CN104003726B - A kind of YAG crystalline ceramics for white LED lamp and preparation method thereof - Google Patents

A kind of YAG crystalline ceramics for white LED lamp and preparation method thereof Download PDF

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CN104003726B
CN104003726B CN201410202347.4A CN201410202347A CN104003726B CN 104003726 B CN104003726 B CN 104003726B CN 201410202347 A CN201410202347 A CN 201410202347A CN 104003726 B CN104003726 B CN 104003726B
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crystalline ceramics
raw material
led lamp
calcining
white led
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CN104003726A (en
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俞立军
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JIANGSU CHENGYING LIGHTING ELECTRICAL APPLIANCE CO Ltd
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JIANGSU CHENGYING LIGHTING ELECTRICAL APPLIANCE CO Ltd
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Abstract

For a YAG crystalline ceramics for white LED lamp, fire raw material and be made up of the raw material of following weight part, Al 2o 3220-300 part, Y 2o 3300-380 part, SiO 260-75 part, CeO 215-20 part, Pr 2o 35-10 part, Eu 2o 32-5 part, Lu 2o 32-4 part, LiF 1-2 part, B 2o 33-5 part, SiC 3-5 part, CaO 0.5-1 part, the purity of described raw material is all at more than 99.99wt%, and described crystalline ceramics reaches 65%-75% at the light penetration of visible region, and colour temperature is 4000-5000k.Compared with prior art, this crystalline ceramics is in shrinking percentage, and transparence, there is improvement colour rendering index and colour temperature aspect.Have thermal conductivity high, chemical stability is good, and the life-span is long, the feature that luminous efficiency is high.

Description

A kind of YAG crystalline ceramics for white LED lamp and preparation method thereof
Technical field
The present invention relates to a kind of crystalline ceramics, especially a kind of white light LEDs YAG (yttrium aluminum garnet) transparent ceramic material and preparation method thereof, belongs to technical field prepared by special light function ceramics.
Background technology
White light LEDs, since appearance, just because the advantages such as its long service life, energy-efficient, environmental protection are described as the forth generation lighting source after incandescent light, luminescent lamp, geseous discharge, has been widely used in the fields such as LCD, mobile phone, digital camera.In recent years, along with the develop rapidly of the semiconductor lighting industry based on white light LEDs, white light LEDs shows huge market potential and application prospect in solid-state illumination, cause the great attention of national governments, company and scientific research institutions, set up the development of special mechanism urges semiconductor illumination technique one after another.
Current white light LEDs utilizes blue LED excited yellow fluorescent material coat to send gold-tinted, and then send white light after blue light and gold-tinted compound.This white light LEDs has the features such as life-span length, environmental protection, contains huge market potential and application prospect.
The main component of this yellow fluorescent powder is the yttrium aluminum garnet (YAG:Ce) of cerium dopping.Traditional powder encapsulation white light LEDs adopts epoxy resin or silica gel to fix blue chip, the shortcoming preparing white light LEO has: on the one hand because the thickness of the fluorescent material and silica gel mixolimnion that are coated in chip surface is difficult to control, white light correlated(color)temperature (CCT) angular distribution is uneven, causes ejecting white light to have the phenomenon of Lan Quan, yellow circle; The on the other hand life-span of white light LEDs short, poor stability.Meanwhile, the heat distributed due to blue LED die and short-wave radiation, cause the organic materials transmittance of fluorescent material on fixing blue LED die to decline, and makes the life-span of white light LEDs be tending towards shortening; Because chip pyrotoxin is close to by fluorescent material, temperature rise causes fluorescent material performance degradation, have impact on the stability of product.
The key addressed these problems is the packaged type changing fluorescent material.In recent years, people attempted, by features such as high for the homogeneity of pottery, good stability and long service life, utilizing in the encapsulation of white light LEDs, carrying out large quantifier elimination to YAG:Ce pottery, and achieve certain achievement.
2005, first NEC glass company prepares the Ce:YAG devitrified glass ceramics fluor for white light LEDs, because it has many advantages of glass and pottery concurrently, as hard, heat-resisting, humidity, corrosion-resistant etc., be used on white-light LED encapsulation and achieve good effect.
The people such as Jong study fluorescent material and far put packaged type, have both reduced fluorescent material temperature, additionally reduce the absorption of chip to fluorescent material scattered light, improve light extraction efficiency.The people such as Shunsuke study glass-ceramic fluorescent material, but due to glass matrix be Al2O3-SiO2, and adopt traditional high temperature solid-state method, so preparation temperature is up to 1500 ~ 1650 DEG C.
Chinese patent CN102501478A discloses a kind of composite transparent ceramic for white-light LED fluorescence conversion and preparation method thereof, this composite transparent ceramic is bonded by upper and lower two-layer crystalline ceramics, upper strata crystalline ceramics adopts the YAG crystalline ceramics of Pr modification, and lower floor adopts the YAG crystalline ceramics of Ce modification.Adopt blue-ray LED to excite this composite transparent ceramic, the ruddiness of generation and through blue light form the white light of high-quality, there is colour rendering index high, the feature of colour temperature gentleness.
Chinese patent CN102390982A discloses a kind of low-temperature co-burning ceramic material emitted white light and preparation method thereof, and the molar percentage of each component of this stupalith is: CaO:10-20%, B 2o 3: 50-60%, SiO 2: 50-60%, photoactivation agent ion 1-9%.This pottery adopts Sol-gol method, and sintering temperature is lower, and shrinking percentage is between 13-17%.The stupalith prepared may be used for the fields such as illumination and display.
Summary of the invention
Ce:YAG transparent ceramic material that the object of the present invention is to provide a kind of improvement for high-capacity LED lighting field and preparation method thereof, compared with prior art, this crystalline ceramics is in shrinking percentage, and transparence, there is improvement colour rendering index and colour temperature aspect.Have thermal conductivity high, chemical stability is good, and the life-span is long, the feature that luminous efficiency is high.
The present invention adds additive SiO at traditional Ce:YAG transparent ceramic material 2its content is for the surface topography to yttrium aluminum garnet matrix, and crystalline structure and phase purity have important impact, and the present invention utilizes traditional solid phase method optimization and improves the preparation technology of YAG:Ce remote phosphor, optimize the doping mass ratio of SiO2, the present inventor finds to work as SiO unexpectedly 2doping ratio when 10-15%, transparency and the transmittance of the modification YAG pottery obtained are maximum, simultaneously appropriate SiO 2the calcining temperature that can reduce Ce:YAG transparent ceramic material.This may be because appropriate SiO 2define solid sols after adding Ce:YAG transparent ceramic material, contribute to forming room in crystalline structure, thus improve transparence.
The present inventor also optimizes LiF and Pr from conventional rare earth addition 2o 3, Eu 2o 3, Lu 2o 3introduce in ceramic systems, the rare earth element increased improves the surrounding environment of crystal field, cause the division of energy level, result in and launch peak position migration, make the crystalline ceramics prepared through blue light illumination, make the emmission spectrum of pottery that suitable red shift occur, the light that the LED lamp adopting this ceramic preparation to go out sends is closer to natural daylight, when using the blue light of 460nm as light source, the colour temperature of the white light LEDs of preparation controls at 4000-5000K, in addition a small amount of LiF and rare earth element Pr 2o 3, Eu 2o 3, Lu 2o 3introducing also contribute to improve luminous intensity.Preferred Pr 2o 3, Eu 2o 3, Lu 2o 3mass ratio be 1-2:1:1.
B 2o 3, SiC and CaO introducing, improve crystallite size size and distribution in pottery, reduce the ceramic shrinkage rate that roasting causes, thus further improve pottery quality.
Improvements of the present invention are also the improvement of calcining process, and the present invention calcines for some time under being warmed up to comparatively high temps again after adopting and first calcining for some time at a lower temperature.Such treatment process makes grain-size reduce, thus improves the transparence of crystalline ceramics further.
For a YAG crystalline ceramics for white LED lamp, it is characterized in that, the raw material firing described YAG crystalline ceramics is made up of the raw material of following weight part, Al 2o 3220-300 part, Y 2o 3300-380 part, SiO 260-75 part, CeO 215-20 part, Pr 2o 35-10 part, Eu 2o 32-5 part, Lu2O3 2-4 part, LiF 1-2 part, B 2o 33-5 part, SiC 3-5 part, CaO 0.5-1 part, the purity of described raw material is all at more than 99.99wt%.
SiO in described crystalline ceramics 2mass percent preferably control at 10-15%, be more preferably 12-14%.
Described crystalline ceramics reaches 65%-75% at the light penetration of visible region.
The colour temperature of described crystalline ceramics is 4000-5000k.
For the preparation of a method for the YAG crystalline ceramics of white LED lamp, it comprises the following steps:
A) feed particles proportionally prepared is added dehydrated alcohol, pulverize with ball mill, discharging obtains raw material powder after drying and sieving;
B) carry out dry-pressing formed to the raw material powder that step a) obtains, control pressure is 50-100MPa, and the hold-time is 1-10 minute;
C) to step b) in the shaping plain embryo that obtains carry out vacuum calcining, the temperature of calcining controls at 1250-1300 DEG C, and calcination time is 7-10 hour, and calcining pressure is 10-20MPa;
D) through step b) after vacuum calcining, continue to be warmed up to 1520-1580 DEG C, calcination time is 12-15 hour, and calcining pressure is 5-10MPa, obtains described crystalline ceramics.
Step a) described in sieve after the granularity of raw material powder that obtains be less than 20 microns.
Described step c) calcining temperature preferably control at 1260 DEG C.
Described steps d) calcining temperature control at 1550 DEG C.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, it should be noted, these embodiments are only for illustrating technical scheme of the present invention instead of limiting protection scope of the present invention.
Embodiment 1
The quality group of crystalline ceramics becomes: Al 2o 3280 parts, Y 2o 3360 parts, SiO 265 parts, CeO 220 parts, Pr 2o 310 parts, Eu 2o 35 parts, Lu 2o 34 parts, LiF 2 parts, B 2o 35 parts, SiC 5 parts, CaO01 part.Above-mentioned raw materials is carried out pre-mixing, puts into ball mill, add dehydrated alcohol 500ml, then ball milling 10 hours, dries in 100 DEG C of baking ovens, crosses 600 mesh sieves after grinding.Then make plain embryo at 80MPa pressure, then thick embryo is placed in crucible.Be heated to 1250 DEG C, heat-up rate is 20 DEG C/min, is incubated 7 hours, with 10 DEG C/min continue be warmed up to 1520 DEG C after and be incubated 12 hours, then naturally cooling.Finally grinding and buffing is carried out to the crystalline ceramics fired, and obtain crystalline ceramics product A 1.
Embodiment 2
The quality group of crystalline ceramics becomes: Al 2o 3260 parts, Y 2o 3320 parts, SiO 270 parts, CeO 215 parts, Pr 2o 35 parts, Eu 2o 32 parts, Lu 2o 32 parts, LiF 1 part, B 2o 33 parts, SiC 3 parts, CaO0.5 part.Above-mentioned raw materials is carried out pre-mixing, puts into ball mill, add dehydrated alcohol 500ml, then ball milling 10 hours, dries in 100 DEG C of baking ovens, crosses 600 mesh sieves after grinding.Then make plain embryo at 100MPa pressure, then thick embryo is placed in crucible.Be heated to 1300 DEG C, heat-up rate is 20 DEG C/min, be incubated 10 hours, is incubated 15 hour, then naturally cooling after continuing to be warmed up to 1580 DEG C with the speed of 10 DEG C/min.Finally grinding and buffing is carried out to the crystalline ceramics fired, and obtain crystalline ceramics product A 2.
Comparative example 1
The raw material composition that comparative example 1 adopts and embodiment 1 is basic, difference is SiO 2add-on change 100 parts into.
The quality group of crystalline ceramics becomes: Al 2o 3280 parts, Y 2o 3360 parts, SiO 2100 parts, CeO 220 parts, Pr 2o 310 parts, Eu 2o 35 parts, Lu 2o 34 parts, LiF 2 parts, B 2o 35 parts, SiC 5 parts, CaO01 part.Above-mentioned raw materials is carried out pre-mixing, puts into ball mill, add dehydrated alcohol 500ml, then ball milling 10 hours, dries in 100 DEG C of baking ovens, crosses 600 mesh sieves after grinding.Then make plain embryo at 80MPa pressure, then thick embryo is placed in crucible.Be heated to 1250 DEG C, heat-up rate is 20 DEG C/min, be incubated 7 hours, is incubated 12 hour, then naturally cooling after being warmed up to 1520 DEG C with 1 speed of 10 DEG C/min.Finally grinding and buffing is carried out to the crystalline ceramics fired, and obtain crystalline ceramics product D1.
Comparative example 2
Comparative example 2 adopts the raw material composition identical with embodiment 1, and difference is calcination stage to be changed into a temperature lower calcination.
The quality group of crystalline ceramics becomes: Al 2o 3280 parts, Y 2o 3360 parts, SiO 265 parts, CeO 220 parts, Pr 2o 310 parts, Eu 2o 35 parts, Lu 2o 34 parts, LiF 2 parts, B 2o 35 parts, SiC 5 parts, CaO01 part.Above-mentioned raw materials is carried out pre-mixing, puts into ball mill, add dehydrated alcohol 500ml, then ball milling 10 hours, dries in 100 DEG C of baking ovens, crosses 600 mesh sieves after grinding.Then make plain embryo at 80MPa pressure, then thick embryo is placed in crucible.Be heated to 1520 DEG C, heat-up rate is 20 DEG C/min, is incubated 20 hours, then naturally cooling.Finally grinding and buffing is carried out to the crystalline ceramics fired, and obtain crystalline ceramics product D2.
Comparative example 3
LiF, Pr is not added in comparative example 3 raw material composition 2o 3, Eu 2o 3and Lu 2o 3, other raw material is identical with embodiment 1 with preparation process.
The raw materials quality of crystalline ceramics consists of: Al 2o 3280 parts, Y 2o 3360 parts, SiO 265 parts, CeO 220 parts, B 2o 35 parts, SiC 5 parts, CaO 01 part.Above-mentioned raw materials is carried out pre-mixing, puts into ball mill, add dehydrated alcohol 500ml, then ball milling 10 hours, dries in 100 DEG C of baking ovens, crosses 600 mesh sieves after grinding.Then make plain embryo at 80MPa pressure, then thick embryo is placed in crucible.Be heated to 1250 DEG C, heat-up rate is 20 DEG C/min, be incubated 7 hours, is incubated 12 hour, then naturally cooling after being warmed up to 1520 DEG C with the speed of 10 DEG C/min.Finally grinding and buffing is carried out to the crystalline ceramics fired, and obtain crystalline ceramics product D3.
The performance of all embodiments prepared and comparative example tested, the performance of preparing product is as shown in table 1: (all optical performance tests are all to test the test-results obtained during 460nm blue-light excited):
Table 1

Claims (4)

1. for a YAG crystalline ceramics for white LED lamp, it is characterized in that, the raw material firing described YAG crystalline ceramics is made up of the raw material of following weight part, Al 2o 3220-300 part, Y 2o 3300-380 part, SiO 260-75 part, CeO 215-20 part, Pr 2o 35-10 part, Eu 2o 32-5 part, Lu 2o 32-4 part, LiF 1-2 part, B 2o 33-5 part, SiC 3-5 part, CaO 0.5-1 part, the purity of described raw material is all at more than 99.99wt%, and described crystalline ceramics reaches 65%-75% at the light penetration of visible region; The preparation method of the described YAG crystalline ceramics for white LED lamp comprises the following steps:
A) feed particles proportionally prepared is added dehydrated alcohol, pulverize with ball mill, discharging obtains raw material powder after drying and sieving;
B) carry out dry-pressing formed to the raw material powder that step a) obtains, control pressure is 50-100MPa, and the hold-time is 1-10 minute;
C) to step b) in the shaping plain embryo that obtains carry out vacuum calcining, the temperature of calcining controls at 1250-1300 DEG C, and calcination time is 7-10 hour, and calcining pressure is 10-20MPa;
D) through step b) after vacuum calcining, be warmed up to 1520-1580 DEG C, calcination time is 12-15 hour, and calcining pressure is 5-10MPa, obtains described YAG crystalline ceramics.
2. the YAG crystalline ceramics for white LED lamp according to claim 1, is characterized in that the granularity of the raw material powder obtained after sieving described in step a) is less than 20 microns.
3. the YAG crystalline ceramics for white LED lamp according to claim 1, is characterized in that step c) in calcining temperature be 1260 DEG C.
4. the YAG crystalline ceramics for white LED lamp according to claim 1, is characterized in that steps d) in calcining temperature be 1550 DEG C.
CN201410202347.4A 2014-05-13 2014-05-13 A kind of YAG crystalline ceramics for white LED lamp and preparation method thereof Expired - Fee Related CN104003726B (en)

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CN104291823B (en) * 2014-09-10 2016-04-13 江苏诚赢照明电器有限公司 A kind of YAG crystalline ceramics and preparation method thereof
CN106565218A (en) * 2016-11-01 2017-04-19 安徽江威精密制造有限公司 Fluorescent ceramic base with excellent compressive property for high-power LED and preparation method of fluorescent ceramic base
CN109437900A (en) * 2018-12-12 2019-03-08 中国科学院宁波材料技术与工程研究所 A kind of fluorescence ceramics block, preparation method and its application in laser lighting
CN113213909B (en) * 2021-04-23 2022-11-29 江苏师范大学 YAG-based transparent ceramic resisting ultraviolet radiation and preparation method thereof
CN115895655B (en) * 2022-09-15 2023-10-31 包头稀土研究院 Light-modifying material, method for producing same, and use thereof

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CN103253863A (en) * 2013-05-06 2013-08-21 浙江大学 Rare-earth-doped nitrogen oxide luminescent glass ceramic and preparation method for same

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DE102004048041B4 (en) * 2004-09-29 2013-03-07 Schott Ag Use of a glass or a glass ceramic for light wave conversion

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CN102910899A (en) * 2012-11-16 2013-02-06 北京雷生强式科技有限责任公司 Preparation method of yttrium aluminium garnet doped transparent laser ceramics
CN103253863A (en) * 2013-05-06 2013-08-21 浙江大学 Rare-earth-doped nitrogen oxide luminescent glass ceramic and preparation method for same

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