CN107541211A - Blue luminescent phosphor suitable near ultraviolet excitation and its preparation method and application - Google Patents

Blue luminescent phosphor suitable near ultraviolet excitation and its preparation method and application Download PDF

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Publication number
CN107541211A
CN107541211A CN201710777752.2A CN201710777752A CN107541211A CN 107541211 A CN107541211 A CN 107541211A CN 201710777752 A CN201710777752 A CN 201710777752A CN 107541211 A CN107541211 A CN 107541211A
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luminescent phosphor
near ultraviolet
ultraviolet excitation
blue luminescent
blue
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CN107541211B (en
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郝振东
张晟
张家骅
张霞
张亮亮
潘国徽
武华君
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The present invention relates to a kind of blue luminescent phosphor suitable near ultraviolet excitation and its preparation method and application, belong to field of light emitting materials.Blue luminescent phosphor provided by the invention suitable near ultraviolet excitation, its formula are:Sr1‑xMxLu2‑yLnyO4:Ce3+ m,An, wherein M represents one kind or any combination in Mg, Ca and Ba;Ln represents one kind or any combination in Y, La, Gd and Sc;A represents one kind or any combination in Li, Na, K, Rb and Cs;0≤x≤0.5,0≤y≤1,0.0001≤m≤0.01;0≤n≤0.01.The blue-light-emitting effectively excites position to be located at 380 450nm scopes, and emission peak position is located at 445 480nm scopes.The preparation method of the blue luminescent phosphor is simple, pollution-free, cost is low.The blue luminescent phosphor have effectively achieved the light transformation for launching blue light under near ultraviolet excitation.The fluorescent material can be applied to blue light emitting device or device as a kind of blue luminescent phosphor suitable near ultraviolet excitation, can also be mixed with other colour light emitting fluorescent material and be applied to white light emitting device or device.

Description

Blue luminescent phosphor suitable near ultraviolet excitation and its preparation method and application
Technical field
The invention belongs to field of light emitting materials, and in particular to a kind of blue luminescent phosphor suitable near ultraviolet excitation and Its preparation method and application.
Background technology
White light LEDs (Light Emitting Diode:Light emitting diode) there is efficient, energy-conservation, long lifespan, can It is widely used on various lighting installations, such as stop-light, street lamp, auto lamp, outdoor display screen and billboard, it is a kind of Environmental protection, the green illumination light source of energy-conservation, it is the new light sources for 21 century substituting traditional lighting device.
Currently, the mainstream scheme of White-light LED illumination is using blue-light LED chip coating yellow fluorescent powder, yellow fluorescent powder The blue light that the gold-tinted sent and tube core transmit is into white light.However, the program due to lack in spectrum green glow and feux rouges into Point, cause the colour rendering of device poor, be not suitable for room lighting, especially such as gallery, room and exhibition center place.It is white to improve Light LED color developing, there has been proposed using black light LED chip coating red, green, blue three primary colors fluorescent powder, utilize three The three primary colours light that primary colours fluorescent material is sent realizes white light emission, can mention colour rendering high by more than 90.Wherein, exploitation is suitable near purple Outer light activated red, green, blue three primary colors fluorescent powder is crucial.
At present, the generally acknowledged blue light fluorescent powder suitable near ultraviolet excitation of industry has BaMgAl10O17:Eu2+(BAM)、 Sr2MgSi2O7:Eu2+And Sr5(PO4)3Cl:Eu2+Deng.Recently, notification number is that the B patents of CN 105219378 disclose one kind newly Type silicate blue fluorescent powder Na2(Ca0.5Sr0.5-x)(SiO4):xEu2+.However, BAM blue powder heat resistanceheat resistant stability is poor, Sr2MgSi2O7:Eu2+、Sr5(PO4)3Cl:Eu2+And Na2(Ca0.5Sr0.5-x)(SiO4):xEu2+Excited in 400nm black lights area Efficiency drastically declines.Therefore it is adapted to the novel blue light fluorescent material that black light area excites, thermal stability is excellent to need further Exploitation.
The content of the invention
The purpose of the present invention be a kind of suitable black light area of exploitation excite, the novel blue light fluorescence that thermal stability is excellent Powder, and then a kind of blue luminescent phosphor suitable near ultraviolet excitation and its preparation method and application is provided.
To achieve these goals, technical scheme is specific as follows:
A kind of blue luminescent phosphor suitable near ultraviolet excitation, its formula are:Sr1-xMxLu2-yLnyO4:Ce3+ m,An, Wherein M represents one kind or any combination in Mg, Ca and Ba;Ln represents one kind or any combination in Y, La, Gd and Sc;A generations One kind or any combination in table Li, Na, K, Rb and Cs;0≤x≤0.5,0≤y≤1,0.0001≤m≤0.01;0≤n≤ 0.01。
In the above-mentioned technical solutions, the blue luminescent phosphor expression formula suitable near ultraviolet excitation is:SrLu2O4: Ce3+ 0.002
A kind of preparation method of blue luminescent phosphor suitable near ultraviolet excitation, comprises the following steps:
1) each metallic element compound in formula is stoichiometrically weighed, abundant finely ground mixing;
The metallic element compound is metal oxides or metallic element salt compounds;
2) by the mixture that step 1) obtains at 1500-1650 DEG C of temperature, under reducing atmosphere, sintering 4-8 hours are Obtain sintered body;
3) after the sintered body grinding obtained step 2), scrubbed, filtering, drying are suitable to the indigo plant of near ultraviolet excitation Color luminescent phosphor.
In the above-mentioned technical solutions, in step 2):The reducing atmosphere is with CO or H2And N2Gaseous mixture is as also Primordial Qi Atmosphere.
In the above-mentioned technical solutions, in step 2):The temperature of the sintering is 1550-1600 DEG C, and the time is 4 hours.
A kind of application of blue luminescent phosphor suitable near ultraviolet excitation, the blue luminescent phosphor is as near purple Outer smooth LED light-converting material, applied to blue light emitting device or device.
A kind of application of blue luminescent phosphor suitable near ultraviolet excitation, the blue luminescent phosphor and other face Color luminescent phosphor mixes, applied to white light emitting device or device.
In the above-mentioned technical solutions, other described colour light emitting fluorescent material are the green glow and feux rouges for being adapted near ultraviolet excitation Fluorescent material.
The beneficial effects of the invention are as follows:
Blue luminescent phosphor provided by the invention suitable near ultraviolet excitation, utilize rare earth element ce3+The 4f- of ion 5d band structures, the blue light hair that peak is located at 445-480nm scopes can be sent in the case where 380-450nm range of wavelength light excites Penetrate, have effectively achieved the light transformation for launching blue light under near ultraviolet excitation.
The preparation method of blue luminescent phosphor provided by the invention suitable near ultraviolet excitation is simple, it is pollution-free, into This is low.
Blue luminescent phosphor provided by the invention suitable near ultraviolet excitation, it can turn as black light LED light Conversion materials, blue light emitting device or device are realized, or mixed with other colour light emitting fluorescent material, realize white light emitting device or dress Put.The fluorescent material may also have certain answer in the field such as FED (Field Emission Display) and PDP (plasma scope) With.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 is embodiment 1SrLu2O4:Ce3+XRD diffracting spectrums.
Fig. 2 is embodiment 1SrLu2O4:Ce3+Launching light spectrogram (403nm is excited).
Fig. 3 is embodiment 1SrLu2O4:Ce3+Exciting light spectrogram (monitoring 458nm).
Fig. 4 is embodiment 1SrLu2O4:Ce3+Alternating temperature Strength Changes figure.
Fig. 5 is embodiment 1SrLu2O4:Ce3+The white light LEDs electroluminescent light spectrogram of encapsulation.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
A kind of blue luminescent phosphor suitable near ultraviolet excitation, its formula are:Sr1-xMxLu2-yLnyO4:Ce3+ m,An, Wherein M represents one kind or any combination in Mg, Ca and Ba;Ln represents one kind or any combination in Y, La, Gd and Sc;A generations One kind or any combination in table Li, Na, K, Rb and Cs;0≤x≤0.5,0≤y≤1,0.0001≤m≤0.01;0≤n≤ 0.01.M and Ln is characteristics of luminescence conditioning agent, and A is charge compensator, and the general expression of the fluorescent material is:SrLu2O4:Ce3+
A kind of preparation method of blue luminescent phosphor suitable near ultraviolet excitation, comprises the following steps:
1) each metallic element compound in formula is stoichiometrically weighed, abundant finely ground mixing;
The metallic element compound is metal oxides or metallic element salt compounds;
2) mixture for obtaining step 1), insert in high-purity corundum or other kinds of crucible, in temperature 1500-1650 In DEG C, in CO or H2And N2Under gaseous mixture reducing atmosphere condition, sintering 4-8 hours obtain sintered body;It is preferred that sintering time is 1550-1600 DEG C, the time is 4 hours.
3) after step to be obtained to the sintered body grinding 2) obtained, scrubbed, filtering, drying are suitable near ultraviolet excitation Blue luminescent phosphor.
A kind of application of blue luminescent phosphor suitable near ultraviolet excitation, the blue luminescent phosphor is as near purple Outer smooth LED light-converting material, applied to blue light emitting device or device, or the blue luminescent phosphor and other colors Luminescent phosphor mixes, applied to white light emitting device or device.Other described colour light emitting fluorescent material can be to be adapted to nearly purple Outer light activated green glow and red light fluorescent powder.
Embodiment 1:Prepare Sr1-xMxLu2-yLnyO4:Ce3+ m,An, wherein x=0;Y=0;M=0.002;N=0;It is expressed Formula is:SrLu2O4:Ce3+ 0.002.Stoichiometrically weigh SrCO3, Lu2O3And CeO2, by the fully finely ground mixing of the raw material weighed Afterwards, high-purity corundum crucible is inserted, in 1600 DEG C, H2And N2Under reducing atmosphere condition, sinter 4 hours, after cooling discharging, slightly grind Mill, scrubbed, filtering, drying to the blue luminescent phosphor sample.Its XRD diffracting spectrum is as shown in figure 1, and standard card Sheet data contrasts, it is seen that the sample is the SrLu of pure phase2O4Structure.Its emission spectrum and excitation spectrum as shown in Figure 2,3, excite Effective excites scope covering 380-450nm is composed, excites peak to be located near 403nm;Emission spectra covers 417-600nm, hair Peak is penetrated to be located near 458nm.Fig. 4 is the alternating temperature spectrum of the sample, and at 150 DEG C, its luminous intensity is still at 25 DEG C 86%, show that it has excellent heat endurance, possess application performance.Fig. 5 is that the sample coordinates 405nm ultraviolet chips, group The spectrum of the white light LEDs of yellow and red fluorescence powder acquisition is closed, can be obtained by the different proportion of component high aobvious under different-colour The white light of colour index.
Embodiment 2 is to embodiment 122:Preparation process is all identical with embodiment 1, its chemical formula, synthesis temperature, roasting time All it is listed in subordinate list 1 with glow color, embodiment 2 is carried out in CO reducing atmosphere conditions, embodiment 2 to the institute of embodiment 122 With the oxide or salt compounds that raw material is each metallic element.
The embodiment 1-122 of subordinate list 1 chemical formula, synthesis temperature, roasting time and glow color
Method of manufacturing fluorescent material of the invention is simple as can be seen from the above embodiments, and pollution-free, cost is low, chemically Can be stable.The material is by as a kind of blue light emitting material of the very suitable near ultraviolet excitation with practical value.
Utilize the method for blue luminescent phosphor provided by the invention and black light LED die encapsulation blue light emitting device It is as follows:
1) nearly ultraviolet leds die bonding is on LED support, and by the both positive and negative polarity of LED chip by metal wire or Conducting resinl is connected with support both positive and negative polarity;
2) blue luminescent phosphor provided by the invention is mixed with encapsulating materials such as epoxy resin or silica gel, stirring is equal It is even, stand 0.5h and exclude bubble, form arogel;
3) arogel in step 2) is coated in LED support, covers LED chip and metal wire;
4) LED support in step 3) is put into baking oven, 120-150 DEG C of solidification 2-4h, you can obtain blue illuminator Part.
Utilize the method for blue luminescent phosphor provided by the invention and black light LED die encapsulation white light emitting device It is as follows:
1) nearly ultraviolet leds die bonding is on LED support, and by the both positive and negative polarity of LED chip by metal wire or Conducting resinl is connected with support both positive and negative polarity;
2) green glow and red light fluorescent powder of blue luminescent phosphor provided by the invention and suitable near ultraviolet excitation are pressed Certain proportion is well mixed;
3) the bluish-green red fluorescence being well mixed in step 2) is mixed into powder to mix with encapsulating materials such as epoxy resin or silica gel, stirred Mix uniformly, stand 0.5h and exclude bubble, form arogel;
4) arogel of step 3) is coated in LED support, covers LED chip and metal wire;
5) LED support in step 4) is put into baking oven, 120-150 DEG C of solidification 2-4h, you can obtain white-light emitting device Part.
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 (8)

1. a kind of blue luminescent phosphor suitable near ultraviolet excitation, it is characterised in that its formula is:Sr1-xMxLu2- yLnyO4:Ce3+ m,An, wherein M represents one kind or any combination in Mg, Ca and Ba;Ln represents one kind in Y, La, Gd and Sc Or any combination;A represents one kind or any combination in Li, Na, K, Rb and Cs;0≤x≤0.5,0≤y≤1,0.0001≤m ≤0.01;0≤n≤0.01.
2. it is suitable to the blue luminescent phosphor of near ultraviolet excitation according to claim 1, it is characterised in that its expression formula For:SrLu2O4:Ce3+ 0.002
3. a kind of preparation method of the blue luminescent phosphor suitable near ultraviolet excitation described in claim 1 or 2, its feature It is, comprises the following steps:
1) each metallic element compound in formula is stoichiometrically weighed, abundant finely ground mixing;
The metallic element compound is metal oxides or metallic element salt compounds;
2) by the mixture that step 1) obtains at 1500-1650 DEG C of temperature, under reducing atmosphere, sintering 4-8 hours obtain Sintered body;
3) after the sintered body grinding obtained step 2), scrubbed, filtering, drying are suitable to the blueness hair of near ultraviolet excitation Emitting phosphor.
4. preparation method according to claim 3, it is characterised in that in step 2):The reducing atmosphere is with CO or H2 And N2Gaseous mixture is as reducing atmosphere.
5. preparation method according to claim 3, it is characterised in that in step 2):The temperature of the sintering is 1550- 1600 DEG C, the time is 4 hours.
6. a kind of application of the blue luminescent phosphor suitable near ultraviolet excitation described in claim 1 or 2, its feature exist In light-converting material of the blue luminescent phosphor as black light LED, applied to blue light emitting device or device.
7. a kind of application of the blue luminescent phosphor suitable near ultraviolet excitation described in claim 1 or 2, its feature exist In the blue luminescent phosphor mixes with other colour light emitting fluorescent material, applied to white light emitting device or device.
8. the application of the blue luminescent phosphor according to claim 7 suitable near ultraviolet excitation, it is characterised in that institute It is the green glow and red light fluorescent powder for being adapted near ultraviolet excitation to state other colour light emitting fluorescent material.
CN201710777752.2A 2017-09-01 2017-09-01 Blue light-emitting fluorescent powder suitable for near ultraviolet light excitation and preparation method and application thereof Active CN107541211B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330971A (en) * 2019-07-17 2019-10-15 重庆理工大学 A kind of upper conversion temperature-measurement material of high sensitivity and its preparation method and application
CN111139074A (en) * 2020-01-21 2020-05-12 济南大学 Temperature-sensitive fluorescent powder and preparation method and application thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102994084A (en) * 2012-12-12 2013-03-27 中国科学院长春光学精密机械与物理研究所 Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102994084A (en) * 2012-12-12 2013-03-27 中国科学院长春光学精密机械与物理研究所 Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GEN LI等: "Synthesis, structure and photoluminescence properties of Ce3+-doped SrSc2O4: a new scandate green-emitting phosphor with blue excitation", 《NEW J.CHEM.》 *
KYEONG-HO KIM等: "Synthesis of SrLu2O4:Eu2+ red phosphors and their photoluminescence properties", 《JOURNAL OF LUMINESCENCE》 *
SONGBIN LIU等: "Intense upconversion luminescence and energy-transfer mechanism of Ho3+/Yb3+ co-doped SrLu2O4 phosphor", 《J AM CERAM SOC》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330971A (en) * 2019-07-17 2019-10-15 重庆理工大学 A kind of upper conversion temperature-measurement material of high sensitivity and its preparation method and application
CN110330971B (en) * 2019-07-17 2022-04-22 重庆理工大学 High-sensitivity up-conversion temperature measurement material and preparation method and application thereof
CN111139074A (en) * 2020-01-21 2020-05-12 济南大学 Temperature-sensitive fluorescent powder and preparation method and application thereof

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