CN107603605A - A kind of white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation - Google Patents
A kind of white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation Download PDFInfo
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- CN107603605A CN107603605A CN201710920332.5A CN201710920332A CN107603605A CN 107603605 A CN107603605 A CN 107603605A CN 201710920332 A CN201710920332 A CN 201710920332A CN 107603605 A CN107603605 A CN 107603605A
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- ultraviolet
- white light
- luminescent material
- light leds
- blue green
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Abstract
A kind of white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation, its chemical formula are：Ca1.65‑ySr0.35‑ xSi1‑zO4:Eux, Cey/Lz, 0.001≤x≤0.08,0.001≤y≤0.15,0≤z≤0.5 in formula, the one or more in L Al, Ga and B.The preparation method of the material, comprises the following steps：(1) with carbonate or oxide containing Ca, carbonate or oxide containing Sr, simple substance, oxide or salt containing Si, the oxide of Eu or Ce oxide and L is raw material, adds solvent, and ground and mixed is uniformly dried afterwards；(2) (1) products therefrom is regrind, in mixed gas protected lower carry out high-temperature roasting, final product is produced after cooling, with existing blue BAM and green (Ba, Sr)2SiO4Compare, luminescent material provided by the invention has wider array of excites scope, preferably can match with ultraviolet/black light LED chip.
Description
Technical field
The invention belongs to luminescent material technical field, and in particular to a kind of white light suitable for ultraviolet/near ultraviolet excitation
LED blue green luminescent materials and preparation method thereof.
Background technology
White light emitting diode (LED), as a kind of new solid state illumination technology, have using low-tension supply, power consumption
Less, the advantages of strong applicability, stability are high, the response time is short, environmentally safe, multicolor luminous etc., will progressively substitute power consumption
Larger incandescent lamp and the fluorescent lamp of mercury pollution.Therefore, corresponding measure and policy have all been formulated to send out in many countries and regions
Open up white light LEDs.
At present, white light LEDs mainly have three kinds of implementations：First, the LED of combination three kinds of fluorescent material of red, green and blue；Second,
Using blue-ray LED combination yellow fluorescent powder (Y3Al5O12,YAG)；It is third, glimmering using ultraviolet black light LED combination red, green and blue
Light powder.However, at present can really Commercialization application only the second way.
One of the critical material of fluorescence transition material as white light LEDs, the development to high efficiency semiconductor illumination are most important.
Before this, white light LEDs mainly realize that is, a part of blue light excites fluorescence by the way of blue-ray LED combines YAG yellow fluorescent powders
Powder produces gold-tinted, and gold-tinted combines with some blue light and realizes white light.But now widely used YAG fluorescent powder, because it lacks
Feux rouges component, the white light colour temperature obtained in this way is higher, and colour rendering index is low, and thermal characteristics is undesirable.Thus, in order to overcome
These shortcomings, the third above-mentioned realize that the scheme of white light LEDs is widely paid close attention to.The exploitation of new blue green fluorescent material
It is a wherein critically important part.
The content of the invention
For problems of the prior art, swash it is an object of the invention to one kind suitable for ultraviolet/black light
The white light LEDs of hair blue green luminescent material.It is a further object of the present invention to provide the method for preparing above-mentioned luminescent material.
To achieve the above object, the present invention uses following scheme：
A kind of white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation, its chemical formula are：
Ca1.65-ySr0.35-xSi1-zO4:Eux, Cey/Lz, 0.001≤x≤0.08,0.001≤y≤0.15,0≤z≤0.5 in formula, L is
One or more in Al, Ga and B.
A kind of white light LEDs suitable for ultraviolet/near ultraviolet excitation are lighted the preparation method of material with blue green, including with
Lower step：
(1) chemical formula Ca is pressed1.65-ySr0.35-xSi1-zO4:Eux, Cey/LzIt is former that the molar percentage of middle each element weighs reaction
Material, solvent is added, is dried after being fully ground, then grind；
(2) sinter, taken out after cooling under reducing atmosphere, produced；
Wherein, one kind or more in 0.001≤x≤0.08,0.001≤y≤0.15,0≤z≤0.5, L Al, Ga and B
Kind.
Preferably, the white light LEDs suitable for ultraviolet/near ultraviolet excitation are lighted with blue green the preparation method of material, including
Following steps：
(1) chemical formula Ca is pressed1.65-ySr0.35-xSi1-zO4:Eux, Cey/LzThe molar percentage of middle each element is weighed containing Ca's
Carbonate or oxide, carbonate or oxide containing Sr, silica or silicon nitride, the oxygen of Eu or Ce oxide and L
Compound, solvent is added, dried after grinding fully, then grind；
(2) sinter, taken out after cooling under reducing atmosphere, produced.
Preferably, the solvent is ethanol.
Preferably, the time ground again is 1-5min.
Preferably, the drying temperature is 80-100 DEG C, drying time 10-12h.
Preferably, the temperature of the sintering is 1100-1300 DEG C, time 6-12h.
It is further preferred that the temperature of the sintering is 1200-1250 DEG C, drying time 8-10h.
Preferably, the gas in the reducing atmosphere is H2And N2Mixed gas.
It is further preferred that H2And N2Percent by volume be 10-30:70-90.
Beneficial effects of the present invention
1st, preparation method of the present invention synthesizes obtained europium and/or cerium ion-doped silicate luminescent material, chemistry
Form as Ca1.65-ySr0.35-xSi1-zO4:Eux, Cey/Lz, x=0.001-0.08, y=0.001-0.15, z=0-0.5, L in formula
For the one or more in Al, Ga and B；In the case where ultraviolet/black light (250-420nm) excites, luminescent material energy of the invention
Enough launch bright blue green light, it can be encapsulated into white light hair with the LED chip after rouge and powder mixing with ultraviolet/black light
Optical diode, applied to illumination；
2nd, compared with existing blue BAM fluorescent material, blue colour fluorescent powder (such as Ca of the invention being prepared1.65- ySr0.35Si1-zO4:Cey/ L) excites scope is wider, the position of excitation peak is 370nm or so, can preferably with ultraviolet chip phase
Matching；The position of the blue colour fluorescent powder emission peak being prepared of the present invention and halfwidth can increase with the increase of L content
Greatly, and its emissive porwer can strengthen under some L doping conditions；
3rd, with (Ba, Sr)2SiO4Compare, green emitting phosphor (such as Ca that the present invention is prepared1.65Sr0.35-xSiO4:Eux),
Excites scope is wider, preferably can match with ultraviolet/black light LED chip；The green emitting phosphor emission peak of the present invention
In 510nm or so, halfwidth is about 87nm for position, and its intensity at 150 DEG C is about 66% under normal temperature, better than (Ba, Sr)2SiO449%, sample does not carry out subsequent treatment, and luminous quantum efficiency can be up to 69%；
4th, for luminescent material of the invention in the case where 365nm is excited, the emission peak of transmitting most strong sample is to be located at 436 Hes respectively
508nm broadband emission；
5th, luminescent material of the invention has to preparing white light LEDs that are efficient, possessing potential application with luminescent material
Certain promotional value；
6th, preparation method technique of the present invention is simple, it is easy to accomplish the purpose of volume production, while it is pollution-free, cost is low.
Brief description of the drawings
Fig. 1 is the XRD spectrum for the blue green luminescent material that embodiment 1-6 is prepared, respectively the a-f in corresponding diagram 1
Figure；
Fig. 2 be the blue green luminescent materials that are prepared of embodiment 1-6 excite and launching light spectrogram, corresponding diagram 2 respectively
In a-f figure；
Fig. 3 is sample Ca1.65Sr0.35-xSiO4:EuxIn the case where 365nm excites with Eu2+The increase d of doped parameterx color is sat
Mark variation diagram.
Embodiment
Raw material used in the present invention is analytically pure CaCO3, SrCO3, SiO2, Al (OH)3/Ga2O3/H3BO3With it is high-purity
CeO2Or Eu2O3(99.99%), the present invention is described in further detail with reference to embodiment and accompanying drawing, but the present invention
It is not limited to these embodiments.
Embodiment 1
Material is chosen according to chemical formula Ca1.60Sr0.35SiO4:Ce0.05, it is pure to weigh analysis respectively according to its molar percentage
CaCO3, SrCO3, SiO2With high-purity CeO2(99.99%), add after appropriate ethanol is fully ground, after drying and grind
One minute, it is fitted into crucible in 1250 DEG C of reducing atmosphere H2/N28h is sintered under (20%/80%), is taken out after cooling, after grinding i.e.
It can obtain final product.
Embodiment 2
Material is chosen according to chemical formula Ca1.60Sr0.35Si0.7O4:Ce0.05/ 0.30Al, claim respectively according to its molar percentage
Take analytically pure CaCO3, SrCO3, SiO2, Al (OH)3With high-purity CeO2(99.99%) appropriate ethanol, is added to be fully ground
Afterwards, after drying and grind one minute, be fitted into crucible in 1250 DEG C of reducing atmosphere H2/N28h is sintered under (20%/80%), is cooled down
After take out, after grinding i.e. can obtain final product.
Embodiment 3
Material is chosen according to chemical formula Ca1.60Sr0.35Si0.7O4:Ce0.05/ 0.30Ga, claim respectively according to its molar percentage
Take analytically pure CaCO3, SrCO3, SiO2, Ga2O3With high-purity CeO2(99.99%), add after appropriate ethanol is fully ground,
After drying and grind one minute, be fitted into crucible in 1250 DEG C of reducing atmosphere H2/N28h is sintered under (20%/80%), is taken after cooling
Go out, final product is can obtain after grinding.
Embodiment 4
Material is chosen according to chemical formula Ca1.60Sr0.35Si0.7O4:Ce0.05/ 0.30B, claim respectively according to its molar percentage
Take analytically pure CaCO3, SrCO3, SiO2, H3BO3With high-purity CeO2(99.99%), add after appropriate ethanol is fully ground,
After drying and grind one minute, be fitted into crucible in 1300 DEG C of reducing atmosphere H2/N28h is sintered under (20%/80%), is taken after cooling
Go out, final product is can obtain after grinding.
Embodiment 5
Material is chosen according to chemical formula Ca1.65Sr0.34SiO4:Eu0.01, it is pure to weigh analysis respectively according to its molar percentage
CaCO3, SrCO3, SiO2With high-purity Eu2O3(99.99%), add after appropriate ethanol is fully ground, after drying and grind
One minute, it is fitted into crucible in 1250 DEG C of reducing atmosphere H2/N28h is sintered under (20%/80%), is taken out after cooling, after grinding i.e.
It can obtain final product.
Embodiment 6
Material is chosen according to chemical formula Ca1.60Sr0.34SiO4:Eu0.01,Ce0.05, weighed respectively point according to its molar percentage
Analyse pure CaCO3, SrCO3, SiO2With high-purity Eu2O3(99.99%), CeO2(99.99%) appropriate ethanol, is added fully to grind
After mill, after drying and grind one minute, be fitted into crucible in 1100 DEG C of reducing atmosphere H2/N210h is sintered under (20%/80%), it is cold
But take out afterwards, final product is can obtain after grinding.
Understood referring to Fig. 1-Fig. 3, the blue Ca prepared by above-described embodiment1.65-ySr0.35Si1-zO4:Cey/LzFluorescent material swashs
Hair scope is wider, and the position of excitation peak is 370nm or so, is more suitable for matching ultraviolet chip.The green Ca of preparation1.65Sr0.35- xSiO4:EuxFluorescent material and (Ba, Sr)2SiO4Compare, excites scope more extensively can preferably with ultraviolet/black light LED chip
Match.Simultaneously in the case where 365nm is excited, the emission peak for launching most strong sample is the broadband emission positioned at 436 and 508nm respectively.
The position of blue colour fluorescent powder emission peak and halfwidth can increase with the increase of L content.And its emissive porwer is mixed in some L
It can strengthen under the conditions of miscellaneous.The emission peak positions of green emitting phosphor are about 87nm in 510nm or so, its halfwidth.It is at 150 DEG C
Intensity is about 66% under normal temperature, better than (Ba, Sr)2SiO449%, sample does not carry out subsequent treatment, luminous quantum efficiency energy
Up to 69%.
Embodiment 7
Material is chosen according to chemical formula Ca1.60Sr0.35Si0.80O4:Ce0.05,Al0.10,Ga0.10According to its Mole percent score
Also known as take analytically pure CaCO3, SrCO3, SiO2, Ga2O3, Al (OH)3With high-purity CeO2(99.99%) appropriate second, is added
After alcohol is fully ground, after drying and grinds one minute, be fitted into crucible in 1200 DEG C of reducing atmosphere H2/N2Burnt under (20%/80%)
9h is tied, is taken out after cooling, final product is can obtain after grinding.
Embodiment 8
Material is chosen according to chemical formula Ca1.60Sr0.35Si0.70O4:Ce0.05,Al0.10,Ga0.10,B0.10According to its Mole percent
Than weighing analytically pure CaCO respectively3, SrCO3, SiO2, Ga2O3, Al (OH)3, H3BO3With high-purity CeO2(99.99%), add
After appropriate ethanol is fully ground, after drying and grinds one minute, be fitted into crucible in 1250 DEG C of reducing atmosphere H2/N2(20%/
80%) 9h is sintered under, is taken out after cooling, final product is can obtain after grinding.
The white light LEDs blue green fluorescent material for ultraviolet/near ultraviolet excitation that remaining embodiment is not prepared, as long as chemical
Form as Ca1.65-ySr0.35-xSi1-zO4:Eux, Cey/Lz, x=0.001-0.08, y=0.001-0.15, z=0-0.5, L in formula
For the one or more in Al, Ga and B.Meet the blue green fluorescent material of above-mentioned condition can disclosed in above-described embodiment bar
It is prepared under part, will not enumerate here.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
- A kind of 1. white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation, it is characterised in that its chemistry Formula is：Ca1.65-ySr0.35-xSi1-zO4:Eux, Cey/Lz, 0.001≤x≤0.08 in formula, 0.001≤y≤0.15,0≤z≤ One or more in 0.5, L Al, Ga and B.
- 2. the white light LEDs blue green luminescent material according to claim 1 suitable for ultraviolet/near ultraviolet excitation Preparation method, it is characterised in that comprise the following steps：(1) chemical formula Ca is pressed1.65-ySr0.35-xSi1-zO4:Eux, Cey/LzThe molar percentage of middle each element weighs reaction raw materials, adds Enter solvent, dried after being fully ground, then grind；(2) sinter, taken out after cooling under reducing atmosphere, produced；Wherein, the one or more in 0.001≤x≤0.08,0.001≤y≤0.15,0≤z≤0.5, L Al, Ga and B.
- 3. the white light LEDs blue green luminescent material according to claim 1 suitable for ultraviolet/near ultraviolet excitation Preparation method, it is characterised in that comprise the following steps：(1) chemical formula Ca is pressed1.65-ySr0.35-xSi1-zO4:Eux, Cey/LzThe molar percentage of middle each element weighs the carbonic acid containing Ca Salt or oxide, carbonate or oxide containing Sr, silica or silicon nitride, the oxide of Eu or Ce oxide and L, Solvent is added, is dried after grinding fully, then grind；(2) sinter, taken out after cooling under reducing atmosphere, produced.
- 4. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the solvent is ethanol.
- 5. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the time ground again is 1-5min.
- 6. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the drying temperature be 80-100 DEG C, drying time 10-12h.
- 7. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the temperature of the sintering be 1100-1300 DEG C, time 6-12h.
- 8. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the temperature of the sintering be 1200-1250 DEG C, time 8-10h.
- 9. the white light LEDs blue green luminescent material suitable for ultraviolet/near ultraviolet excitation according to Claims 2 or 3 Preparation method, it is characterised in that the gas in the reducing atmosphere is H2And N2Mixed gas.
- 10. the white light LEDs blue green luminescent material according to claim 9 suitable for ultraviolet/near ultraviolet excitation Preparation method, it is characterised in that H2And N2Percent by volume be 10-30:70-90.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994914A (en) * | 2020-08-10 | 2020-11-27 | 苏州鼎安科技有限公司 | Ion co-doped beta-dicalcium silicate powder, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154073A (en) * | 2015-07-20 | 2015-12-16 | 中国科学院长春应用化学研究所 | Blue/green fluorescent powder suitable for ultraviolet light/near ultraviolet light excitated white LED and preparation method for blue/green fluorescent powder |
-
2017
- 2017-09-30 CN CN201710920332.5A patent/CN107603605A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154073A (en) * | 2015-07-20 | 2015-12-16 | 中国科学院长春应用化学研究所 | Blue/green fluorescent powder suitable for ultraviolet light/near ultraviolet light excitated white LED and preparation method for blue/green fluorescent powder |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994914A (en) * | 2020-08-10 | 2020-11-27 | 苏州鼎安科技有限公司 | Ion co-doped beta-dicalcium silicate powder, preparation method and application |
| CN111994914B (en) * | 2020-08-10 | 2023-11-28 | 苏州鼎安科技有限公司 | Ion co-doped beta-dicalcium silicate powder, preparation method and application |
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