CN105969347A - Method for acquiring up-conversion white light - Google Patents

Method for acquiring up-conversion white light Download PDF

Info

Publication number
CN105969347A
CN105969347A CN201610379038.3A CN201610379038A CN105969347A CN 105969347 A CN105969347 A CN 105969347A CN 201610379038 A CN201610379038 A CN 201610379038A CN 105969347 A CN105969347 A CN 105969347A
Authority
CN
China
Prior art keywords
white light
conversion
doping content
light
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610379038.3A
Other languages
Chinese (zh)
Inventor
秦伟平
李洋洋
刘晓辉
郭俊杰
秦冠仕
吴长锋
尹升燕
狄卫华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201610379038.3A priority Critical patent/CN105969347A/en
Publication of CN105969347A publication Critical patent/CN105969347A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/779—Halogenides
    • C09K11/7791—Halogenides with alkali or alkaline earth metals
    • 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 aims to provide a method for acquiring up-conversion white light under 0-980 nm near-infrared light excitation. Firstly, a Yb<3+>/Eu<3+>/Y<3+> up-conversion luminescent material doped with CaF2 is prepared. Under 0-980 nm near-infrared light excitation, Yb<3+> ions in the material serve as sensitizer for transmitting energy to Eu<3+> and exciting Eu<3+> and also serve as activator for cooperation for emission of 480-540 nm blue and green light. Eu<3+> serves as activator for red and blue luminescence. Furthermore, Y<3+> with different dosage concentrations is used for quenching Yb<3+> cooperative luminescence, and therefore the purpose of adjusting the proportion of the three primary colors is achieved, and material up-conversion white light emission is achieved when the concentration of Y<3+> is 1 mol%.

Description

A kind of method obtaining conversion of white light
Technical field
The invention belongs to up-converting phosphor technology field, be specifically related to a kind of method obtaining conversion of white light.
Background technology
In recent years, the method utilizing HONGGUANG, green glow, three kinds of primary lights of blue light to be combined synthesizing white light has had More report.Such as, Downing etc. are at Pr3+/Er3+/Tm3+The fluoride glass HMFGs of codope In achieve conversion of white light launch.Wherein, Pr3+, Er3+, Tm3+There is provided respectively the HONGGUANG in three primary colours light, Green glow and blue light.It is recognised that utilize in the method for primary lights synthesis white light involved report before from Rare earth ion be mainly Tm3+, Er3+, Ho3+And Pr3+。
Summary of the invention
It is an object of the invention to provide a kind of method obtaining conversion of white light.First, preparation Yb3+/Eu3+/Y3+ Codope CaF2Up-conversion luminescent material.～under 980nm near infrared light excites, the Yb in material3+ It is Eu that ion serves not only as sensitizer3+Transmission energy also makes it excite, and launches simultaneously as activator cooperation The blue green light of 480～540nm.Eu3+Then provide red and blue-light-emitting as activator.Further, profit With the Y of different levels of doping3+Quencher Yb3+Cooperative luminescence, thus reach to regulate the purpose of three kinds of primary colours ratios, And at Y3+Concentration is that the upper conversion of white light achieving material during 1mol% is launched.
A kind of method obtaining conversion of white light that the present invention provides, it is characterised in that:
(1), by trivalent ytterbium ion (Yb3+), trivalent europium ion (Eu3+), trivalent ruthenium ion (Y3+) altogether With being doped in alkaline earth metal fluoride substrate material；With the molar concentration of whole metal cations with for 100% Calculate, wherein, Yb3+Doping content be 0mol%～1.5mol%；Eu3+Doping content be 0.01mol%～0.10mol%；Y3+Doping content scope be 0mol%～2mol%；
(2), under the exciting of 980nm near infrared light, two Yb3+The indigo plant of 480～540nm is launched in cooperation Normal complexion green fluorescence, Eu3+Emission of ions blueness and red fluorescence, thus provide three bases obtained needed for white light Coloured light, utilizes the Y of different levels of doping3+To Yb3+The quenching effect of cooperative luminescence regulates and changes on material Glow color, regulates three kinds of primary colours ratios, it is achieved the upper conversion of white light of material is launched.
Preferably, described Y3+Doping content be 1mol%, Yb3+Doping content be 1mol%, Eu3+ Doping content be 0.05mol%.
Preferably, described alkali earth metal fluoride is CaF2。
Compared with prior art, present invention have the advantage that
The present invention have selected the Eu that can simultaneously provide blue light and HONGGUANG3+And and Yb3+And Eu3+Between do not have The Y of energy transitive relation3+, and both ions are at CaF2:Yb3+/Eu3+/Y3+White light system plays Important effect.Only Yb in material3+And Eu3+Between exist energy transmission, reduce between rare earth ion Cross-relaxation phenomenon；Utilize Y3+The color of the change regulation up-conversion luminescence of ion concentration so that luminescence is more Add the white portion being accessible to chromaticity coordinates.Additionally, with traditional Yb3+/Tm3+/Er3+And Yb3+/Tm3+/Ho3+ Compare etc. system, use Eu3+And Y3+, expand the selection model of conversion of white light material to some degree Enclose.
Accompanying drawing explanation
Fig. 1: doping variable concentrations x% (x=0,0.1,0.5,1,1.5) Yb3+CaF2Sample is closely Up-conversion emission spectrum under infrared ray excited；
Fig. 2: under near infrared light excites, doping variable concentrations y% (y=0.01,0.03,0.05,0.07, 0.10)Eu3+CaF2: 1%Yb3+/ y%Eu3+The Up-conversion emission spectrum of sample；
Fig. 3: under near infrared light excites, adulterate variable concentrations z% (z=0,0.5,1,2) Y3+'s CaF2: 1%Yb3+/ 0.05%Eu3+/ z%Y3+The Up-conversion emission spectrum of sample；
Fig. 4: Yb3+And Eu3+Energy diagram and upper conversion energy transfer mechanism figure；
Fig. 5: under near infrared light excites, CaF2: 1%Yb3+/ 0.05%Eu3+/ z%Y3+Sample 500nm sends out Penetrate peak (Yb3+Ion pair cooperation launch) life curve.
Detailed description of the invention
Embodiment 1:
It is prepared for Yb with high temperature solid-state fusion method3+(0,0.1,0.5,1,1.5mol%) CaF singly mixed2 Dusty material.The raw material that experiment is used is CaF2、YbF3.Weigh CaF the most respectively2(pure Degree 99.99%) 0.3900 gram, 0.3896 gram, 0.3881 gram, 0.3861 gram, 0.3842 gram and YbF3 (purity 99.99%) 0 gram, 0.0012 gram, 0.0058 gram, 0.0115 gram, 0.0173 gram, by two kinds Mixed being incorporated in agate mortar of powder is fully ground.After grinding subsequently, sample is placed in the high temperature having argon gas atmosphere In tube furnace, calcine 2 hours under the conditions of 1400 DEG C.Reaction takes out sample after terminating, and sample is carried out light Spectrum test.Fig. 1 is doping variable concentrations Yb3+The Up-conversion emission spectrum of material.Spectrum is analyzed table Bright, the wide emission peak being positioned at 480nm～550nm comes from two Yb3+Cooperative luminescence.It can be seen that Work as Yb3+Cooperative luminescence maximum intensity when concentration is 1%.
Embodiment 2:
Use test method same as in Example 1 and with reference to embodiment 1 result, select Yb3+Doping content For 1mol%, Eu3+Doping content respectively 0.01,0.03,0.05,0.07,0.10mol% is prepared for series Yb3+And Eu3+The CaF of codope2Dusty material, corresponding Eu2O3Quality be respectively 0.0002 gram, 0.0006 gram, 0.0009 gram, 0.0014 gram and 0.0018 gram.From the emission spectrum of Fig. 2 it can be seen that With Yb3+Singly mix CaF2Material is compared, CaF2:Yb3+/Eu3+The spectrum of series of samples all occurs in that Eu3+ Characteristic emission peak.Along with Eu3+Concentration increases, Yb3+The luminous intensity of ion pair is gradually lowered, Eu3+'s Emission peak intensity first increases and reduces afterwards.Work as Eu3+When concentration is 0.05mol%, Eu in material3+Emission peak Maximum intensity.
Embodiment 3:
With reference to the result of embodiment 1 and 2, high temperature solid-state method is used to be prepared for Yb3+(1mol%), Eu3+(0.05 Mol%), Y3+(0,0.5,1,2mol%, corresponding YF3Quality be respectively 0 gram, 0.0036 gram, 0.0073 Gram and 0.0146 gram) three CaF mixed2Dusty material, and sample is carried out spectrum test.Fig. 3 spectrum is deposited At two Yb3+Cooperation launch and Eu3+Series of features peak, along with Y3+The increase of doping molar fraction, Yb3+Cooperation transmitting gradually weakens.Work as Y3+When molar concentration is 2mol%, Yb3+The cooperation of ion pair is launched several Do not observe, work as Y3+When molar concentration is 1mol%, the ratio of three kinds of primary colours reaches optimal, it is thus achieved that Upper conversion of white light is launched, and its chromaticity coordinate is (0.31,0.33).
Under 980nm light excites, give CaF2:Yb3+/Eu3+/Y3+The upper conversion topology mechanism choice of material, See Fig. 4.Green portions comes from two Yb3+Cooperation launch.For red light portion, Yb3+-dimers will Energy passes to Eu3+And population arrives it5D1Energy level, the most radiationless relaxes towards5D0Energy level, obtains peak value position At 608nm and 625nm5D0→7F2Red emission.It addition, it is metastable5D0With5D1Energy level Continue the energy jump absorbing a near-infrared photon to higher5D4Energy level, is then passed through a series of radiationless Relax towards5D3,5D2,5D1,5D,0, continue to be positioned at 417nm, 424nm to the peak value that more low-lying level transition obtains, Multiple emission peaks of 434nm, 446nm and 470nm, it is provided that the blue light components in three primary colours.
Under 980nm pulsed light excites, measure CaF2: 1%Yb3+/ 0.05%Eu3+/ z%Y3+(z=0,0.5, 1,2) dynamics data that at sample 500nm, cooperation is launched.Fig. 5 is seen according to the curve that acquired results is drawn. CaF2:Yb3+The curve of sample is the single exponential function curve of approximation.At CaF2:Yb3+/Eu3+In, Yb3+- Ion pair transfers energy to Eu3+Make Yb3+The cooperative luminescence fluorescence lifetime of ion shortens, along with in sample The Y of doping3+Concentration is gradually increased, and the life-span of 500nm emission peak shortens further.In general, Y3+With Yb3+And Y3+With Eu3+Between do not have energy to transmit, this illustrates Yb3+Ion pair and Eu3+Between also exist Relatively effective energy transmits.

Claims (3)

1. the method obtaining upper conversion of white light, it is characterised in that:
(1), by trivalent ytterbium ion (Yb3+), trivalent europium ion (Eu3+), trivalent ruthenium ion (Y3+) altogether With being doped in alkaline earth metal fluoride substrate material；With the molar concentration of whole metal cations with for 100% Calculate, wherein, Yb3+Doping content be 0mol%～1.5mol%；Eu3+Doping content be 0.01mol %～0.10mol%；Y3+Doping content scope be 0mol%～2mol%；
(2), under the exciting of 980nm near infrared light, two Yb3+The indigo plant of 480～540nm is launched in cooperation Normal complexion green fluorescence, Eu3+Emission of ions blueness and red fluorescence, thus provide three bases obtained needed for white light Coloured light, utilizes Y3+To Yb3+The quenching effect of cooperative luminescence regulates material up-conversion luminescence color, regulation Three kinds of primary colours ratios, it is achieved the upper conversion of white light of material is launched.
A kind of method obtaining conversion of white light the most as claimed in claim 1, it is characterised in that: described Y3+Doping content be 1mol%, Yb3+Doping content be 1mol%, Eu3+Doping content be 0.05 Mol%.
A kind of method obtaining conversion of white light the most as claimed in claim 1, it is characterised in that: described Alkali earth metal fluoride is CaF2。
CN201610379038.3A 2016-05-31 2016-05-31 Method for acquiring up-conversion white light Pending CN105969347A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610379038.3A CN105969347A (en) 2016-05-31 2016-05-31 Method for acquiring up-conversion white light

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610379038.3A CN105969347A (en) 2016-05-31 2016-05-31 Method for acquiring up-conversion white light

Publications (1)

Publication Number Publication Date
CN105969347A true CN105969347A (en) 2016-09-28

Family

ID=57010013

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610379038.3A Pending CN105969347A (en) 2016-05-31 2016-05-31 Method for acquiring up-conversion white light

Country Status (1)

Country Link
CN (1) CN105969347A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163945A (en) * 2017-07-05 2017-09-15 山东大学 A kind of rear-earth-doped fluorination lutetium sodium up-conversion luminescence nanomaterial and preparation method thereof
CN107748147A (en) * 2017-10-09 2018-03-02 合肥工业大学 A kind of white luminous upper conversion nano particle and based on the test strips that multicomponent tumor-marker analyte detection is realized while its
CN109181684A (en) * 2018-08-17 2019-01-11 中国科学院上海硅酸盐研究所 A kind of crystalline material and preparation method thereof for realizing white light emission by upper conversion
CN110452701A (en) * 2019-08-21 2019-11-15 哈尔滨学院 The method that mixing based on rear-earth-doped upper conversion nano crystalline substance fine-tunes coloration

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618284A (en) * 2012-03-15 2012-08-01 吉林大学 Bioluminescent nanoparticle with 800-nanometer strong near infrared up-conversion emission characteristic and application thereof
CN103224787A (en) * 2013-04-19 2013-07-31 中国科学院福建物质结构研究所 Rare earth-doped alkaline earth metal fluoride nano material, and preparation method and application thereof
CN103289701A (en) * 2013-07-02 2013-09-11 哈尔滨工业大学 Method for preparing heterogeneous nuclear shell structure CaF2:20Yb, 2Ho@NaXF4 nanocrystalline
CN103343007A (en) * 2013-07-02 2013-10-09 哈尔滨工业大学 Small-size heterogeneous nuclear shell CaF2: 2Er3+, 20Yb3+@ NaXF4nanocrystalline preparation
WO2013181076A1 (en) * 2012-05-30 2013-12-05 University Of Massachusetts Medical School Coated up-conversion nanoparticles
CN103865519A (en) * 2014-03-27 2014-06-18 合肥工业大学 Preparation method for up-conversion luminescent nano-probe and application of up-conversion luminescent nano-probe to measurement of antioxidant activity of substance
CN104099091A (en) * 2013-04-09 2014-10-15 海洋王照明科技股份有限公司 Neodymium-and-ytterbium-codoped alkaline earth fluoride glass up-conversion luminescent material, and preparation method and application thereof
CN105219379A (en) * 2015-11-02 2016-01-06 吉林大学 A kind of method of quencher up-conversion luminescence

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618284A (en) * 2012-03-15 2012-08-01 吉林大学 Bioluminescent nanoparticle with 800-nanometer strong near infrared up-conversion emission characteristic and application thereof
WO2013181076A1 (en) * 2012-05-30 2013-12-05 University Of Massachusetts Medical School Coated up-conversion nanoparticles
CN104099091A (en) * 2013-04-09 2014-10-15 海洋王照明科技股份有限公司 Neodymium-and-ytterbium-codoped alkaline earth fluoride glass up-conversion luminescent material, and preparation method and application thereof
CN103224787A (en) * 2013-04-19 2013-07-31 中国科学院福建物质结构研究所 Rare earth-doped alkaline earth metal fluoride nano material, and preparation method and application thereof
CN103289701A (en) * 2013-07-02 2013-09-11 哈尔滨工业大学 Method for preparing heterogeneous nuclear shell structure CaF2:20Yb, 2Ho@NaXF4 nanocrystalline
CN103343007A (en) * 2013-07-02 2013-10-09 哈尔滨工业大学 Small-size heterogeneous nuclear shell CaF2: 2Er3+, 20Yb3+@ NaXF4nanocrystalline preparation
CN103865519A (en) * 2014-03-27 2014-06-18 合肥工业大学 Preparation method for up-conversion luminescent nano-probe and application of up-conversion luminescent nano-probe to measurement of antioxidant activity of substance
CN105219379A (en) * 2015-11-02 2016-01-06 吉林大学 A kind of method of quencher up-conversion luminescence

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANGYANG LI等: "White upconversion luminescence in CaF2:Yb3+/Eu3+ powders via the incorporation of Y3+ ions", 《PHYS.CHEM.CHEM.PHYS》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163945A (en) * 2017-07-05 2017-09-15 山东大学 A kind of rear-earth-doped fluorination lutetium sodium up-conversion luminescence nanomaterial and preparation method thereof
CN107163945B (en) * 2017-07-05 2019-09-06 山东大学 Rear-earth-doped fluorination lutetium sodium up-conversion luminescence nanomaterial of one kind and preparation method thereof
CN107748147A (en) * 2017-10-09 2018-03-02 合肥工业大学 A kind of white luminous upper conversion nano particle and based on the test strips that multicomponent tumor-marker analyte detection is realized while its
CN107748147B (en) * 2017-10-09 2020-10-23 合肥工业大学 White luminous up-conversion nano-particles and test strip based on same and capable of simultaneously realizing detection of multi-component tumor markers
CN109181684A (en) * 2018-08-17 2019-01-11 中国科学院上海硅酸盐研究所 A kind of crystalline material and preparation method thereof for realizing white light emission by upper conversion
CN109181684B (en) * 2018-08-17 2021-07-13 中国科学院上海硅酸盐研究所 Crystal material for realizing white light emission through up-conversion and preparation method thereof
CN110452701A (en) * 2019-08-21 2019-11-15 哈尔滨学院 The method that mixing based on rear-earth-doped upper conversion nano crystalline substance fine-tunes coloration
CN110452701B (en) * 2019-08-21 2022-07-26 哈尔滨学院 Method for finely adjusting chromaticity by mixing based on rare earth doped up-conversion nanocrystalline

Similar Documents

Publication Publication Date Title
CN102120931B (en) Red fluorophor and preparation method thereof
CN105969347A (en) Method for acquiring up-conversion white light
CN105778913B (en) A kind of list matrix three adulterates white light phosphor and preparation method and application
CN108350356A (en) Metal fluoride red-emitting phosphor and use its light-emitting component
CN101402857B (en) Red luminous material for LED and producing process thereof
CN105219382A (en) Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application
CN105131953B (en) A kind of near ultraviolet excited white light LED rare earth ion doped new polysilicate green emitting phosphors and preparation method thereof
CN106634997A (en) Composite phosphate fluorophor and application thereof
CN106554777A (en) A kind of colourity is with adjustable luminescent material of temperature and preparation method and application
CN104531144A (en) CaMg&lt;2&gt;Al&lt;16&gt;O&lt;27&gt;:Mn &lt;4+&gt; red fluorescent powder and preparation technology thereof
CN107629794A (en) A kind of europium ion Eu3+The bismuthino luminescent material of activation, preparation method and application
CN106634996A (en) Fluorophor and application method thereof
CN104232081B (en) A kind of light converting function material and its preparation method and application
CN106753346A (en) Nitrogen oxides fluorophor and its luminescent device
CN105255491B (en) A kind of photochromic adjustable fluorescent material and preparation method thereof
CN105038783B (en) Additive Mn germanate solid solution red fluorescence powder and preparation method
CN105899641A (en) Phosphor and light emitting device
CN101705094B (en) Near ultraviolet excited blue-green fluorescent powder for semiconductor illumination and preparation method thereof
CN107163943A (en) It is a kind of to be suitable near ultraviolet excitated regulatable fluorescent material of spectrum and preparation method thereof
CN106554778A (en) A kind of single-substrate single-doping white luminescent material and preparation method and application
CN114574206A (en) Fluorescent powder for white light-emitting diode and synthetic method and application thereof
CN108148591A (en) A kind of nitride red fluorophor, preparation method and white light-emitting diodes lighting source
CN104194781B (en) Long persistence luminescent material with single substrate and adjustable persistence colors and preparation method of long persistence luminescent material
CN106085423A (en) Conversion of white light material C aF in one2: Yb3+/ Eu3+/ Y3+
CN106701082B (en) A kind of preparation method based on Sm2+ ion up-conversion luminescence composite materials

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160928

WD01 Invention patent application deemed withdrawn after publication