CN106479497B - A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof - Google Patents
A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN106479497B CN106479497B CN201610854827.8A CN201610854827A CN106479497B CN 106479497 B CN106479497 B CN 106479497B CN 201610854827 A CN201610854827 A CN 201610854827A CN 106479497 B CN106479497 B CN 106479497B
- Authority
- CN
- China
- Prior art keywords
- yttrium
- luminescent material
- erbium
- conversion luminescent
- solution
- 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.)
- Active
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
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
Abstract
The invention discloses a kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof, the Y of the chemical composition doping er element of the material2O3；The pattern of the material is the micron ball formed with laminated structure, wherein the quantity ratio for the micron ball that grain size is 16 μm is more than 95%, and the quantity ratio for the laminated structure that thickness is 0.1 0.2 μm is more than 99%.Its method is that erbium source and yttrium source are added into the solution of precipitation from homogeneous solution agent, through post-processing up to up-conversion luminescent material after being reacted using hydro-thermal method.The upper conversion luminescent material performance of the present invention is stablized, and particle diameter distribution is uniform, good crystallinity, and luminous efficiency is high.
Description
Technical field
The invention belongs to luminescent material technical fields, and in particular to a kind of High-efficiency up-conversion emission for infrared excitation is glimmering
Luminescent material and preparation method thereof.
Background technology
Numerous studies reported the up-conversion luminescence phenomenon of ion doping material in recent years.Rare earth ion is in ultraviolet-visible-
There is abundant energy level in infra-red range, and these energy levels all have longer fluorescence lifetime, therefore rare earth ion is very suitable
Cooperation is the active ions of up-conversion luminescent material.The Upconversion luminescence of rare earth ion doped material has prodigious using valence
Value can be widely applied to information processing, optical storage, temperature measurement, bioluminescence measurement, solar cell and laser anti-counterfeit etc.
Aspect.
So far, the host material of common rear-earth-doped up-conversion luminescence has：Fluoride, oxygen fluoride, sulfide
Deng.Wherein, the NaYF of hexagonal phase4It is the highest host material of upper transfer efficiency in the known up-conversion of current research.But
It is that fluoride itself is toxic, pollutes the environment.
Therefore some new methods and new material are found to improve the emphasis that luminous efficiency is up-conversion luminescence research.
Invention content
The purpose of the present invention is to provide a kind of efficient infrared excitation up-conversion luminescent materials and preparation method thereof, prepare
Method is simple, and the upper high conversion efficiency of the material of preparation has broad application prospects.
To achieve the above object, the technical scheme is that：
A kind of efficient infrared excitation up-conversion luminescent material, the Y of the chemical composition doping er element of the material2O3；It is described
The pattern of material is the micron ball formed with laminated structure, wherein the quantity ratio for the micron ball that grain size is 1-6 μm is more than 95%,
The quantity ratio for the laminated structure that thickness is 0.1-0.2 μm is more than 99%.
Preferably, the quantity ratio of micron ball of the grain size less than 1 μm is less than 5%.
Preferably, the quantity ratio of micron ball of the grain size more than 6 μm is less than 5%.
Preferably, the doping of erbium is the 1-5% of material total material amount.
A kind of preparation method of above-mentioned up-conversion luminescent material, erbium source and yttrium source are added to the solution of precipitation from homogeneous solution agent
In, through post-processing up to up-conversion luminescent material after being reacted using hydro-thermal method.
The hydro-thermal method used in the present invention is also known as hydrothermal method, belongs to the scope of liquid chemical method.It refer to the pressure appearance in sealing
In device, using water as solvent, the chemical reaction that is carried out under conditions of high temperature and pressure.
Preferably, step is：
(1) yttrium source is added in the solution of precipitation from homogeneous solution agent, clear solution is formed after being sufficiently stirred；
(2) a certain amount of erbium source is added in the clear solution of step (1), is sufficiently stirred until solution is transparent；
(3) clear solution of step (2) is transferred to closed in reaction kettle, progress hydro-thermal method reaction；
(4) product obtained by step (3) post-process up to up-conversion luminescent material.
Preferably, in the solution of precipitation from homogeneous solution agent precipitation from homogeneous solution agent a concentration of 0.01~1mol/L.
It is further preferred that when yttrium source is added in step (1), in the hydroxide ion and yttrium source in the solution of precipitation from homogeneous solution agent
Ruthenium ion molar ratio be 15:1~5.
It is further preferred that the molar concentration of ruthenium ion is 0.01~1mol/L in solution when yttrium source is added in step (1).
Preferably, the condition of the hydro-thermal method is to keep the temperature 8-24 hours at 150-200 DEG C in closed reaction kettle.
Preferably, the post-processing includes calcining.
Preferably, the post-processing includes washing, filtering, dry, calcining successively.
It is further preferred that the calcination temperature is 500-800 DEG C.
It is further preferred that the calcination time is 1-6 hours.
The yttrium source used in the present invention is can provide the compound of ruthenium ion in its aqueous solution.
The erbium source used in the present invention is can provide the compound of erbium ion in its aqueous solution.
Preferably, the yttrium source is at least one of yttrium carbonate, yttrium chloride, acetic acid yttrium, yttrium sulfate, yttrium nitrate.
Preferably, the erbium source is at least one in ErF_3 films, erbium nitrate, carbonic acid erbium, erbium chloride, erbium sulfate, carbonic acid erbium
Kind.
Preferably, the precipitation from homogeneous solution agent is at least one of urea, hexamethylenetetramine.
A kind of above-mentioned up-conversion luminescent material is information processing, optical storage, temperature measure, bioluminescence measures, solar energy
Application in battery or laser anti-counterfeit.
Beneficial effects of the present invention are：
1. the upper conversion luminescent material performance of the present invention is stablized, particle diameter distribution is uniform, good crystallinity, and luminous efficiency is high.
2. the material of the present invention is 10mW in pump power, under wavelength 1550nm laser excitations, you can obtain bright upper
Conversion shines；Pump power is the important indicator for weighing up-conversion luminescent material, under identical luminous intensity, required pump power
Lower, the light efficiency is higher.The pump power of the up-conversion luminescent material of the present invention is greatlyd improve down to 10mW
The luminous efficiency of material, closer to practical application.
3. the NaYF with the highest host material hexagonal phase of upper transfer efficiency at present4Material is compared, upper conversion of the invention
The luminous efficiency of luminescent material is better than the NaYF synthesized under the same terms4Up-conversion luminescent material, and the upper conversion hair of the present invention
Luminescent material is free of fluorine element, nontoxic.
4. patent of the present invention obtains the Yttrium oxide material of Er ions by hydro-thermal method, using precipitation from homogeneous solution agent, in high temperature height
Pressure can slow release hydroxide ion thus greatly reduce pump to control the crystallinity of material crystalline pattern and material
Pu power, greatly improves luminous efficiency.This method can be completed at a lower temperature, nontoxic, environmental-friendly, obtain
The product crystallinity arrived is high, and pattern is specific single, has efficient up-conversion luminescence performance.
5. the preparation method of up-conversion luminescent material of the present invention is simple, there are the spies such as energy saving, time saving, nontoxic and environmental-friendly
Point can be suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD diffraction analysis and control collection of illustrative plates of the Er ions Yttrium oxide material of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope image of the Er ions Yttrium oxide material of the embodiment of the present invention 1, wherein a is that scale is 10 μm
The SEM figures of (ten lattice are 10 μm, and a lattice are 1 μm), a are the SEM figures that scale is 2 μm (ten lattice are 2 μm, and a lattice are 0.2 μm)；
Fig. 3 is the up-conversion luminescence collection of illustrative plates of the Er ions Yttrium oxide material of the embodiment of the present invention 1.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
0.357g hexamethylenetetramines are dissolved in deionized water, aqueous slkali is configured to, 0.6316g nitric acid is then added
Yttrium obtains clear solution after being sufficiently stirred.It weighs a certain amount of yttrium nitrate and the above solution is added, be sufficiently stirred, obtain clear solution,
Molar ratio Y:Er=97:3.Be subsequently placed at it is closed in reaction kettle, 180 DEG C heat preservation for 24 hours, obtain white product.By production after cooling
Object washs, filters, is dried to obtain white powder, brilliant using the yttrium oxide that obtains doping erbium ion for 4 hours is calcined at 700 DEG C
Body.
The yttrium oxide crystal of obtained doping erbium ion is subjected to XRD diffraction analysis, scanning electron microscope image respectively and is above turned
The characterization of light collection of illustrative plates is changed, characterization result is as shown in Figs. 1-3.
Scanning electron microscope image, as shown in Fig. 2, the pattern in the yttrium oxide crystal of its doping erbium ion prepared is sheet knot
The micron ball of composition, wherein the quantity ratio for the micron ball that grain size is 1-6 μm is more than 95%, the sheet knot that thickness is 0.1-0.2 μm
The quantity ratio of structure is more than 99%.
By preparation doping erbium ion yttrium oxide crystal pump power be 10mW, under wavelength 1550nm laser excitations,
It can be obtained macroscopic bright up-conversion luminescence.
Embodiment 2
0.7g urea is dissolved in deionized water, aqueous slkali is configured to, 0.6316g yttrium nitrates are then added, are sufficiently stirred
After obtain clear solution.It weighs a certain amount of carbonic acid erbium and the above solution is added, be sufficiently stirred, obtain clear solution, molar ratio Y:Er
=95:5.Be subsequently placed at it is closed in reaction kettle, 120 DEG C heat preservation 10h, obtain white product.By product after cooling washing, mistake
Filter, be dried to obtain white powder, using calcined at 500 DEG C obtain within 3 hours doping erbium ion yttrium oxide object crystal.
Embodiment 3
0.7g urea is dissolved in deionized water, aqueous slkali is configured to, 0.4316g yttrium chlorides are then added, are sufficiently stirred
After obtain clear solution.It weighs a certain amount of erbium nitrate and the above solution is added, be sufficiently stirred, obtain clear solution, molar ratio Y:Er
=97:3.Be subsequently placed at it is closed in reaction kettle, 120 DEG C heat preservation 10h, obtain white product.By product after cooling washing, mistake
Filter, be dried to obtain white powder, using calcined at 500 DEG C obtain within 2 hours doping erbium ion yttrium oxide crystal.
Embodiment 4
0.6g urea is dissolved in deionized water, aqueous slkali is configured to, 0.6316g yttrium nitrates are then added, are sufficiently stirred
After obtain clear solution.It weighs a certain amount of yttrium nitrate and the above solution is added, be sufficiently stirred, obtain clear solution, molar ratio Y:Er
=98:2.Be subsequently placed at it is closed in reaction kettle, 160 DEG C heat preservation 10h, obtain white product.By product after cooling washing, mistake
It filters, be dried to obtain white powder, the yttrium oxide crystal for obtaining doping erbium ion for 3 hours is calcined at by 800 DEG C.
XRD diffraction analysis, scanning electron microscope (SEM) photograph are carried out by the yttrium oxide crystal of the doping erbium ion prepared to embodiment 2-4
The characterization of picture and up-conversion luminescence collection of illustrative plates, characterization result are identical as the result of embodiment 1.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection domain
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.
Claims (6)
1. a kind of efficient infrared excitation up-conversion luminescent material, characterized in that the chemical composition doping er element of the material
Y2O3；The pattern of the material is the micron ball formed with laminated structure, wherein the quantity for the micron ball that grain size is 1-6 μm is than big
In 95%, the quantity ratio for the laminated structure that thickness is 0.1-0.2 μm is more than 99%.
2. a kind of efficient infrared excitation up-conversion luminescent material as described in claim 1, characterized in that grain size is less than 1 μm
The quantity ratio of micron ball is less than 5%.
3. a kind of efficient infrared excitation up-conversion luminescent material as described in claim 1, characterized in that grain size is more than 6 μm
The quantity ratio of micron ball is less than 5%.
4. a kind of efficient infrared excitation up-conversion luminescent material as described in claim 1, characterized in that the doping of erbium is material
Expect the 1-5% of total material amount.
5. a kind of preparation method of up-conversion luminescent material as described in claim 1-4 is any, characterized in that step is：
(1) yttrium source is added in the solution of precipitation from homogeneous solution agent, clear solution is formed after being sufficiently stirred；
(2) a certain amount of erbium source is added in the clear solution of step (1), is sufficiently stirred until solution is transparent；
(3) clear solution of step (2) is transferred to closed in reaction kettle, progress hydro-thermal method reaction；
(4) product obtained by step (3) post-process up to up-conversion luminescent material；
When yttrium source is added in step (1), the molar ratio of hydroxide ion and the ruthenium ion in yttrium source in the solution of precipitation from homogeneous solution agent
It is 15:1~5；
The molar concentration of ruthenium ion is 0.01~1mol/L in solution when yttrium source is added in step (1)；
The condition of the hydro-thermal method is to keep the temperature 8-24 hours at 150-200 DEG C in closed reaction kettle；
The post-processing includes washing, filtering, dry, calcining successively, and the calcination temperature is 500-800 DEG C, when the calcining
Between be 1-6 hours；
The yttrium source is at least one of yttrium carbonate, yttrium chloride, acetic acid yttrium, yttrium sulfate, yttrium nitrate；
The erbium source is at least one of ErF_3 films, erbium nitrate, carbonic acid erbium, erbium chloride, erbium sulfate, carbonic acid erbium；
The precipitation from homogeneous solution agent is at least one of urea, hexamethylenetetramine.
6. a kind of up-conversion luminescent material as described in claim 1-4 is any is in information processing, optical storage, temperature measurement, life
Application in object fluoremetry, solar cell or laser anti-counterfeit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610854827.8A CN106479497B (en) | 2016-09-27 | 2016-09-27 | A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610854827.8A CN106479497B (en) | 2016-09-27 | 2016-09-27 | A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106479497A CN106479497A (en) | 2017-03-08 |
| CN106479497B true CN106479497B (en) | 2018-08-31 |
Family
ID=58267969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610854827.8A Active CN106479497B (en) | 2016-09-27 | 2016-09-27 | A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106479497B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057544A (en) * | 2019-12-04 | 2020-04-24 | 西安交通大学 | Lamellar bismuth-doped yttrium oxide fluorescent powder and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000071637A1 (en) * | 1999-05-20 | 2000-11-30 | Isis Innovation Limited | Coated phosphors |
| CN102942926A (en) * | 2012-11-09 | 2013-02-27 | 沈阳化工大学 | Preparation method of hollow light-emitting rare-earth microsphere |
| CN103849398A (en) * | 2012-11-30 | 2014-06-11 | 洛阳新巨能高热技术有限公司 | Compound agricultural film light conversion agent and its preparation method |
| CN105038793A (en) * | 2015-08-03 | 2015-11-11 | 江门市远大发光材料有限公司 | Y2O3:Eu<3+> red powder having high specific surface area and preparation method thereof |
-
2016
- 2016-09-27 CN CN201610854827.8A patent/CN106479497B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000071637A1 (en) * | 1999-05-20 | 2000-11-30 | Isis Innovation Limited | Coated phosphors |
| CN102942926A (en) * | 2012-11-09 | 2013-02-27 | 沈阳化工大学 | Preparation method of hollow light-emitting rare-earth microsphere |
| CN103849398A (en) * | 2012-11-30 | 2014-06-11 | 洛阳新巨能高热技术有限公司 | Compound agricultural film light conversion agent and its preparation method |
| CN105038793A (en) * | 2015-08-03 | 2015-11-11 | 江门市远大发光材料有限公司 | Y2O3:Eu<3+> red powder having high specific surface area and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Optical characterization of Er3+: Y2O3 nanoparticles for biosensor applications;Kelly L. Nash;《Proc. of SPIE》;20071231;64490J * |
| Synthesis of Er3+ Doped Y2O3 Nanophosphors;Nallusamy Venkatachalam;《J. Am. Ceram. Soc.》;20091231;1006–1010 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106479497A (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Antimony doped Cs 2 SnCl 6 with bright and stable emission | |
| Ntwaeaborwa et al. | Structural, optical and photoluminescence properties of Eu3+ doped ZnO nanoparticles | |
| CN100378192C (en) | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method | |
| CN102321475B (en) | Oxide up-conversion light-emitting material of perovskite structure and preparation method thereof | |
| CN101177611A (en) | High luminous intensity up-conversion fluorescence nano-crystal oxide and preparation method thereof | |
| CN106753371A (en) | A kind of holmium ytterbium codope bismuth tungstate fluorescent material and preparation method thereof | |
| CN107418560B (en) | Preparation method of efficient sulfur-doped zinc oxide nano material | |
| Rajkumar et al. | A highly intense double perovskite BaSrYZrO5. 5: Eu3+ phosphor for latent fingerprint and security ink applications | |
| Sun et al. | Preparation, characterization, and luminescence properties of double perovskite SrLaMgSbO 6: Mn 4+ far-red emitting phosphors for indoor plant growth lighting | |
| Zhao et al. | Highly efficient saturated visible up-conversion photoluminescent Y 2 O 3: Er 3+ microspheres pumped with a 1.55 μm laser diode | |
| CN105018087B (en) | Eu3+Adulterate laminated perovskite structure La2CuO4The preparation method of fluorescent powder | |
| CN106479497B (en) | A kind of efficient infrared excitation up-conversion luminescent material and preparation method thereof | |
| Pathak et al. | NIR emission and Ce3+–Nd3+ energy transfer in LaCaAl3O7 phosphor prepared by combustion synthesis | |
| Yu et al. | Highly efficient far-red emitting Mn4+-activated Li3La3W2O12 phosphors for plant growth LED lighting | |
| CN104910909A (en) | Erbium-doped lanthanum titanate fluorescent compound, and preparation method and application thereof | |
| CN105038785A (en) | (SrxCay)0.97TiO3:Eu3+0.03 fluorescent powder and preparing method thereof | |
| CN105038791A (en) | Preparation method of spherical red phosphor powder capable of being excited by ultraviolet-blue light | |
| CN106479501B (en) | Up-conversion luminescence rare earth Lu base fluoride materials and preparation method thereof | |
| CN108130084A (en) | A kind of ytterbium-thulium codope oxygen fluoride fluorescent material and preparation method thereof | |
| CN104830344B (en) | A kind of Er3+,Yb3+The preparation method being co-doped with YOF redness upconverting fluorescent material | |
| CN104673308B (en) | Material for realizing near-infrared luminescence under ultraviolet excitation and preparation method thereof | |
| CN103450892B (en) | A kind of method improving Eu ion characteristic glow peak intensity in zno-based matter | |
| CN108559501B (en) | Hydrothermal preparation method of chromium-doped aluminum oxide photoluminescent material | |
| CN112126432A (en) | Yb-Er co-doped bismuth oxyfluoride compound up-conversion material and preparation method thereof | |
| CN104164236A (en) | Self-activation vanadate fluorescent powder, preparation method and applications thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |