CN108192610A - A kind of ultraviolet light and blue light activated red light flourescent material and its preparation method and application - Google Patents
A kind of ultraviolet light and blue light activated red light flourescent material and its preparation method and application Download PDFInfo
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- CN108192610A CN108192610A CN201810028825.2A CN201810028825A CN108192610A CN 108192610 A CN108192610 A CN 108192610A CN 201810028825 A CN201810028825 A CN 201810028825A CN 108192610 A CN108192610 A CN 108192610A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a kind of ultraviolet light and blue light activated red light flourescent material and its preparation method and application, the chemical formula of the fluorescent material is L2+yM6‑x(Si2O7)(SiO4)2:xEu3+, L is one or both of for alkali metal Li, Na, K, Cs, and M is one or more of alkaline-earth metal Ca, Sr, Ba, 0 ＜ x ＜ 2,0≤y ＜ 3.Preparation method is to weigh the compound containing L, the compound containing M and the compound containing Si respectively, after ground and mixed by obtained mixture in air atmosphere, 1,000 1300 DEG C roasting 1 10h, obtained solid is red light flourescent material.The fluorescent material transmitting feux rouges of the present invention, excitation wavelength is in 250 ~ 500 nm, and for emission wavelength in 550 ~ 750 nm, preparation method is simple, pollution-free, at low cost, available for LED component to realize the white light emission of high-color rendering.
Description
Technical field
The invention belongs to fluorescent material technical fields, and in particular to a kind of ultraviolet light and blue light activated red light flourescent material
And its preparation method and application.
Background technology
White light LEDs show wide market application due to the advantages that its is small, long lifespan, radiationless, energy conservation and environmental protection
Value and prospect.Compared to the mode that other tradition realize white light, white light LEDs have higher photoelectric conversion efficiency, greatly save
The about energy helps to reduce the discharge of greenhouse gases, so as to providing more clean environment.At present, white light LEDs are in liquid
The numerous areas such as crystal display backlight, indicator light, indoor and outdoor lighting are applied, and white light emitting diode is consolidated as forth generation
Body cold light source is quickly grown in illumination and display field, just gradually substitution conventional light source
At present, most white light LEDs product is to realize white light emission by the way of chip and fluorescent material combination, product
Luminous efficiency and stability can substantially meet practical application request.It is using blue chip to realize the common combination of white light
+ yellow light fluorescent material+red light flourescent material or ultraviolet chip+green-emitting fluorescent material+red light flourescent material.With a series of
Novel green light, yellow light material are reported successively, and it is more and more to realize that green light, the type of yellow light material may be selected in white light emission.But
It is warm white to be obtained, it is necessary to enhance the transmitting of red light portion, simplest solution is that red light material is combined to indigo plant
In light conversion hysteria WLED, but the available red light material of white light LEDs is fewer at present.Such as Y2O3：Eu3+Have at about 254 nm
Stronger absorption absorbs weaker in about near ultraviolet and blue light region.So invent a kind of near ultraviolet LED chip excitation（About
400 nm）Or blue-light LED chip（About 450 ~ 460 nm）The red fluorescence material for having stronger absorption is extremely urgent.Cause
This, studies novel red light flourescent material and is of great practical significance.
Invention content
The technical issues of red light material missing available present invention aim to address current white light LEDs, provide a kind of purple
Outer light and blue light activated red light flourescent material and its preparation method and application.
A kind of ultraviolet light and blue light activated red light flourescent material, chemical formula L2+yM6-x(Si2O7)(SiO4)2:xEu3 +；
Wherein, L is one or both of for alkali metal Li, Na, K, Cs, and M is one or more of alkaline-earth metal Ca, Sr, Ba,
0 ＜ x ＜ 2,0≤y ＜ 3.
Further, x=0.1, y=0.1.
The preparation method of above-mentioned ultraviolet light and blue light activated red light flourescent material, includes the following steps：
Step 1, the compound containing L, the compound containing M and the compound containing Si, ground and mixed are weighed respectively obtains mixture；
Step 2, mixture step 1 obtained in air atmosphere, 1000-1300 DEG C of roasting 1-10h, obtained solid is
Red light flourescent material；
The compound containing L is in the compound containing Li, the compound containing Na, the compound containing K or the compound containing Cs
It is one or more of；
The compound containing M is one or more of the compound containing Ba, the compound containing Sr or compound containing Ca.
Further, the compound of the Li is selected from nitrate containing Li, hydroxide containing Li or carbonate containing Li；The Na
Compound be selected from nitrate containing Na, hydroxide containing Na or carbonate containing Na；The compound containing K be selected from nitrate containing K,
Hydroxide containing K or carbonate containing K；The compound containing Cs is selected from nitrate containing Cs, hydroxide containing Cs or carbonic acid containing Cs
Salt.
Further, the compound containing Ba is selected from oxide containing Ba, carbonate containing Ba, nitrate containing Ba or containing Ba's
Hydroxide；The compound containing Sr is selected from oxide containing Sr, carbonate containing Sr, nitrate containing Sr or hydroxide containing Sr；
The compound containing Ca is selected from oxide containing Ca, carbonate containing Ca, nitrate containing Ca or hydroxide containing Ca.
Further, it also needs to add in fluxing agent in step 1.
Further, the fluxing agent is boric acid, ammonium fluoride, ammonium acid fluoride, aluminum fluoride, alkali earth metal fluoride or rare earth
The mixture of one or more of metal fluoride.
Further, the dosage of the fluxing agent is always rubbed for the compound containing L, the compound containing M and the compound containing Si
The 1-10% of your amount.
The application of above-mentioned ultraviolet light and blue light activated red light flourescent material in white light LEDs are prepared.
Beneficial effects of the present invention are：
1st, fluorescent material of the invention launches feux rouges under ultraviolet light and blue light excitation, and excitation wavelength is in 200-500 nm, hair
Optical wavelength is in 550-750 nm.
2nd, the abundant raw material of fluorescent material of the present invention, at low cost, preparation method simple possible, it is easily operated, be easy to volume production,
It is pollution-free, at low cost.
3rd, red light flourescent material of the invention is applied to white light LEDs, while is suitble to ultraviolet and blue chip, excitation wavelength model
It encloses wide, efficient, stable.
Description of the drawings
Fig. 1 is fluorescent material Na prepared by the embodiment of the present invention 12Ba5.94(Si2O7)(SiO4)2:0.06Eu3+XRD (X-rays
Diffraction) spectrogram；
Fig. 2 is fluorescent material Na prepared by the embodiment of the present invention 32Ba5.94(Si2O7)(SiO4)2:0.10Eu3+Excitation spectrum
Figure；
Fig. 3 is fluorescent material Na prepared by the embodiment of the present invention 32Ba5.94(Si2O7)(SiO4)2:0.10Eu3+Emission spectrum
Figure；
Fig. 4 is fluorescent material Na prepared by the embodiment of the present invention 82Ba5.8(Si2O7)(SiO4)2:0.2Eu3+Exciting light spectrogram；
Fig. 5 is fluorescent material Na prepared by the embodiment of the present invention 82Ba5.8(Si2O7)(SiO4)2:0.2Eu3+Launching light spectrogram.
Specific embodiment
Technical scheme of the present invention is described further with reference to specific embodiment.
Embodiment 1
Weigh BaCO30.9393 gram, Na2CO3 0.0848 gram, SiO2 0.1923 gram, Eu2O3It 0.0070 gram, is fully ground
Mill mixing, is put into corundum crucible, is put into air and is roasted 4 hours in 1050 DEG C, and after natural cooling when takes out, grinding distribution
Afterwards, a kind of novel ultraviolet light and blue light activated red light flourescent material are obtained, consisting of Na2Ba5.95(Si2O7)(SiO4)2:
0.05Eu3+。
Fig. 1 is Na2Ba5.95(Si2O7)(SiO4)2:0.05Eu3+XRD (X-ray diffractogram) spectrogram；It can from figure
Go out, fluorescent material and Na of the invention2Ba6(Si2O7)(SiO4)2Standard card absorption peak position it is basically identical, it is not miscellaneous
Peak illustrates the structural formula of the invention that is prepared for really for Na2Ba5.95(Si2O7)(SiO4)2:0.05Eu3+Fluorescent powder.
Embodiment 2
Weigh BaCO3 0.9314 gram, Na2CO3 0.0933 gram, SiO2 0.1923 gram, Eu2O3 It 0.0141 gram, is fully ground
Mill mixing, is put into corundum crucible, is put into air and is roasted 4 hours in 1050 DEG C, and after natural cooling when takes out, grinding distribution
Afterwards, a kind of novel ultraviolet light and blue light activated red light flourescent material are obtained, consisting of Na2.1Ba5.9(Si2O7)(SiO4)2:
0.10Eu3+。
Embodiment 3
Weigh BaCO30.9393 gram, NaNO3 0.1360 gram, SiO2 0.1923 gram, Eu2O3It 0.0141 gram, is fully ground
Mixing, is put into corundum crucible, is put into air and is roasted 4 hours in 1050 DEG C, and after natural cooling when takes out, after grinding distribution,
A kind of novel ultraviolet light and blue light activated red light flourescent material are obtained, consisting of Na2Ba5.94(Si2O7)(SiO4)2:
0.10Eu3+。
Fig. 2 and Fig. 3 is respectively Na2Ba5.94(Si2O7)(SiO4)2:0.10Eu3+Exciting light spectrogram and launching light spectrogram；From
It can be seen from the figure that, fluorescent material of the invention launches feux rouges under ultraviolet light and blue light excitation, in 613nm Detection wavelength items
Under part, sample shows the sharp line absorption such as 394 nm, 450 nm, and under the conditions of 394 nm excitation wavelengths, sample shows 613
The sharp line strong light emission such as nm, 711 nm.
Embodiment 4
Weigh BaCO3 0.9393 gram, K2CO3 0.1106 gram, SiO2 0.1923 gram, Eu2O3It 0.0141 gram, is fully ground
Mixing, is put into corundum crucible, is put into air and is roasted 4 hours in 1050 DEG C, and after natural cooling when takes out, after grinding distribution,
A kind of novel ultraviolet light and blue light activated red light flourescent material are obtained, consisting of K2Ba5.94(Si2O7)(SiO4)2:
0.10Eu3+。
Embodiment 5
Weigh 0.7286 gram of BaO, Na2CO3 0.0848 gram, SiO2 0.1923 gram, Eu2O30.0141 gram, it is fully ground
Mixing, is put into corundum crucible, is put into air and is roasted 4 hours in 1050 DEG C, and after natural cooling when takes out, after grinding distribution,
A kind of novel ultraviolet light and blue light activated red light flourescent material are obtained, consisting of Na2Ba5.94(Si2O7)(SiO4)2:
0.10Eu3+。
Embodiment 6
Weigh BaCO3 0.7894 gram, CaCO3 0.0073 gram, Na2CO3 0.0848 gram, SiO2 0.1923 gram, Eu2O3 0.0141
Gram, it gram carries out being fully ground mixing, be put into corundum crucible, be put into air and roasted 4 hours in 1050 DEG C, when after natural cooling
It takes out, after grinding distribution, a kind of novel ultraviolet light and blue light activated red light flourescent material is obtained, consisting of Na2Ba5Ca0.9
(Si2O7)(SiO4)2:0.10Eu3+。
Embodiment 7
Weigh BaCO30.6157 gram, SrCO3 0.3542 gram, Na2CO3 0.0848 gram, SiO2 0.1923 gram, Eu2O3 0.0141
Gram, H3BO3 0.0185, it gram carries out being fully ground mixing, be put into corundum crucible, be put into air and roasted 4 hours in 1050 DEG C,
It is taken out when after natural cooling, after grinding distribution, obtains a kind of novel ultraviolet light and blue light activated red light flourescent material, composition
For Na2Ba3.9Sr2(Si2O7)(SiO4)2:0.1Eu3+。
Embodiment 8
Weigh Ba (OH)20.7115 gram, Na2CO3 0.0848 gram, SiO2 0.1923 gram, Eu2O30.0282 gram, H3BO3
0.0185, it gram carries out being fully ground mixing, be put into corundum crucible, be put into air and roasted 4 hours in 1050 DEG C, natural cooling
It is taken out when afterwards, after grinding distribution, obtains a kind of novel ultraviolet light and blue light activated red light flourescent material, consisting of
Na2Ba5.8(Si2O7)(SiO4)2:0.2Eu3+。
Fig. 4 and Fig. 5 is respectively Na2Ba5.94(Si2O7)(SiO4)2:0.10Eu3+Exciting light spectrogram and launching light spectrogram；From
It can be seen from the figure that, fluorescent material of the invention launches feux rouges under ultraviolet light and blue light excitation, in 702 nm Detection wavelengths
Under the conditions of, sample shows the sharp line absorption such as 394 nm, 450 nm, and under the conditions of 394 nm excitation wavelengths, sample shows 613
The sharp line strong light emission such as nm, 711 nm.
The explanation of above example is only intended to help to understand preparation method and its central idea of the invention.It should refer to
Go out, it, without departing from the principle of the present invention, can also be to this hair for the those skilled in the art being related to
Bright some improvement and modification can also be carried out, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (9)
1. a kind of ultraviolet light and blue light activated red light flourescent material, it is characterised in that：
Its chemical formula is L2+yM6-x(Si2O7)(SiO4)2:xEu3+；
Wherein, L is one or both of for alkali metal Li, Na, K, Cs, and M is one or more of alkaline-earth metal Ca, Sr, Ba,
0 ＜ x ＜ 2,0≤y ＜ 3.
2. ultraviolet light according to claim 1 and blue light activated red light flourescent material, it is characterised in that：X=0.1, y
= 0.1。
3. the preparation method of ultraviolet light described in claim 1 and blue light activated red light flourescent material, it is characterised in that：Including
Following steps：
Step 1, the compound containing L, the compound containing M and the compound containing Si, ground and mixed are weighed respectively obtains mixture；
Step 2, mixture step 1 obtained in air atmosphere, 1000-1300 DEG C of roasting 1-10h, obtained solid is
Red light flourescent material；
The compound containing L is in the compound containing Li, the compound containing Na, the compound containing K or the compound containing Cs
It is one or more of；
The compound containing M is one or more of the compound containing Ba, the compound containing Sr or compound containing Ca.
4. the preparation method of ultraviolet light according to claim 3 and blue light activated red light flourescent material, it is characterised in that：
The compound of the Li is selected from nitrate containing Li, hydroxide containing Li or carbonate containing Li；The compound of the Na is selected from containing Na
Nitrate, hydroxide containing Na or carbonate containing Na；The compound containing K is selected from nitrate containing K, hydroxide containing K or containing K
Carbonate；The compound containing Cs is selected from nitrate containing Cs, hydroxide containing Cs or carbonate containing Cs.
5. the preparation method of ultraviolet light according to claim 3 and blue light activated red light flourescent material, it is characterised in that：
The compound containing Ba is selected from oxide containing Ba, carbonate containing Ba, nitrate containing Ba or the hydroxide containing Ba；It is described to contain Sr
Compound be selected from oxide containing Sr, carbonate containing Sr, nitrate containing Sr or hydroxide containing Sr；The compound choosing containing Ca
Self-contained Ca oxides, carbonate containing Ca, nitrate containing Ca or hydroxide containing Ca.
6. the preparation method of ultraviolet light according to claim 3 and blue light activated red light flourescent material, it is characterised in that：
It also needs to add in fluxing agent in step 1.
7. the preparation method of ultraviolet light according to claim 6 and blue light activated red light flourescent material, it is characterised in that：
The fluxing agent is one in boric acid, ammonium fluoride, ammonium acid fluoride, aluminum fluoride, alkali earth metal fluoride or rare earth metal fluoride
Kind or several mixtures.
8. the preparation method of ultraviolet light according to claim 6 and blue light activated red light flourescent material, it is characterised in that：
The dosage of the fluxing agent is the 1-10% of the compound containing L, the compound containing M and the compound integral molar quantity containing Si.
9. the application of ultraviolet light and blue light activated red light flourescent material in white light LEDs are prepared described in claims 1 or 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810028825.2A CN108192610B (en) | 2018-01-12 | 2018-01-12 | Ultraviolet light and blue light excited red light fluorescent material and preparation method and application thereof |
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|---|---|---|---|
| CN201810028825.2A CN108192610B (en) | 2018-01-12 | 2018-01-12 | Ultraviolet light and blue light excited red light fluorescent material and preparation method and application thereof |
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| CN108192610B CN108192610B (en) | 2021-03-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046067A (en) * | 2021-03-18 | 2021-06-29 | 唐山学院 | Eu (Eu)3+/K+Codoped sodium barium fluoborate-based red phosphor and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN105131953A (en) * | 2015-09-09 | 2015-12-09 | 太原理工大学 | Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder |
-
2018
- 2018-01-12 CN CN201810028825.2A patent/CN108192610B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131953A (en) * | 2015-09-09 | 2015-12-09 | 太原理工大学 | Rare earth ion doping novel polysilicate green fluorescent powder for near ultraviolet stimulated white light LED and preparation method of novel polysilicate green fluorescent powder |
Non-Patent Citations (2)
| Title |
|---|
| 游潘丽等: "《白光LED用硅酸盐发光材料研究》", 31 July 2014, 四川大学出版社 * |
| 韩甲: "Solid-state reaction preparation and photoluminescence properties of Na2Ba6(Si2O7)(SiO4)2:Eu2+ phosphors", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046067A (en) * | 2021-03-18 | 2021-06-29 | 唐山学院 | Eu (Eu)3+/K+Codoped sodium barium fluoborate-based red phosphor and preparation method thereof |
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