CN104150763B - A kind of emitting red light glass material and preparation method thereof - Google Patents

A kind of emitting red light glass material and preparation method thereof Download PDF

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Publication number
CN104150763B
CN104150763B CN201410394060.6A CN201410394060A CN104150763B CN 104150763 B CN104150763 B CN 104150763B CN 201410394060 A CN201410394060 A CN 201410394060A CN 104150763 B CN104150763 B CN 104150763B
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glass
emitting red
red light
molfraction
glass material
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CN104150763A (en
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余雪
黎千跃
徐旭辉
王婷
邱建备
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The present invention discloses a kind of emitting red light glass material and preparation method thereof <b>, </b> and belongs to rare earth luminescent material technical field.Described emitting red light glass material is with Na 2o, CaO, GeO 2, SiO 2and rare earth compound is that raw material prepares.Its preparation method obtains melten glass liquid after founding after each component mixing; Be poured in mould after the clarification of melten glass liquid and obtained glass, fast this glass is put into the retort furnace being warming up to this glass transformation temperature and be incubated, be cooled to room temperature.This material can by near ultraviolet, blue-light excited, and launch bright crimson fluorescent, be expected to be applied to UV chip LED in the market,, blue colour fluorescent powder green with other forms white light LEDs, also can be used for the white light LEDs encapsulated by blue chip LED and YAG:Ce in the market, to improve the lower present situation of its colour rendering index, realize the widespread use of white light LEDs.

Description

A kind of emitting red light glass material and preparation method thereof
Technical field
The present invention relates to a kind of emitting red light glass material and preparation method thereof ,belong to rare earth luminescent material technical field.
Background technology
White light-emitting diodes (W-LED, white-light-emittingdiode) as a kind of junction semiconductor electroluminescent device, have that operating voltage is low, current consumption is few, quality is light, volume is little, the life-span is long, radiationless, pollution-free, luminescence response fast, shock resistance and the series of advantages such as security is good and receive much concern, be referred to as forth generation solid cold light source.Current white light LEDs realizes white light mainly through two kinds of approach: one is fluorescent conversion type, namely with single led chip and phosphor combination luminescence; Another kind method adopts red, green, blue three-color LED chip portfolio luminous.
White light LEDs receives showing great attention to of people as the green illumination light source of energy-conserving and environment-protective of new generation, utilize UV-light, purple light or blue-ray LED excitated fluorescent powder and produce the main flow that white light is the development of current white light LEDs, the development of progress to white light LEDs of phosphor technologies has very important effect, and its performance directly affects the brightness of white light LEDs, chromaticity coordinates, colour temperature and color developing etc.Current ultraviolet leds technology is still immature, and existing red fluorescence powder is poor at the excitating performance of purple light or blue-ray LED luminescence band, and luminous efficiency is lower, becomes the bottleneck of LED fluorescent material and even white light LEDs development.The LED red fluorescence material researched and developed mainly contains Ca 3(VO 4) 2: Eu 3+, YVO 4: Eu 3+, Y 2o 3: Eu 3+, Bi 3+, Y 2o 2s:Eu 3+, CaO:Eu 3+, CaMoO 4: Eu 3+, (Gd, Y, Eu) 2(MoO 4) 3: Sm 3+deng.But current for liquid crystal display (LCD) white light LEDs, its performance can not meet the requirement of general lighting.Because the optical throughput of a LED chip is too little, to such an extent as to need hundreds of white light LEDs could meet the requirement of general lighting to optical throughput.Addressing this problem topmost method is exactly the output rating increasing LED.This method makes the increase of single led chip optical throughput become possibility, but the temperature of blue LED die also can be made to raise with inch, and this will make the luminous efficiency of the red fluorescence powder be coated on blue LED die and work-ing life decline.Therefore, possess the research and development of higher stability red fluorescence powder, significant to the application of high-power LED fluorescent powder.
Summary of the invention
The object of the invention is for the problems referred to above, propose a kind of stable chemical nature, good luminous performance, thermostability high, can effectively be excited by UV-light, purple light or blue-light LED chip and produce the glass material of red emission, described emitting red light glass material is prepared by following several raw material, and each raw material and molfraction thereof are: Na 2the molfraction of O is 4, the molfraction of CaO is 7-x, GeO 2molfraction be 57, SiO 2molfraction be 22, rare earth compound Bi 2o 3and Eu 2o 3, wherein, Bi 2o 3molfraction is x, Eu 2o 3molfraction is 0.2, and described x is 0 ~ 0.0036.
Another object of the present invention is to the preparation method providing described red glass fluorescent material, concrete steps comprise as follows:
(1) obtain melten glass liquid by founding after each component mixing, glass melting temperature is 1500 DEG C, and melting time is 20 ~ 60 minutes;
(2) after the clarification of melten glass liquid, be poured in mould and obtained glass, put into the retort furnace being warming up to this glass transformation temperature and be incubated 1 hour, after being then cooled to 100 DEG C with the speed of 5 ~ 10 DEG C/h, close retort furnace power supply Temperature fall to room temperature.
Ultraviolet leds chip of the present invention, refers to that emission wavelength is the photodiode of 200nm ~ 380nm; Purple LED chip of the present invention, refers to that emission wavelength is the photodiode of 380nm ~ 420nm; Blue-light LED chip of the present invention, refers to that emission wavelength is the photodiode of 420nm ~ 490nm.
Beneficial effect of the present invention is:
(1) red fluorescence powder that the present invention relates to effectively excite wide ranges, be suitable for ultraviolet, purple light or blue-light excited, can white light LEDs be widely used in;
(2) emitting red light glass of the present invention, physicochemical property are stablized, and luminous efficiency is higher;
(3) synthetic method of the glass that the present invention relates to is simple, does not need special conversion unit, and suitability for industrialized production is convenient.
Accompanying drawing explanation
Fig. 1 is the Na of the embodiment of the present invention 1 gained 2o-CaO-GeO 2-SiO 2: 0.2mol%Eu 3+the spectrogram exciting and monitor 612nm gained of fluorescent glass 393nm;
Fig. 2 is the thermal quenching correlation curve of embodiment 5 and business powder YAG:Ce;
Fig. 3 is that embodiment 2 ~ 6 excites the spectrogram of lower gained at 300nm.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but protection scope of the present invention is not limited to described content.
Embodiment 1
The glass material of the present embodiment is 4Na 2o-6.8CaO-57GeO 2-22SiO 2-0.2Eu 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2and Eu (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix, put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, melting time is obtain glass melting liquid in 50 minutes, after fused solution clarification, be cast in the stainless steel mould of preheating and obtained NCGS:0.2Eu 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, be then cooled to 100 DEG C with the speed of 8 DEG C/h, powered-down, be automatically cooled to room temperature, can 4Na be obtained 2o-6.8CaO-57GeO 2-22SiO 2-0.2Eu 2o 3luminous glass material.
The Na that the present embodiment prepares 2o-CaO-GeO 2-SiO 2: 0.2mol%Eu 3+as shown in Figure 1, this fluorescent glass can effectively excite and produce red emission the spectrogram exciting and monitor 612nm gained of fluorescent glass 393nm as seen from the figure.
Embodiment 2
The glass material of the present embodiment is 4Na 2o-6.7988CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0012Bi 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2(99.99%), Eu 2o 3and Bi (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix; Put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, and melting time is obtain glass melting liquid in 20 minutes, after fused solution clarification, is cast in the stainless steel mould of preheating and obtains NCGS:0.2Eu 2o 3, 0.0012Bi 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, then 100 DEG C are cooled to the speed of 7 DEG C/h, powered-down, is cooled to room temperature automatically, can obtain luminous glass material of the present invention.
Embodiment 3
The glass material of the present embodiment is 4Na 2o-6.7982CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0018Bi 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2(99.99%), Eu 2o 3and Bi (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix; Put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, and melting time is obtain glass melting liquid in 40 minutes, after fused solution clarification, is cast in the stainless steel mould of preheating and obtains NCGS:0.2Eu 2o 3, 0.0018Bi 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, then 100 DEG C are cooled to the speed of 6 DEG C/h, powered-down, is cooled to room temperature automatically, can obtain luminous glass material of the present invention.
Embodiment 4
As shown in Figure 1, the glass material of the present embodiment is 4Na 2o-6.7976CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0024Bi 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2(99.99%), Eu 2o 3and Bi (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix; Put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, and melting time is obtain glass melting liquid in 60 minutes, after fused solution clarification, is cast in the stainless steel mould of preheating and obtains NCGS:0.2Eu 2o 3, 0.0024Bi 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, then 100 DEG C are cooled to the speed of 5 DEG C/h, powered-down, is cooled to room temperature automatically, can obtain luminous glass material of the present invention.
Embodiment 5
The glass material of the present embodiment is 4Na 2o-6.7964CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0036Bi 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2(99.99%), Eu 2o 3and Bi (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix; Put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, and melting time is obtain glass melting liquid in 30 minutes, after fused solution clarification, is cast in the stainless steel mould of preheating and obtains NCGS:0.2Eu 2o 3, 0.0036Bi 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, then 100 DEG C are cooled to the speed of 10 DEG C/h, powered-down, is cooled to room temperature automatically, can obtain luminous glass material of the present invention.
The 4Na that the present embodiment prepares 2o-6.7964CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0036Bi 2o 3as shown in Figure 2, as seen from Figure 2 when temperature is lower than 150 DEG C, the thermal quenching performance of fluorescent glass is better than business powder to the thermal quenching correlation curve of luminous glass material and business powder YAG:Ce.
Embodiment 6
The glass material of the present embodiment is 4Na 2o-6.797CaO-57GeO 2-22SiO 2-0.2Eu 2o 3-0.0030Bi 2o 3, concrete preparation method is:
(1) by mole%, precise Na 2cO 3(99.99%), CaCO 3(99.99%), GeO 2(99.99%), SiO 2(99.99%), Eu 2o 3and Bi (99.99%) 2o 3(99.99%) be mixed in agate mortar, grinding 0.5h makes it mix; Put into alumina crucible after mixing and be placed in silicon carbon rod electric furnace and found, temperature of fusion is 1500 DEG C, and melting time is obtain glass melting liquid in 50 minutes, after fused solution clarification, is cast in preheating not
NCGS:0.2Eu is obtained in rust steel die 2o 3, 0.0030Bi 2o 3glass;
(2) fast above-mentioned glass is put into be warming up to material transition temperature L(550 DEG C) retort furnace be incubated l hour, then 100 DEG C are cooled to the speed of 10 DEG C/h, powered-down, is cooled to room temperature automatically, can obtain luminous glass material of the present invention.
The luminous glass material that embodiment 2 ~ 6 obtains excites the spectrogram of lower gained as shown in Figure 3 at 300nm, as seen from Figure 3 Bi 2o 3add can to Eu 2o 3luminescence carry out sensitization.

Claims (4)

1. an emitting red light glass material, is characterized in that: described emitting red light glass material is prepared by following several raw material, and each raw material and molfraction thereof are: Na 2the molfraction of O is 4, the molfraction of CaO is 7-x, GeO 2molfraction be 57, SiO 2molfraction be 22, compd B i 2o 3and Eu 2o 3, wherein, Bi 2o 3molfraction is x, Eu 2o 3molfraction is 0.2.
2. emitting red light glass material according to claim 1, is characterized in that: described x is 0 ~ 0.0036.
3. the preparation method of emitting red light glass material according to claim 1, is characterized in that, specifically comprise the following steps:
(1) melten glass liquid is obtained by founding after each component mixing;
(2) after the clarification of melten glass liquid, be poured in mould and obtained glass, put into the retort furnace being warming up to this glass transformation temperature and be incubated 1 hour, after being then cooled to 100 DEG C with the speed of 5 ~ 10 DEG C/h, closed retort furnace power supply Temperature fall to room temperature.
4. the preparation method of emitting red light glass material according to claim 3, is characterized in that, described in step (1), the glass melting temperature of melting process is 1500 DEG C, and melting time is 20 ~ 60 minutes.
CN201410394060.6A 2014-08-12 2014-08-12 A kind of emitting red light glass material and preparation method thereof Expired - Fee Related CN104150763B (en)

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CN106479500B (en) * 2016-09-29 2018-08-28 华南农业大学 A kind of luminescent glass ceramic and its preparation method and the application in LED illumination device
CN108623167A (en) * 2017-12-19 2018-10-09 嘉兴迪迈科技有限公司 A kind of laser glass material and preparation method thereof

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JP2005145759A (en) * 2003-11-17 2005-06-09 Asahi Glass Co Ltd Method for manufacturing optical amplification glass and optical waveguide
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