CN106544020B - The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing - Google Patents
The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing Download PDFInfo
- Publication number
- CN106544020B CN106544020B CN201610846700.1A CN201610846700A CN106544020B CN 106544020 B CN106544020 B CN 106544020B CN 201610846700 A CN201610846700 A CN 201610846700A CN 106544020 B CN106544020 B CN 106544020B
- Authority
- CN
- China
- Prior art keywords
- solution
- preparation
- added
- deionized water
- nano
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 title claims abstract description 19
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- -1 rare earth nitrate Chemical class 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 3
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000004332 silver Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005395 radioluminescence Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
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 kind of rear-earth-doped tungstate luminescent material of nano-Ag particles enhancing, chemical composition NaGd1‑x‑yErxYby(WO4)2: zAg, wherein x, y, z is Er respectively3+、Yb3+With the mole percent of Ag doping, 0.5mol%≤x≤3.0mol%, 0≤y≤20mol%, 0 < z≤2mol%.The present invention utilizes the surface plasmon resonance effect of nano-Ag particles, realize the very big enhancing of tungstate luminescent material luminous intensity, with the increasing of the elargol scale of construction, the fluorescence intensity of sample starts to increase, and green light maximal gain factor can achieve 50%, while synthesis technology of the present invention is simple, it is repeatable high, material therefor is environmentally friendly, it is easy to accomplish industrialized production can be used for showing, illuminate, laser anti-counterfeit etc..
Description
Technical field
The invention belongs to up-conversion luminescent material technical field, it is related to a kind of Tungstate fluorescent powder and preparation method thereof, tool
Body is related to a kind of rear-earth-doped tungstate luminescent material and preparation method thereof of silver nano-grain enhancing.
Background technique
Currently, rare earth up-conversion luminescent material is shown in laser, solar battery, infrared detector, 3 D stereo, light
Fibre communication, biological identification and the fields such as anti-fake show good application prospect, cause the extensive concern of people.However because of it
Lower luminous efficiency limits it in the process of industrialization in each field.
In numerous luminescent materials, there is excellent spectral property, luminous spectrum by the luminescent material of matrix of tungstates
With narrow, excitation purity height；Light absorpting ability is strong, high conversion efficiency；Launch wavelength distributed area field width；Physics, chemistry and optical property are steady
It is fixed.Compound alkali metal rare earth ion tungstates ARe (WO4)2(wherein A indicates that alkali metal ion, Re indicate rare earth ion) is exactly it
One of.It generally falls into tetragonal crystal system or monoclinic system, the Re in formula3+It is easy to the trivalent rare earth ion similar in radius
Replace, and to the solubility of rare earth ion height, it is not easy to generate concentration quenching.Therefore the tungstates structure can for rare earth from
Son provides good crystalline field, is suitable as good luminous host material.The prior art will not be based on silver nano-grain table
The enhancement effect of fluorescence of surface plasma resonance is introduced into tungstate luminescent material to enhance its illumination effect.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of rear-earth-doped tungstates hair of nano-Ag particles enhancing
Luminescent material and preparation method further increase the luminous efficiency of rear-earth-doped luminous material, such material is excited with 980nmLD
Under excellent up-conversion luminescence phenomenon, and preparation method is simple, pollution-free, has good chemical stability and stable luminescence
Property.
The technical scheme adopted by the invention is that:
A kind of rear-earth-doped tungstate luminescent material of nano-Ag particles enhancing, chemical composition NaGd1-x-yErxYby
(WO4)2: zAg, wherein x, y, z is Er respectively3+、Yb3+The mole percent adulterated with Ag, 0.5mol%≤x≤3.0mol%, 0
≤ y≤20mol%, 0 < z≤2mol%.
The preparation method of the rear-earth-doped tungstate luminescent material of nano-Ag particles enhancing the following steps are included:
It prepares silver colloidal solution: deionized water, silver nitrate solution and sodium citrate is mixed into 800~1000r/min stirring 5
Sodium borohydride solution is added after~7min and is protected from light standing after at colloid；
Prepare Na2WO4Solution: sodium tungstate is dissolved in after being stirred in deionized water and 40 DEG C of -60 DEG C of heating stirrings of ethylene glycol is added
Dissolution adjusts pH value of solution=9~10；
Prepare rare earth nitrate solution: by Er2O3, Yb2O3, Gd2O3It is dissolved in 40 DEG C of -60 DEG C of heating in dust technology or dilute hydrochloric acid
Stirring, adds deionized water to obtain transparent clear solution and pH value of solution=3~4 until the reaction is complete；
The rare earth nitrate solution of the preparation is added to the Na of preparation2WO4In solution, 800 behind adjusting pH=7~8~
1000r/min stirs 20-30min and forms mixed solution；
The silver colloidal solution of the preparation is added to 800~1000r/min in the mixed solution and stirs 20-30min
2~3MPa afterwards, react under the conditions of 180 DEG C -200 DEG C 18-24h sediment；
The sediment is centrifuged, is washed, dries 750 DEG C of -850 DEG C of annealing 2-4h after 2-4h at 60 DEG C -80 DEG C.
The beneficial effects of the invention are as follows
1, the present invention utilizes the surface plasmon resonance effect of nano-Ag particles, realizes tungstate luminescent material and shines
The very big enhancing of intensity, with the increasing of the elargol scale of construction, the fluorescence intensity of sample starts to increase, and green light maximal gain factor can be with
Reach 50%, provides new scheme to improve luminous efficiency.
2, synthesis technology of the present invention is simple, and repeatability is high, and material therefor is environmentally friendly, it is easy to accomplish industrialized life
It produces.
3, it is wide prepare rear-earth-doped tungstate luminescent material purposes by the present invention, can be used for showing, illuminate, laser anti-counterfeit etc. just
Face.
Detailed description of the invention
Fig. 1 is the XRD spectrum that comparative example 1 and embodiment 1-4 prepare sample；
Fig. 2 is the SEM figure that embodiment 2 prepares sample；
Fig. 3 (a) is the Up-conversion emission spectrum that embodiment 1-4 prepares sample, excitation light source 980nmLD；Fig. 3 (b) is
The different silver colloid ratios of Er/Yb doping adulterate the gain map of resulting visible light wave range.
Fig. 4 is the Up-conversion emission spectrum that comparative example 2, embodiment 5 and 6 prepare sample, excitation light source 980nmLD.
Fig. 5 is the abosrption spectrogram that comparative example 1 and embodiment 2 prepare sample.
Specific embodiment
The interaction of metal silver nano-grain and light can generate local surface plasma resonance effect, metal silver nanoparticle
The local fields around rare earth ion can be enhanced in particle, so that the rare earth ion in excitation state increases, or it may be said that
It is so that rare earth ion radiation transistion enhances, the process for inhibiting other pairs of radioluminescences unfavorable is existed with this to improve rare earth ion
The luminous efficiency of specific band.
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments, it should be noted that the present invention is not
Following specific embodiments are confined to, all equivalent transformations made on the basis of the technical solutions of the present application each falls within protection model of the invention
It encloses.
Embodiment 1:
The present embodiment provides a kind of rear-earth-doped tungstate luminescent material of nano-Ag particles enhancing, and chemical composition is
NaGd1-x-yErxYby(WO4)2: zAg, wherein x, y are Er respectively3+And Yb3+The mole percent of doping, z are moles of Ag doping
Percentage, x=0.5mol%, y=5mol%, z=0.25mol%.
The present embodiment nano-Ag particles enhancing rear-earth-doped tungstate luminescent material the preparation method is as follows:
Step 1 takes 18ml deionized water, and the silver nitrate solution of 3ml, 20mM/L is added, adds the lemon of 9ml, 20mM/L
Lemon acid sodium solution carries out that the sodium borohydride solution of 3ml, 20mM/L is added dropwise after continuing 5~7min of stirring, and solution is rapidly by white
Discoloration is yellow, forms colloid later, is eventually adding PVP solution 0.4ml, is stood in the place of being protected from light.The wherein number of nano-Ag particles
Amount is regulated and controled by the volume of Ag colloidal sol, and introducing the volume of Ag colloidal sol in this experiment is 4ml；
Step 2, weighs 0.012mol sodium tungstate and is dissolved in 14ml deionized water and stir evenly, and complexing agent second is added later
Glycol (VEG: water=2:1) it is dissolved in 60 DEG C of heating stirrings, and its PH=9 is adjusted with the NaOH of 2mol/L, obtain solution A；
Step 3 stoichiometrically weighs 0.015mmolEr respectively2O3, 0.15mmolYb2O3, 2.84mmol Gd2O3
It is put into the beaker equipped with 10ml deionized water, is dissolved in dust technology or dilute hydrochloric acid, obtains transparent clarification in 60 DEG C of heating stirrings
Solution obtain transparent clear solution, and PH=4 until the reaction is complete repeatedly plus deionized water, obtain solution B；
B solution is added dropwise in solution A by step 4, is generated white flock precipitate, is adjusted the PH=7 of solution, is continued
Stir 30min；
Silver colloidal solution is added stirring number 30min in above-mentioned mixed liquor, is put in reaction kettle, 200 by step 5
It is reacted for 24 hours under the conditions of DEG C；
Step 6, after reaction, for several times by product centrifuge separation, washing, dry 4h, finally exists at 60 DEG C -80 DEG C
Anneal 4h at 850 DEG C.
Comparative example 1:
This comparative example provides a kind of rear-earth-doped tungstate luminescent material, chemical composition NaGd1-x-yErxYby(WO4)2,
Wherein x, y are Er respectively3+And Yb3+The mole percent of doping, x=0.5mol%, y=5mol%.
The rear-earth-doped tungstate luminescent material of this comparative example the preparation method is as follows:
Step 1, weighs 0.012mol sodium tungstate and is dissolved in 14ml deionized water and stir evenly, and complexing agent second is added later
Glycol (VEG: water=2:1) it is dissolved in 40 DEG C of heating stirrings, and its PH=10 is adjusted with the NaOH of 2mol/L, obtain solution A；
Step 2 stoichiometrically weighs 0.015mmolEr respectively2O3, 0.15mmolYb2O3, 2.84mmol Gd2O3
It is put into the beaker equipped with 10ml deionized water, is dissolved in dust technology or dilute hydrochloric acid, obtains transparent clarification in 40 DEG C of heating stirrings
Solution obtain transparent clear solution, and PH=3 until the reaction is complete repeatedly plus deionized water, obtain solution B；
B solution is added dropwise in solution A by step 3, is generated white flock precipitate, is adjusted the PH=8 of solution, is continued
Stir 20min；
Step 4, the mixture that step 3 is obtained are put in reaction kettle, react 18h under the conditions of 180 DEG C；
Step 5, after reaction, for several times by product centrifuge separation, washing, the dry 2h at 60 DEG C, finally at 750 DEG C
Lower annealing 2h.
Embodiment 2:
The present embodiment prepares NaGd1-x-yErxYby(WO4)2: same as Example 1, x=the step of zAg material
0.5mol%, y=5mol%, the difference is that z=0.5mol%, i.e., the volume that Ag colloidal sol is introduced in the present embodiment is 8ml.
Embodiment 3:
The present embodiment prepares NaGd1-x-yErxYby(WO4)2: same as Example 1, x=the step of zAg material
0.5mol%, y=5mol%, the difference is that the volume that z=1.0mol%, i.e. the present embodiment introduce Ag colloidal sol is 16ml.
Embodiment 4:
The present embodiment prepares NaGd1-x-yErxYby(WO4)2: same as Example 1, x=the step of zAg material
0.5mol%, y=5mol%, the difference is that z=2.0mol%, i.e., the volume that Ag colloidal sol is introduced in the present embodiment is 32ml.
Comparative example 2
This comparative example prepares NaGd1-x-yErxYby(WO4)2The step of powder body material, is identical as comparative example 1, the difference is that x=
3.0mol%, y=0mol%, z=0mol%.
Embodiment 5
The present embodiment prepares NaGd1-x-yErxYby(WO4)2: the step of zAg material, is same as Example 2, unlike, x
=3mol%, y=0, z=2.0mol%, the volume for introducing Ag colloidal sol is 32ml.
Embodiment 6
The present embodiment prepares NaGd1-x-yErxYby(WO4)2: the step of zAg material, is same as Example 2, unlike x=
3mol%, y=20mol%, z=2.0mol%, the volume for introducing Ag colloidal sol is 32ml.
Fig. 1 is the XRD spectrum that comparative example 1, embodiment 1-4 prepare sample.As seen from the figure, the position of the diffraction maximum of all samples
It sets corresponding with the peak position of PDF card (25-0829) of standard, and does not detect other miscellaneous peaks, belong to pure tetragonal phase.It is real
It applies a 1-4 to show after adulterating Er/Yb and Ag nano particles (average grain diameter is in 50nm) being added, has not been changed NaGd (WO4)2's
Crystal structure.And embodiment 1-4 sample all has stronger diffraction maximum, illustrates that sample has good crystallinity.
Fig. 2 is the SEM figure that embodiment 2 prepares sample.Most of particle surface is smooth as seen from the figure, but the shape of particle
Shape is not regular enough, and size is not uniform enough, and has the little particle of part to adhere on surface.
Fig. 3 (a) is under 980nm LD pumping, and embodiment 1-4 prepares the Up-conversion emission spectrum of sample.As can be seen that
NaGd (the WO of Er/Yb doping4)2It is Green band and emitting red light band respectively there are two visible light luminous zone, and green light is sent out
It penetrates much larger than red emission.The peak wavelength of two of them green emissive band is located at 530nm and 552nm, respectively corresponds Er3+From
Son2H11/2→4I15/2With4S3/2→4I15/2Transition；The peak wavelength of red emission band is located at 656nm and 670nm, corresponding4F9/2
→4I15/2Transition.And with the increase of silver colloid doping, significant change, silver colloid is had occurred in the emissive porwer of sample
Concentration effect at 1% is best.Fig. 3 (b) reflects the integrated intensity of feux rouges and green light with the variation of silver colloid doping.Wherein
NaGd (WO is adulterated with the Er/Yb undoped with silver colloid4)2The integrated intensity numerical value of material does normalized.As can be seen that working as
When introducing a small amount of silver colloid, the fluorescence intensity of sample has a degree of decrease；And with the increasing of the elargol scale of construction, sample
Fluorescence intensity starts to increase, and green light maximal gain factor can achieve 50%, and (green light maximal gain factor can achieve herein
50% refers to that the luminous intensity after Ag colloid is added is compared with it using the NGW green light integrated intensity of Er/Yb doping as 1
Gain factor out is normalized)；Continue the doping of increase silver colloid later, the fluorescence intensity of sample can be sent out again
Raw bust is especially changed with green light the most obvious.
Fig. 4 is under 980nm LD pumping, and comparative example 2 and embodiment 5-6 prepare the Up-conversion emission spectrum of sample.It can be with
Find out, when only adulterating Er3+When, the up-conversion luminescence of sample is weaker (comparative example 2)；After Ag colloid is added, luminous intensity is obvious
Enhancing, green light gain factor are 30% (embodiment 5)；Work as Er3+/Yb3+After being co-doped with and Ag colloid being added, intensity is than the above two
There is great enhancing (embodiment 6).Fig. 3 and Fig. 4 shows the surface plasmons of nanometer Ag generation to up-conversion
Absorption and fluorescent effect have certain humidification.
Fig. 5 is the absorption spectrum of 2 sample of comparative example 1 and embodiment, and the corresponding spectral transition in each peak, Ag are labelled in Fig. 5
After colloid is added, the absorption peak between 400-600nm is significantly broadened, this is because the surface plasma resonance of Ag nano particles is inhaled
Caused by receipts, which create surface plasma body resonant vibration enhancement effect of fluorescences, and the up-conversion luminescence of sample is made to have high shine
Intensity and luminous efficiency.
Claims (2)
1. a kind of rear-earth-doped tungstate luminescent material of nano-Ag particles enhancing, which is characterized in that the nano-Ag particles increase
Strong rear-earth-doped tungstate luminescent material chemical composition is NaGd1-x-yErxYby(WO4)2: zAg, wherein x, y, z is Er respectively3 +、Yb3+With the mole percent of Ag doping；
X=0.5mol%, y=5mol%, z=1.0mol%；
The preparation method of the rear-earth-doped tungstate luminescent material of the nano-Ag particles enhancing, comprising the following steps:
It prepares silver colloidal solution: sodium borohydride solution is added after deionized water, silver nitrate solution and sodium citrate are mixed
Standing is protected from light after at colloid；
Prepare Na2WO4Solution: sodium tungstate is dissolved in after being stirred in deionized water and the dissolution of ethylene glycol heating stirring is added, adjust solution
PH=9~10；
Prepare rare earth nitrate solution: by Er2O3, Yb2O3, Gd2O3It is dissolved in heating stirring in dust technology, adds deionized water until anti-
Transparent clear solution and pH value of solution=3~4 should be obtained completely；
The rare earth nitrate solution of the preparation is added to the Na of preparation2WO4In solution, formation is stirred after adjusting pH=7~8
Mixed solution；
The silver colloidal solution of the preparation is added to after being stirred in the mixed solution and reacts to obtain sediment；
The sediment is centrifuged, washed, dried and made annealing treatment；
It is 800~1000r/min, 5~7min that condition, which is mixed, in the deionized water, silver nitrate solution and sodium citrate；Institute
State preparation Na2WO4Heating temperature is 40~60 DEG C when solution；Heating temperature when preparing rare earth nitrate solution is 40~60
℃；The stirring form mixed solution and the silver colloidal solution to be added to the stirring condition stirred in mixed solution be 800
~1000r/min, 20~30min；Reacted after the stirring sediment reaction condition be 2~3MPa, 180~200 DEG C, 18
~for 24 hours；The drying condition is dry 2~4h at 60~80 DEG C；The annealing conditions are 750~850 DEG C of 2~4h of annealing.
2. the preparation method of the rear-earth-doped tungstate luminescent material of the enhancing of nano-Ag particles described in claim 1, feature exist
In, comprising the following steps:
It prepares silver colloidal solution: sodium borohydride solution is added after deionized water, silver nitrate solution and sodium citrate are mixed
Standing is protected from light after at colloid；
Prepare Na2WO4Solution: sodium tungstate is dissolved in after being stirred in deionized water and the dissolution of ethylene glycol heating stirring is added, adjust solution
PH=9~10；
Prepare rare earth nitrate solution: by Er2O3, Yb2O3, Gd2O3It is dissolved in heating stirring in dust technology, adds deionized water until anti-
Transparent clear solution and pH value of solution=3~4 should be obtained completely；
The rare earth nitrate solution of the preparation is added to the Na of preparation2WO4In solution, formation is stirred after adjusting pH=7~8
Mixed solution；
The silver colloidal solution of the preparation is added to after being stirred in the mixed solution and reacts to obtain sediment；
The sediment is centrifuged, washed, dried and made annealing treatment；
It is 800~1000r/min, 5~7min that condition, which is mixed, in the deionized water, silver nitrate solution and sodium citrate；Institute
State preparation Na2WO4Heating temperature is 40~60 DEG C when solution；Heating temperature when preparing rare earth nitrate solution is 40~60
℃；The stirring form mixed solution and the silver colloidal solution to be added to the stirring condition stirred in mixed solution be 800
~1000r/min, 20~30min；Reacted after the stirring sediment reaction condition be 2~3MPa, 180~200 DEG C, 18
~for 24 hours；The drying condition is dry 2~4h at 60~80 DEG C；The annealing conditions are 750~850 DEG C of 2~4h of annealing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846700.1A CN106544020B (en) | 2016-09-23 | 2016-09-23 | The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846700.1A CN106544020B (en) | 2016-09-23 | 2016-09-23 | The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106544020A CN106544020A (en) | 2017-03-29 |
| CN106544020B true CN106544020B (en) | 2019-03-22 |
Family
ID=58367966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610846700.1A Expired - Fee Related CN106544020B (en) | 2016-09-23 | 2016-09-23 | The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106544020B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109465033A (en) * | 2017-09-08 | 2019-03-15 | 梅玉杰 | A kind of preparation method for the carbon nano tube air purifier removing formaldehyde |
| CN108978047B (en) * | 2018-08-02 | 2020-10-30 | 青岛大学 | High-concentration co-doped nanofiber membrane for single-drop trace fluorescence detection and preparation method and application thereof |
| CN111334283B (en) * | 2020-03-21 | 2023-07-07 | 济南大学 | Up-conversion luminescent nano material modified by silver alkyne surface as well as preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517019A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Method for improving photoluminescence efficiency of upconversion material |
| CN103351859A (en) * | 2013-08-05 | 2013-10-16 | 黑龙江大学 | Method for preparing Ag/Y2O3:Yb<3+>/Er<3+> composite nanotubes with up-conversion light emitting function |
| CN104316214A (en) * | 2014-09-22 | 2015-01-28 | 西北大学 | Application of ALn(MoO4)2 up-conversion luminescent material doped with Er3+ and Yb3+ in optical temperature sensor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090127510A1 (en) * | 2005-05-23 | 2009-05-21 | Keio University | Fine particle and red fluorescence conversion medium using the same |
-
2016
- 2016-09-23 CN CN201610846700.1A patent/CN106544020B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517019A (en) * | 2011-11-04 | 2012-06-27 | 南开大学 | Method for improving photoluminescence efficiency of upconversion material |
| CN103351859A (en) * | 2013-08-05 | 2013-10-16 | 黑龙江大学 | Method for preparing Ag/Y2O3:Yb<3+>/Er<3+> composite nanotubes with up-conversion light emitting function |
| CN104316214A (en) * | 2014-09-22 | 2015-01-28 | 西北大学 | Application of ALn(MoO4)2 up-conversion luminescent material doped with Er3+ and Yb3+ in optical temperature sensor |
Non-Patent Citations (2)
| Title |
|---|
| Hydrothermal synthesis and upconversion luminescence of NaGd(WO)2 co-doped with ho3+ and yb3+;Xiaochen Yu等;《Journal of Luminescence》;20141231;1-4 |
| Near infrared to visible upconversion emission in Er3+/Yb3+ co-doped NaGd(WO4)2 nanoparticles obtained by hydrothermal method;Xiaochen Yu等;《Journal of Luminescence》;20141231;第154卷;111-115 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106544020A (en) | 2017-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102337136B (en) | Metal-nanoparticle-doped oxide luminescent material with hollow structure and preparation method thereof | |
| CN106544020B (en) | The rear-earth-doped tungstate luminescent material and preparation method of nano-Ag particles enhancing | |
| CN105754585B (en) | A kind of nanocrystalline preparation method of the Coated with Oleic Acid rare earth calcirm-fluoride of High Efficiency Luminescence | |
| CN107603623B (en) | Small-size β -NaREF4Preparation method of fluorescent powder | |
| Yang et al. | Controlled morphology and EDTA-induced pure green upconversion luminescence of Er 3+/Ho 3+-Yb 3+ co-doped NaCe (MoO 4) 2 phosphor | |
| Huang et al. | Understanding the effect of Mn 2+ on Yb 3+/Er 3+ upconversion and obtaining a maximum upconversion fluorescence enhancement in inert-core/active-shell/inert-shell structures | |
| CN103102880A (en) | Simple spectrum band up-conversion luminescence nanocrystalline and preparation method thereof | |
| CN108192607B (en) | Up-conversion strong red light emission TiO2Preparation and application of nano material | |
| CN112340773B (en) | Preparation method of nano zirconia luminescent material | |
| CN108165269A (en) | A kind of fluorination lutetium potassium that phase change delay and Up-conversion Intensity greatly improve is nanocrystalline and preparation method thereof | |
| CN105038785A (en) | (SrxCay)0.97TiO3:Eu3+0.03 fluorescent powder and preparing method thereof | |
| Chao et al. | Preparation and luminescence properties of BaWO4: Yb3+/Tm3+ nano-crystal | |
| CN110591706A (en) | Rare earth ion doped cubic phase zirconium tungstate up-conversion nanocrystal and preparation method thereof | |
| CN106966430A (en) | A kind of preparation method of metal vanadate nano material | |
| Shi et al. | Preparation of Y 2 O 3: Eu 3+, Tb 3+ nanopowders with tunable luminescence by ammonium bicarbonate co-precipitation method | |
| Zhang et al. | Enhanced upconversion luminescence in LuPO 4: Ln 3+ phosphors via optically inert ions doping | |
| CN111117616B (en) | Multifunctional down-conversion nano material and preparation method thereof | |
| CN108753288A (en) | Conversion long after glow luminous material and its preparation method and application in a kind of nanometer | |
| CN112442369B (en) | Calcium ion doped enhanced up-conversion red light emitting material and preparation method thereof | |
| CN108130081B (en) | Ytterbium and erbium co-doped gadolinium vanadate green upconversion luminescence nanocrystal and preparation method thereof | |
| CN107312541A (en) | A kind of transition metal ions regulates and controls the preparation method of rare earth upconversion nano material morphology | |
| CN109734120B (en) | Flower-like microsphere structure potassium yttrium tungstate material and preparation method thereof | |
| CN108300478B (en) | Water-soluble terbium-doped lanthanum fluoride nano particle and preparation method thereof | |
| CN112538350A (en) | Ti4+/Mn4+Co-doped far-red fluorescent powder and preparation method thereof | |
| CN106590653B (en) | Er3+/Yb3+Codope up-conversion luminescent material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Chaoguang Inventor after: Duan Li Inventor after: Li Zhe Inventor after: Zhang Dandan Inventor after: Jiang Ziqiang Inventor after: Zhao Peng Inventor after: Other inventor requests not to publish the name Inventor before: Yu Xiaochen Inventor before: Duan Li Inventor before: Li Zhe Inventor before: Zhang Dandan Inventor before: Jiang Ziqiang Inventor before: Zhang Chaoguang Inventor before: Zhao Peng |
|
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yu Xiaochen Inventor after: Zhang Chaoguang Inventor after: Duan Li Inventor after: Li Zhe Inventor after: Zhang Dandan Inventor after: Jiang Ziqiang Inventor after: Zhao Peng Inventor before: Yu Xiaochen Inventor before: Duan Li Inventor before: Li Zhe Inventor before: Zhang Dandan Inventor before: Jiang Ziqiang Inventor before: Zhang Chaoguang Inventor before: Zhao Peng |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190322 |