CN106520118A - Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and preparation method - Google Patents
Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and preparation method Download PDFInfo
- Publication number
- CN106520118A CN106520118A CN201610814097.9A CN201610814097A CN106520118A CN 106520118 A CN106520118 A CN 106520118A CN 201610814097 A CN201610814097 A CN 201610814097A CN 106520118 A CN106520118 A CN 106520118A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- luminescent material
- conversion luminescent
- codope
- preparation
- 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
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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention provides a Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and a preparation method. ZnO is used as a matrix, and rare earth elements Ho<3+> and Yb<3+> and Li<+> are used as doping ions, and the composition formula of the material is Zn[1-x-y-z]Ho[x]Yb[y]Li[z]O. The zinc oxide upconversion luminescence material with high luminescent intensity is prepared through codoping of Ho<3+>/Yb<3+>/Li<+>, the synthesis process is simple, the repeatability is high, employed materials are environmentally friendly, safe and nontoxic, and industrialized production is easy to realize. At the same time, the upconversion luminescence intensity of zinc oxide can be obviously improved by changing Li<+> doping concentration, and can be used to display, illumination, laser anticouterfeit, etc.
Description
Technical field
The invention belongs to up-conversion luminescent material technical field, is related to a kind of Ho3+/Yb3+/Li+Turn on codope zinc oxide
Change luminescent material.
Background technology
In recent years, rear-earth-doped up-conversion luminescent material shown in 3 D stereo due to which, laser anti-counterfeit, bioluminescence mark
The extensive application in the field such as note and short wavelength laser, arouses great concern.But for entirety, up-conversion luminescence effect
Rate is also than relatively low.Some preferable materials of conventional luminescent properties are gone back at aspects such as thermally and chemically stability, mechanical strengths at present
There are some problems not solve, this just brings difficulty to practical application.So it is all to find high conversion efficiency, physical and chemical performance
Good New-type matrix material becomes one of study hotspot of current up-conversion luminescent material.
Zinc oxide (ZnO) as a kind of new direct wide bandgap semiconductor materials, energy gap is at room temperature
3.37eV, with higher exciton binding energy (60meV), has stronger absorption in ultra-violet (UV) band, and its physics and chemical property is steady
It is fixed, with relatively low phonon energy (437cm-1), this makes it possible to become preferable up-conversion luminescence host material.But arrive
So far, the up-conversion luminescence efficiency of rear-earth-doped ZnO material is also than relatively low.Wherein one of reason is that rare earth ion is general very
It is difficult to replace Zn2+The form of lattice point enters ZnO lattices.This is because radius ratio Zn of trivalent rare earth ionses2+Ion is much bigger,
And both electric charges are mismatched.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of Ho3+/Yb3+/Li+On codope zinc oxide, conversion is sent out
Luminescent material and preparation method, solve prior art zinc oxide up-conversion luminescent material complicated process of preparation, and luminous intensity is low, it is impossible to
Carry out the technical problem of high-concentration dopant.
The technical solution adopted in the present invention is：
Ho3+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material, with ZnO as matrix, with rare earth element Ho3+And Yb3 +, and Li+Ion is Doped ions, consisting of, Zn1-x-yHoxYbyLizO, wherein 8.5mol%≤x+y+z≤
15.5mol%.
Preferably, Ho3+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material is consisted of, Zn1-x-yHoxYbyLizO, its
Middle x=1mol%, y=7.5mol%, z≤7mol%.
Ho3+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material preparation method, comprises the following steps：
Step one, zinc acetate or zinc nitrate are dissolved in deionized water, stirring, until zinc acetate or zinc nitrate fully dissolve
Obtain zinc solution；
Step 2, by Ho2O3、Yb2O3And Li2CO3It is dissolved in after mixing in dust technology or dilute hydrochloric acid solution, 40 DEG C～60 DEG C add
Solution is evaporated to obtain powdered rubber for 50 DEG C～70 DEG C to after fully reacting by thermal agitation；
Step 3, powdered rubber obtained by step 2 is dissolved in the water, is stirred to clarify, and step one gained zinc is dropwise added dropwise
Salting liquid, stirs to clarify to obtain solution；
Step 4, triethanolamine or MEA are added dropwise in step 3 resulting solution, to it is initial when occur it is white
Color flocculent deposit is completely dissolved, and obtains colourless transparent solution；
Step 5, polyethylene glycol -600 or PEG-4000 are added in step 4 resulting solution, stirring mixing；
Step 5 resulting solution is proceeded to autoclave by step 6, is reacted 2～6h at 140 DEG C～180 DEG C, is treated high pressure
Reactor is cooled to room temperature, is precipitated thing；
Step 7, step 6 gained sediment is centrifuged, is cleaned, 60 DEG C～80 DEG C 2～4h of drying and grinding after
White powder is obtained, 550 DEG C～750 DEG C 2～4h of annealing of white powder are made annealing treatment.
The invention has the beneficial effects as follows
1st, Ho of the present invention3+/Yb3+/Li+Codope prepares the high zinc oxide up-conversion luminescent material of luminous intensity, synthesizes work
Skill is simple, and repeatable high, material therefor is environmentally friendly, safety non-toxic, it is easy to accomplish industrialized production.
2nd, the zinc oxide up-conversion luminescent material luminous intensity that prepared by the present invention is strong, can be used to showing, illuminates, laser anti-counterfeit
Etc. aspect.
3rd, the Ho that the present invention is provided3+/Yb3+/Li+The preparation method of zinc oxide up-conversion luminescent material, realizes Ho3+/Yb3 +/Li+High-concentration dopant, by change Li+Doping content can significantly improve the Up-conversion Intensity of zinc oxide.
Description of the drawings
Fig. 1 is Ho3+/Yb3+/Li+The XRD spectrum of co-doped nano ZnO；
Fig. 2 is Ho3+/Yb3+/Li+The SEM figures of co-doped nano ZnO；
Fig. 3 (a) is different Li+The Up-conversion emission spectrum of doping content sample, (b) be red-green glow integrated emission intensity with
Li+The variation relation of doping content；
Specific embodiment
Yb3+As sensitized ions, active ions Ho is greatly improved3+Absorption efficiency to pump light, therefore the present invention adopts
Use Ho3+/Yb3+The mode of codope, and the Li that adulterates+After ion, luminous intensity is remarkably reinforced again, it may be possible to due to Li+Ion is very
It is little, it is easier to be located at Ho into ZnO lattices3+Near ion, Ho is changed by charge interaction3+The local crystal field of ion
Symmetry, is adapted to 4f electron transitions, so that changing luminescence enhancement thereon.
The present invention is described in detail with reference to the accompanying drawings and detailed description, it should be noted that the present invention is not
Specific examples below is confined to, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.
Embodiment 1
The present invention provides a kind of Ho3+、Yb3+、Li+Codope ZnO up-conversion luminescent materials, chemical composition is Zn1-x-y- zHoxYbyLizO, wherein Ho3+For active ions, Yb3+For sensitizer, x is Ho3+The mole percent of doping, y are Yb3+Doping
Mole percent, z are Li+The mole percent of doping, and x+y+z=15.5mol%, preparation process are as follows：
Step one, prepares acetic acid zinc solution, takes the Zn (Ac) of 6.585g2, it is dissolved in 30ml deionized waters, stirs, until
1. which be fully dissolved into colourless transparent solution.
Step 2, prepares rare earth nitrades and lithium nitrate.Zn in proportion:Ho:Yb:Li=0.915:0.01:0.075:
0.07 weighs corresponding rare earth oxide (Ho2O3、Yb2O3) and lithium carbonate, it is dissolved in after being well mixed in dilute nitric acid solution, 40
DEG C～60 DEG C of heating stirrings, after fully reacting, solution is evaporated in 50 DEG C～70 DEG C.
Step 3, above-mentioned gained powder is dissolved in 10ml deionized waters, is stirred to clarify, 1. solution is dropwise added dropwise,
Stir to clarify solution 2..
Step 4, weighs 20ml triethanolamines, is added dropwise in 2. solution, occurs white flock precipitate when initial, continues
It is added dropwise, until white precipitate is completely dissolved, finally obtains colourless transparent solution 3..
Step 5, measures polyethylene glycol -600 of 5ml, is added in 3. solution, is sufficiently stirred for so as to is well mixed.
Step 6, above-mentioned gained mixture solution is proceeded in 100ml autoclaves, under the conditions of 140 DEG C～180 DEG C
2～6h of reaction.
Step 7, after reaction terminates, takes out reactor and is cooled to room temperature.By gained sediment centrifugation, clean repeatedly
2～4h is dried at 60 DEG C～80 DEG C afterwards, grinding after drying, is taken out.Finally by above-mentioned gained white powder at 550 DEG C～750 DEG C
2～4h of lower annealing.
Embodiment 2
The present embodiment Ho3+/Yb3+/Li+Chemical composition of codope ZnO up-conversion luminescent materials and preparation method thereof with
Embodiment 1 is identical, except for the difference that x+y+z=13.5mol%, and wherein x is 1mol%, and y is 7.5mol%, and z is 5mol%.
Embodiment 3
The present embodiment Ho3+/Yb3+/Li+Chemical composition of codope ZnO up-conversion luminescent materials and preparation method thereof with
Embodiment 1 is identical, except for the difference that x+y+z=11.5mol%.
Embodiment 4
The present embodiment Ho3+/Yb3+/Li+Chemical composition of codope ZnO up-conversion luminescent materials and preparation method thereof with
Embodiment 1 is identical, except for the difference that x+y+z=9.5mol%.
Embodiment 5
The present embodiment Ho3+/Yb3+/Li+Chemical composition of codope ZnO up-conversion luminescent materials and preparation method thereof with
Embodiment 1 is identical, except for the difference that x+y=8.5mol%, z=0.
Carry out X-ray powder diffraction pattern analysis, SEM figures and sample to exist to sample obtained in above example
980nmLD excites down the Up-conversion emission spectrum for obtaining to be analyzed, as a result as follows：
Fig. 1 is 1 sample Zn of embodiment0.915Ho0.01Yb0.075Li0.075 sample Zn of O and embodiment0.915Ho0.01Yb0.075Li0O
X-ray powder diffraction pattern, standard PDF (JCPDS 36-1451) collection of illustrative plates of the solid line of bottom for ZnO.As shown in Figure 1,
All samples diffraction maximum is sharp, and principal crystalline phase is all the ZnO of hexagonal phase wurtzite structure, and crystalline quality is preferable.Due to Li+And Yb3+
Doping is more, have also appeared a small amount of Yb2O3And LiYbO2Peak.And work as Li+When doping is 7mol%, diffraction maximum is sharper
It is sharp, show that crystallite dimension further increases.
Fig. 2 is sample Zn0.845Ho0.01Yb0.075Li0.07The SEM figures of O.As seen from Figure 2, gained sample is scattered
Flower cone structure, is made up of nanometer rods, rough, has some little nano-particles, it may be possible to which part dephasign is distributed in surface
It is caused.
Fig. 3 (a) is the Up-conversion emission spectrum that the sample prepared according to embodiment scheme is obtained in the case where 980nmLD is excited.
Mix Li+Afterwards, the up-conversion fluorescence of sample has very big change, is mainly manifested in：With Li+The increase of incorporation, luminous intensity
It is remarkably reinforced, particularly green intensity increase is a lot.Work as Li+When doping reaches 5mol% (embodiment 2), up-conversion luminescence is strong
Degree reaches maximum, afterwards with Li+Incorporation, luminous intensity start reduce.Fig. 3 (b) gives the integration of ruddiness and green glow
Strength ratio is with Li+The relation of ion concentration change.As seen from the figure, red-green glow integrates ratio with Li+The change of doping content it is big and
Taper into, and tend towards stability.
Claims (9)
1.Ho3+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material, with ZnO as matrix, it is characterised in that with Ho3+、Yb3+
And Li+Codope is used as Doped ions.
2. Ho as claimed in claim 13+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material, it is characterised in that the Ho3 +/Yb3+/Li+Codope zinc oxide up-conversion luminescent material is consisted of,
Zn1-x-yHoxYbyLizO, wherein 8.5mol%≤x+y+z≤15.5mol%.
3. Ho as claimed in claim 23+/Yb3+/Li+Codope zinc oxide up-conversion luminescent material, it is characterised in that the Ho3 +/Yb3+/Li+Codope zinc oxide up-conversion luminescent material is consisted of,
Zn1-x-yHoxYbyLizO, wherein x=1mol%, y=7.5mol%, z≤7mol%.
4. the arbitrary Ho of claims 1 to 33+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, bag
Include following steps：
Step one, zinc acetate or zinc nitrate are dissolved in deionized water, stirring, until zinc acetate or zinc nitrate fully dissolve and obtain
Zinc solution；
Characterized in that,
Step 2, by Ho2O3、Yb2O3And Li2CO3It is dissolved in after mixing in dust technology or dilute hydrochloric acid solution, heating stirring is to fully instead
Should after solution is evaporated into obtain powdered rubber；
Step 3, powdered rubber obtained by step 2 is dissolved in the water, is stirred to clarify, and step one gained zinc salt is dropwise added dropwise molten
Liquid, the solution for stirring to clarify；
Step 4, triethanolamine or MEA are added dropwise in step 3 resulting solution, to it is initial when occur white wadding
Shape precipitation is completely dissolved, and obtains colourless transparent solution；
Step 5, polyethylene glycol -600 or PEG-4000 are added in step 4 resulting solution, stirring mixing；
Step 6, step 5 resulting solution is proceeded to after autoclave reacted, is treated that autoclave is cooled to room temperature, is obtained
To sediment；
Step 6 gained sediment is centrifuged, is cleaned, being dried and obtaining white powder after grinding, by white by step 7
Powder is made annealing treatment.
5. Ho as claimed in claim 43+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, its feature exist
In in the step 2, heating stirring temperature is 40 DEG C～60 DEG C.
6. Ho as claimed in claim 43+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, its feature exist
In in the step 2, solution evaporated temperature is 50 DEG C～70 DEG C.
7. Ho as claimed in claim 43+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, its feature exist
In the step 6 autoclave reaction condition is 140 DEG C～180 DEG C 2～6h of reaction.
8. Ho as claimed in claim 43+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, its feature exist
In the step 7 drying condition is 60 DEG C～80 DEG C 2～4h of drying.
9. Ho as claimed in claim 43+/Yb3+/Li+The preparation method of codope zinc oxide up-conversion luminescent material, its feature exist
In the step 7 annealing conditions are 550 DEG C～750 DEG C 2～4h of annealing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814097.9A CN106520118A (en) | 2016-09-09 | 2016-09-09 | Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610814097.9A CN106520118A (en) | 2016-09-09 | 2016-09-09 | Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106520118A true CN106520118A (en) | 2017-03-22 |
Family
ID=58343579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610814097.9A Pending CN106520118A (en) | 2016-09-09 | 2016-09-09 | Ho<3+>/Yb<3+>/Li<+> codoped zinc oxide upconversion luminescence material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106520118A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100659067B1 (en) * | 2004-11-04 | 2006-12-21 | 삼성에스디아이 주식회사 | Europium activated gadolinium zinc oxide phorsphors, method of preparing the same and field emission device comprising the same |
| CN101177611A (en) * | 2007-12-07 | 2008-05-14 | 哈尔滨工业大学 | High luminous intensity up-conversion fluorescence nano-crystal oxide and preparation method thereof |
| CN104910899A (en) * | 2015-05-13 | 2015-09-16 | 同济大学 | Rare earth doped ZnO light conversion material with high-efficiency broadband down-conversion luminescence performance and preparation method therefor |
-
2016
- 2016-09-09 CN CN201610814097.9A patent/CN106520118A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100659067B1 (en) * | 2004-11-04 | 2006-12-21 | 삼성에스디아이 주식회사 | Europium activated gadolinium zinc oxide phorsphors, method of preparing the same and field emission device comprising the same |
| CN101177611A (en) * | 2007-12-07 | 2008-05-14 | 哈尔滨工业大学 | High luminous intensity up-conversion fluorescence nano-crystal oxide and preparation method thereof |
| CN104910899A (en) * | 2015-05-13 | 2015-09-16 | 同济大学 | Rare earth doped ZnO light conversion material with high-efficiency broadband down-conversion luminescence performance and preparation method therefor |
Non-Patent Citations (3)
| Title |
|---|
| XIAOCHEN YU等: "Microstructure and upconversion luminescence in Ho3+ and Yb3+ co-doped ZnO naocrystalline powders", 《OPTICS COMMUNICATIONS》 * |
| YUNFENG BAI等: "Enhance upconversion photoluminescence intensity by doping Li+ in Ho3+ and Yb3+ codoped Y2O3 nanocrystals", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| YUNFENG BAI等: "Enhanced upconverted photoluminescence in Er3+ and Yb3+ codoped ZnO nanocrystals with and without Li+ ions", 《OPTICS COMMUNICATIONS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ntwaeaborwa et al. | Structural, optical and photoluminescence properties of Eu3+ doped ZnO nanoparticles | |
| Dhanaraj et al. | Photoluminescence characteristics of Y2O3: Eu3+ nanophosphors prepared using sol− gel thermolysis | |
| Mao et al. | Synthesis and luminescence properties of erbium-doped Y2O3 nanotubes | |
| Chen et al. | Lanthanide activator doped NaYb 1− x Gd x F 4 nanocrystals with tunable down-, up-conversion luminescence and paramagnetic properties | |
| Zhang et al. | Citrate sol-gel combustion preparation and photoluminescence properties of YAG: Ce phosphors | |
| Hou et al. | Facile template free synthesis of KLa (MoO 4) 2: Eu 3+, Tb 3+ microspheres and their multicolor tunable luminescence | |
| Wang et al. | Enhanced upconversion luminescence and single-band red emission of NaErF4 nanocrystals via Mn2+ doping | |
| Li et al. | Facile morphology-controllable hydrothermal synthesis and color tunable luminescence properties of NaGd (MoO 4) 2: Eu 3+, Tb 3+ microcrystals | |
| Chen et al. | Hollow spherical rare-earth-doped yttrium oxysulfate: A novel structure for upconversion | |
| Song et al. | OH− ions-controlled synthesis and upconversion luminescence properties of NaYF4: Yb3+, Er3+ nanocrystals via oleic acid-assisted hydrothermal process | |
| CN105694888B (en) | A kind of Mg2+Adulterate NaREF4Upconverting fluorescent material and preparation method thereof | |
| CN112375566B (en) | CsPbCl 3 Yb quantum dot and preparation method thereof | |
| Li et al. | Facile synthesis, growth mechanism and luminescence properties of uniform La (OH) 3: Ho3+/Yb3+ and La 2 O 3: Ho3+/Yb3+ nanorods | |
| Sun et al. | Upconversion emission enhancement in silica-coated Gd2O3: Tm3+, Yb3+ nanocrystals by incorporation of Li+ ion | |
| CN112940726B (en) | Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof | |
| Wang et al. | Multiple irradiation triggered the formation of luminescent LaVO4: Ln 3+ nanorods and in cellulose gels | |
| CN104927863A (en) | Method for preparing rare earth metal co-doped hexagonal NaYF4 nanocrystalline by use of discarded fluorescent powder | |
| Wang et al. | Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles | |
| CN101942299B (en) | Method for synthesizing ZnS-doped nanometer luminescent material by oil-water interface method | |
| CN105754585A (en) | Preparation method of efficient luminous oleic-acid-coated rare earth calcium fluoride nanocrystal | |
| CN106336865A (en) | Method for liquid-solid-solution synthesis of rare earth doped fluorine zinc potassium luminescent material | |
| Gao et al. | Uniform Lu 2 O 3 hollow microspheres: template-directed synthesis and bright white up-conversion luminescence properties | |
| Lian et al. | Morphology control, luminescence and energy transfer properties of NaCeF 4 and NaCeF 4: Tb 3+/Yb 3+ nanocrystals | |
| Fadlalla et al. | Sol–gel preparation and photoluminescence properties of Ce3+-activated Y3Al5O12 nano-sized powders | |
| CN106497553B (en) | A kind of Ho3+/Yb3+/Gd3+Codope zinc oxide up-conversion luminescent material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |