3-24% of Y2O3, 5-40% of Al2O3 and 0.1-9% of RE2O3, wherein RE2O3 consists of at least one of Ce2O3, Pr2O3, Sm2O3 and Tb2O3. The preparation method comprises the following steps: firstly, performing high temperature melting to prepare CaO-Y2O3-Al2O3-RE2O3-SiO2 glass; and secondly, performing heat treatment to obtain microcrystalline glass of which crystal size ranges from several nanometers to hundreds of nanometers. The microcrystalline glass is transparent, has no precipitated crystal, has good physical and chemical properties, and can absorb the emission wave of the LED and emit yellow light. The microcrystalline glass material provided by the invention has the following advantages: the material is simple in preparation process, low in production cost, high in heat conductivity, uniform in microcrystalline distribution, high in excitation efficiency, easy in rare earth doping process and high in color rendering property, and is very suitable for preparing the white LED for general lighting.

Description

White light LEDs fluorescent glass-ceramics preparation method

Technical field

The present invention relates to fluorescent glass-ceramics in a kind of white light LEDs encapsulation, relate in particular to the preparation method and the composition of fluorescent glass-ceramics.

Background technology

The white light LEDs fluorescent material forms white light mainly based on fluorescent material with blue chip and gold-tinted phosphor combination at present, but there are following five big shortcomings in it:

1, fluorescent material launching efficiency and light conversion efficiency are low;

2, fluorescent powder grain and dispersed uniform are difficult to obtain sound solution;

3, fluorescent material disappearance emitting red light composition is difficult to the white light LEDs that colour temperature, high color rendering index (CRI) are hanged down in preparation;

4, the fluorescent material physical and chemical performance is poor, incompatibility great power LED growth requirement;

5, the fluorescent material patented technology is abroad monopolized.

Patent 200510102388.7 has been announced a YAG chip-type white-light light-emitting-diode, adopt the YAG wafer to replace fluorescent powder, a kind of low-melting-point fluorescent glass for white light LED and preparation method thereof is also disclosed among the CN101643315A, though avoid the poor radiation of fluorescent material, realize the problems such as weather resistance of white light LEDs fluorescent material, but have processing procedure complexity, cost height, preparation cycle is long, problems such as the bad control of stability of material.

Summary of the invention

Technical problem to be solved by this invention provides the white light LEDs fluorescent glass-ceramics that a kind of growth cycle is short, cost is low, be easy to produce in batches.This devitrified glass has the high launching efficiency that obviously is better than fluorescent material, excellent photochromic homogeneity, and growth technique is simple, characteristics such as less investment.

The present invention solves the problems of the technologies described above the technical scheme that is adopted: white light LEDs fluorescent glass-ceramics preparation method, its mole percentage composition is: SiO ₂: 20～50, CaO:10～40, Y ₂O ₃: 3～24, Al ₂O ₃: 5～40, RE ₂O ₃: 0.1～9; RE ₂O ₃Be Ce ₂O ₃, Pr ₂O ₃, Sm ₂O ₃, Tb ₂O ₃The raw material of component is at least a to form.

White light LEDs of the present invention with the concrete preparation process of fluorescence transparent glass-ceramics is:

CaO-Y ₂O ₃-Al ₂O ₃-RE ₂O ₃-SiO ₂Be founding of glass: by following molar percentage prescription: SiO ₂: 20～50, CaO:10～40, Y ₂O ₃: 3～24, Al ₂O ₃: 5～40, RE ₂O ₃: 0.1～9 weighing analytical pure raw material, pour in quartz crucible or the platinum crucible after raw material mixed and melt, temperature of fusion is 1700～1900 ℃, be incubated and after 1～2 hour glass melt poured in the cast iron mould, place the reducing atmosphere retort furnace to anneal then, heat-treated is 1～8 hour near its first crystallization peak, and then be cooled to 30 ℃ with 5 ℃/hour speed, close the annealing furnace power supply, automatically be cooled to room temperature, obtaining transparent crystallite dimension is several devitrified glasses to the hundreds of nanometer scale.

Compared with prior art, characteristics of the present invention are rare earth ion doped in the glass matrix of suitable prescription, handle by heating micritization glass material, make rare earth ion dopedly in the case of crystallization phases, obtain to have the bulk fluorescent glass-ceramics of the homogeneous transparent of fine luminescent effect; This class fluorescent glass-ceramics integrates the advantage of crystal and glass, have the with short production cycle of the excitation of spectra characteristic of crystal substrate excellence and glass matrix, cost is low, be easy to produce in batches, on preparation technology, can realize large size, characteristics such as highly doped, by prescription of the present invention and preparation method, that separates out is rare earth ion doped to the YAG crystalline phase, the rare earth ion doped YAG devitrified glass of preparation is transparent and physical and chemical performance is good, have and the similar spectral response curve of rare earth ion doped YAG crystalline phase, good physics and exciting characteristic, and material preparation method is simple, and production cost is low.

Embodiment

Embodiment one: table 1 is the glass formula and the first recrystallization temperature value of embodiment one.

Table 1

Concrete preparation process is as follows: press the prescription weighing certainweight analytical pure raw material in the table 1, pour in the quartz crucible after raw material mixed and melt, 1700 ℃ of temperature of fusion, be incubated 2 hours, glass melt is poured in the pig mold, placed the retort furnace of reducing atmosphere to carry out 1000 ℃ of annealing then, be cooled to 30 ℃ with 10 ℃/hour speed, close reducing gas and be cooled to room temperature, obtaining transparent crystallite dimension is several fluorescent glass-ceramics to the hundreds of nanometer scale.Embodiment two: table 2 is the glass formula and the first recrystallization temperature value of embodiment two.

Table 2

Concrete preparation process is as follows: press the prescription weighing certainweight analytical pure raw material in the table 2, pour in the quartz crucible after raw material mixed and melt, 1800 ℃ of temperature of fusion, be incubated 2 hours, glass melt is poured in the pig mold, placed the retort furnace of hydrogen atmosphere to carry out 1050 ℃ of annealing then, be cooled to 30 ℃ with 10 ℃/hour speed, close reducing gas and be cooled to room temperature, obtaining transparent crystallite dimension is several fluorescent glass-ceramics to the hundreds of nanometer scale.

Embodiment three: table 3 is the glass formula and the first recrystallization temperature value of embodiment three.

Table 3

Concrete preparation process is as follows: the first step, press the prescription weighing 50 gram analytical pure raw materials in the table 1, pour in the quartz crucible after raw material mixed and melt, 1900 ℃ of temperature of fusion are incubated 2 hours, and glass melt is poured in the pig mold, place the retort furnace of carbon monoxide atmosphere to carry out 1100 ℃ of annealing then, be cooled to 30 ℃ with 10 ℃/hour speed, close reducing gas and be cooled to room temperature, obtaining transparent crystallite dimension is several fluorescent glass-ceramics to the hundreds of nanometer scale.

Claims

1. white light LEDs fluorescent glass-ceramics preparation method is characterized in that it is by comprising SiO ₂, CaO, Y ₂O ₃, Al ₂O ₃, RE ₂O ₃The raw material of component is made, and their mole consists of: SiO ₂: 20～50, CaO:10～40, Y ₂O ₃: 3～24, Al ₂O ₃: 5～40, RE ₂O ₃: 0.1～9.

2. white light LEDs fluorescent glass-ceramics preparation method according to claim 1 is characterized in that: RE ₂O ₃Be Ce ₂O ₃, Pr ₂O ₃, Sm ₂O ₃, Tb ₂O ₃The raw material of component is at least a to form.

3. white light LEDs fluorescent glass-ceramics preparation method according to claim 1 is characterized in that:

CaO-Y ₂O ₃-Al ₂O ₃-RE ₂O ₃-SiO ₂Be founding of glass: by the molar percentage prescription of each raw material: SiO ₂: 20～50, CaO:10～40, Y ₂O ₃: 3～24, Al ₂O ₃: 5～40, RE ₂O ₃: 0.1～9, weighing SiO ₂, CaO, Y ₂O ₃, Al ₂O ₃, RE ₂O ₃The analytical pure raw material, pour in quartz crucible or the platinum crucible after raw material mixed and melt, temperature of fusion is 1700～1900 ℃, be incubated and after 1～2 hour glass melt poured on the cast iron mould, place the reducing atmosphere retort furnace to anneal then, near its first crystallization peak heat-treated 1-8 hour, and then be cooled to 30 ℃ with 5 ℃/hour speed, close the annealing furnace power supply, automatically be cooled to room temperature, obtaining transparent crystallite dimension is several fluorescent glass-ceramics to the hundreds of nanometer scale.