CN103571482B - Erbium ion-doped tungstate up-conversion luminescent material as well as preparation method and application thereof - Google Patents
Erbium ion-doped tungstate up-conversion luminescent material as well as preparation method and application thereof Download PDFInfo
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- CN103571482B CN103571482B CN201310583971.9A CN201310583971A CN103571482B CN 103571482 B CN103571482 B CN 103571482B CN 201310583971 A CN201310583971 A CN 201310583971A CN 103571482 B CN103571482 B CN 103571482B
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 43
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 54
- -1 ytterbium ion Chemical class 0.000 claims description 45
- 238000005245 sintering Methods 0.000 claims description 36
- 238000001354 calcination Methods 0.000 claims description 34
- 229910017922 MgLa Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 16
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 12
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 12
- 229940075624 ytterbium oxide Drugs 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 10
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003836 solid-state method Methods 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 15
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000007850 fluorescent dye Substances 0.000 abstract 1
- 238000001215 fluorescent labelling Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 description 16
- 230000005284 excitation Effects 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 150000003657 tungsten Chemical class 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
- 238000001748 luminescence spectrum Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000005387 chalcogenide glass Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KWMNWMQPPKKDII-UHFFFAOYSA-N erbium ytterbium Chemical compound [Er].[Yb] KWMNWMQPPKKDII-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002165 resonance energy transfer Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BPJYAXCTOHRFDQ-UHFFFAOYSA-L tetracopper;2,4,6-trioxido-1,3,5,2,4,6-trioxatriarsinane;diacetate Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.[O-][As]1O[As]([O-])O[As]([O-])O1.[O-][As]1O[As]([O-])O[As]([O-])O1 BPJYAXCTOHRFDQ-UHFFFAOYSA-L 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to an erbium ion-doped tungstate up-conversion luminescent material as well as a preparation method and application thereof, and belongs to the technical field of inorganic luminescent materials. The chemical formula of the up-conversion luminescent material provided by the invention is MgLa2-2(x+y)Er2xYb2y(WO4)4, wherein x is Er3+ doped mole percent; y is Yb3+ doped mole percent; x is greater than or equal to 0.0001, and smaller than 0.5; y is greater than or equal to 1.0, and smaller than 0.1; x+y is greater than 1.0 and smaller than 0.1. The erbium ion-doped tungstate up-conversion luminescent material uses novel tetra-tungstate as a matrix material and erbium as a doping ion, converts infrared light in a 975-nanometer attachment to green fluorescence with the wavelength range of 510-565 nanometers through the up-conversion mechanism, has high luminescent intensity and high color purity, and can be applied in the fields such as fake prevention, biomolecule fluorescence labeling and three-dimensional display. The preparation method of the up-conversion luminescent material provided by the invention is simple, and generates no environmental pollution.
Description
Technical field
The present invention relates to a kind of luminescent material, preparation method and application thereof, particularly a kind of erbium ion-doped New Tungsten salt luminescent material, preparation method and application thereof, belong to luminescent material technical field.
Background technology
Bluish-green laser has huge application prospect in information processing, medical diagnosis, optical storage and colored display, and the up-conversion luminescence of rare earth ion doped material is one of solution realizing the output of short wavelength's solid statelaser bluish-green laser.Therefore, rare earth ion up-conversion luminescent material attention, and become a study hotspot in luminescence.
Rare earth erbium ion Er
3+owing to having important blue light, green glow and red emission at visible waveband, and Er
3+'s
4i
15/2→
4i
9/2with
4i
15/2→
4i
11/2transition absorption just correspond to 800 and 980 nm semiconductor laser of commercialization, and abundant visible spectrum and cheap excitaton source make Er
3+ion is subject to extensive concern as upper converting activity ion.But, Er
3+ion is more weak in the absorption of 800 and 980 nm, thus have impact on up-conversion luminescence efficiency.Numerous research shows, takes the mode of mixing sensitized ions effectively can improve light conversion efficiency.Sensitized luminescence is a kind of form of rare earth ion interphase interaction, and energy trasfer sensitized ions absorbed by utilizing Resonance energy transfer is to luminous ion.In the method for several raising lasing efficiencies proposed at present, sensitization accounts for very important status.When some material exists without sensitized ions, luminous hardly, and a small amount of sensitized ions is just enough to make luminous intensity increase more than 1 order of magnitude.
Ytterbium ion Yb
3+with the level structure of its uniqueness, in the transmission ofenergy between rare earth ion, occupy critical role.In addition, Yb
3+ion is approximately Er at the absorption cross section of 980 nano wavebands
3+10 times of ion, so by by Yb
3+with Er
3+between larger energy transfer coefficient can greatly improve the absorption of erbium ion to 980 nanometer exciting lights.Therefore, Yb is introduced
3+serve as sensitizing agent and can strengthen Er
3+the pumping efficiency of ion, thus improve up-conversion luminescence efficiency.
Usually, the research of the substrate material of rare earth ion up-conversion luminescence mainly concentrates on the low system of the phonon energies such as crystal, fluorochemical, chalcogenide glass, and in fact, the substrate material as up-conversion luminescence generally should follow following principle: the phonon energy of material is low, chemical stability good, fibre-forming performance is good, solubilize rare earth ions degree is high.The systems such as fluorochemical are Shortcomings in erosion resistance and stability, is difficult to be applied in practical devices.By contrast, oxide crystal has wider infrared penetrating region, phonon energy (~ 500cm that solubilize rare earth ions is good, lower
-1) and higher specific refractory power, and abundant raw material source, low for equipment requirements and environmental protection, is considered to the desirable substrate material making transfer optics.Document (Materials Research Bulletin 48 (2013) 2159-2165) passes through Er
3+/ Yb
3+mix Gd altogether
2(WO
4)
3prepare green up conversion luminescent material, and discuss the impact on luminescent properties such as ion doping concentration and temperature.Document (Materials Chemistry and Physics 133 (2012) 617-620) utilizes Gd
6wO
12: Er
3+/ Yb
3+prepare the up-conversion luminescent material of excellent property, and have extensively studied luminescence mechanism.Publication number is that the Chinese invention patent of CN102191049A discloses a kind of ytterbium erbium double-doped calcium tungstate polycrystal powder green ray up-conversion material and preparation method thereof, and this material can send bright upper conversion green glow in 980 nanometer laser pumpings, exciting power under being 300 mW conditions.But be not yet seen in report with up-conversion luminescent material prepared by erbium ion-doped four tungstate.
Summary of the invention
The object of the invention is to overcome existing up-conversion luminescent material luminescent properties unstable, the deficiency that production cost is high, there is provided a kind of preparation technology simple, luminance purity is good, the up-conversion luminescent material of low in raw material price, excellent property, preparation method and application thereof.
For reaching above object, the technical solution used in the present invention is to provide a kind of erbium ion-doped tungstate up-conversion luminescent material, and its chemical general formula is MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4, wherein,
xfor Er
3+the molecular fraction of doping, y is Yb
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0.
Technical solution of the present invention also provides two kinds of methods preparing tungstate up-conversion luminescent material erbium ion-doped as above, a kind of for adopting high temperature solid-state method, comprises the steps:
1, by chemical formula MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4in the stoichiometric ratio of each element, wherein,
xfor Er
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0, takes respectively containing magnesium ion Mg
2+compound, containing lanthanum ion La
3+compound, containing ytterbium ion Yb
3+compound, containing erbium ion Er
3+compound, containing tungsten ion W
6+compound, grind and mix, after compressing tablet, obtaining sheet precast body;
2, precast body step 1 obtained presintering 1 ~ 2 time in air atmosphere, pre-sintering temperature is 300 ~ 700 DEG C, and sintering time is 1 ~ 12 hour, grinds and mix after naturally cooling, and compressing tablet obtains flap;
3, calcined in air atmosphere by the flap that step 2 obtains, calcining temperature is 700 ~ 1300 DEG C, and calcination time is 2 ~ 15 hours, naturally cools to room temperature, grinds and mix namely to obtain Powdered erbium ion-doped tungstate up-conversion luminescent material.
In the high temperature solid-state method that the present invention adopts, the sintering temperature of step 2 is 350 ~ 680 DEG C, and calcination time is 2 ~ 10 hours; The calcining temperature of step 3 is 750 ~ 1250 DEG C, and calcination time is 3 ~ 10 hours.
The another kind of preparation method that technical solution of the present invention provides, for adopting chemical synthesis, comprises the steps:
1, by chemical formula MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4in the stoichiometric ratio of each element, wherein,
xfor Er
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0, takes respectively containing magnesium ion Mg
2+compound, containing lanthanum ion La
3+compound, containing ytterbium ion Yb
3+compound, containing erbium ion Er
3+compound, containing tungsten ion W
6+compound, they are dissolved in dust technology under magnetic stirring respectively, by volume, with the deionized waters of 2 ~ 4 times dilution;
2, adding complexing agent respectively by 0.5 ~ 2.0 wt% of reactant quality in each raw material, under magnetic stirring to dissolving completely, obtaining the solution of each raw material; Described complexing agent is the one in citric acid or oxalic acid;
The solution of each raw material 3, step (2) obtained slowly mixes, in temperature be under the condition of 50 ~ 100 DEG C stir 1 ~ 2 hour, leave standstill, dry after obtain fluffy presoma;
4, presoma is placed in retort furnace, in air atmosphere presintering 1 ~ 2 time, sintering temperature is 400 ~ 600 DEG C, and sintering time is once 3 ~ 10 hours, after naturally cooling, grinds and mixes;
5, calcined in air atmosphere by the mixture that step 4 obtains, calcining temperature is 600 ~ 1100 DEG C, and calcination time is 1 ~ 15 hour; Be cooled to 200 ~ 400 DEG C, be incubated and be cooled to room temperature after 1 ~ 6 hour, after grinding evenly, namely obtain Powdered erbium ion-doped New Tungsten salt luminescent material.
In the chemical synthesis that the present invention adopts, the sintering temperature of step 4 is 450 ~ 580 DEG C, and calcination time is 4 ~ 9 hours; The calcining temperature of step 5 is 650 ~ 1050 DEG C, and calcination time is 3 ~ 13 hours, and holding temperature is 250 ~ 380 DEG C, and soaking time is 2 ~ 5 hours.
In technical solution of the present invention, described contains magnesium ion Mg
2+compound be one in magnesium oxide, magnesium basic carbonate, magnesium sulfate, magnesium nitrate; Described contains lanthanum ion La
3+compound be one in lanthanum trioxide, lanthanum nitrate; Described contains ytterbium ion Yb
3+compound be one in ytterbium oxide, ytterbium nitrate; Described contains erbium ion Er
3+compound be one in Erbium trioxide, Erbium trinitrate; Described contains tungsten ion W
6+compound be one in Tungsten oxide 99.999, ammonium tungstate.
A preferred version of the present invention is: described contains magnesium ion Mg
2+compound be magnesium basic carbonate; Described contains lanthanum ion La
3+compound be lanthanum trioxide; Described contains ytterbium ion Yb
3+compound be ytterbium oxide; Described contains erbium ion Er
3+compound be Erbium trioxide; Described contains tungsten ion W
6+compound be ammonium tungstate.
Technical solution of the present invention also comprises a kind of application of erbium ion-doped tungstate up-conversion luminescent material, and this luminescent material is applied to anti-counterfeiting mark, biomolecules fluorescent mark, 3 D stereo display.
Principle of the present invention is: with the New Tungsten hydrochlorate synthesized for substrate material, utilize ytterbium ion Yb
3+for sensitizing agent, its absorb infrared photon transit to excited state, subsequently by transmission ofenergy to Er
3+ion, makes
4i
15/2the electronics of ground state finally transits to
4f
7/2excited state, thus realize up-conversion luminescence.
Compared with prior art, the present invention has following beneficial effect:
1, the New Tungsten hydrochlorate prepared by the present invention, structure properties is stablized, and synthesis technique is simple, can as excellent substrate material.
2, the present invention adopts ytterbium ion Yb
3+as sensitized ions, utilize ytterbium ion Yb
3+with erbium ion Er
3+between transmission ofenergy, enhance material in the absorption of 980 nm and realize up-conversion luminescence.Illuminant colour purity is high, has broad application prospects in display, laser anti-counterfeit, biological medicine etc.
3, the abundance of the present invention's raw material, cheap, and preparation process is simple, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 prepares sample MgLa
1.6er
0.1yb
0.3(WO
4)
4scanning electron microscope (SEM) photograph;
Fig. 2 is that the embodiment of the present invention 1 prepares sample MgLa
1.6er
0.1yb
0.3(WO
4)
4the up-conversion luminescence spectrogram obtained under 975 nanometers, excitation energy intensity are 1.1 watts infrared ray excited;
Fig. 3 is that the embodiment of the present invention 2 prepares sample MgLa
1.9er
0.0002yb
0.9998(WO
4)
4the up-conversion luminescence spectrogram obtained under 975 nanometers, excitation energy intensity are 1.3 watts infrared ray excited;
Fig. 4 is that the embodiment of the present invention 3 prepares sample MgLa
1.5er
0.3yb
0.2(WO
4)
4in 975 nanometers, excitation energy intensity is the up-conversion luminescence spectrogram obtained under 2.07 watts infrared ray excited;
Fig. 5 is that the embodiment of the present invention 4 prepares sample MgLa
1.1er
0.45yb
0.45(WO
4)
4in 975 nanometers, excitation energy intensity is the up-conversion luminescence spectrogram obtained under 2.24 watts infrared ray excited;
Fig. 6 is that the embodiment of the present invention 4 prepares sample MgLa
0.2er
0.6yb
1.2(WO
4)
4in 975 nanometers, excitation energy intensity is the up-conversion luminescence spectrogram obtained under 2.41 watts infrared ray excited;
Fig. 7 is that the embodiment of the present invention 4 prepares sample MgLa
0.6er
0.4yb (WO
4)
4in 975 nanometers, excitation energy intensity is the up-conversion luminescence spectrogram obtained under 2.66 watts infrared ray excited.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
Preparation MgLa
1.6er
0.1yb
0.3(WO
4)
4
According to chemical formula MgLa
1.6er
0.1yb
0.3(WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.197 gram, Erbium trioxide Er
2o
3: 0.0638 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams.
Grind in agate mortar and after mixing, be compressing tablet 10min in the pressure environment of 18MPa at pressure, select air atmosphere first sintering, sintering temperature is 350 DEG C, and sintering time 7 hours, is then chilled to room temperature, take out sample, repeat this sintering operation, carry out second time sintering.
After second time sintering, again even for abundant for compound mixed grinding, be compressing tablet 10min in the pressure environment of 18MPa at pressure, be positioned among air atmosphere, third firing is carried out at 750 DEG C, calcination time is 9 hours, is cooled to room temperature, takes out sample and carry out grinding namely to obtain pulverous erbium ion-doped New Tungsten salt luminescent material.
See accompanying drawing 1, it is the scanning electron microscope (SEM) photograph that the present embodiment technical scheme prepares sample, the tungstate MgLa prepared by picture display
1.6er
0.1yb
0.3(WO
4)
4crystallinity is good, exists without other dephasign.
See accompanying drawing 2, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 1.1 watts, as seen from Figure 2, this material launches main peak at 525 nm, for Green upconversion luminescent, this luminescent material can be used for anti-counterfeiting mark, biomolecules fluorescent mark, 3 D stereo display.
Embodiment 2
Preparation MgLa
1.9er
0.0002yb
0.9998(WO
4)
4
According to chemical formula MgLa
1.9er
0.0002yb
0.9998(WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.657 gram, Erbium trioxide Er
2o
3: 0.0002 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams.
Grind in agate mortar and after mixing, be compressing tablet 10min in the pressure environment of 18MPa at pressure, select air atmosphere first sintering, sintering temperature is 500 DEG C, and sintering time 5 hours, is then cooled to room temperature, take out sample, repeat this sintering operation, carry out second time sintering.
After second time sintering, again even for abundant for compound mixed grinding, be compressing tablet 10min in the pressure environment of 18MPa at pressure, be positioned among air atmosphere, third firing is carried out at 1000 DEG C, calcination time is 10 hours, is cooled to room temperature, takes out sample and carry out grinding namely to obtain pulverous erbium ion-doped New Tungsten salt luminescent material.
See accompanying drawing 3, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 1.3 watts, as seen from Figure 3, this material launches main peak at 530 nm, is Green upconversion luminescent.
Embodiment 3
Preparation MgLa
1.5er
0.3yb
0.2(WO
4)
4
According to chemical formula MgLa
1.5er
0.3yb
0.2(WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.131 gram, Erbium trioxide Er
2o
3: 0.191 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams.
Grind in agate mortar and after mixing, be compressing tablet 10min in the pressure environment of 18MPa at pressure, select air atmosphere first sintering, sintering temperature is 680 DEG C, and sintering time 10 hours, is then chilled to room temperature, take out sample, repeat this sintering operation, carry out second time sintering.
After second time sintering, again even for abundant for compound mixed grinding, be compressing tablet 10min in the pressure environment of 18MPa at pressure, be positioned among air atmosphere, third firing is carried out at 1250 DEG C, calcination time is 3 hours, is cooled to room temperature, takes out sample and carry out grinding namely to obtain pulverous erbium ion-doped New Tungsten salt luminescent material.
See accompanying drawing 4, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 2.07 watts, as seen from Figure 4, this material launches main peak at 535 nm, is Green upconversion luminescent.
Embodiment 4
Preparation MgLa
1.1er
0.45yb
0.45(WO
4)
4
According to chemical formula MgLa
1.1er
0.45yb
0.45(WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.296 gram, Erbium trioxide Er
2o
3: 0.287 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams.Grind in agate mortar and after mixing, be compressing tablet 10min in the pressure environment of 18MPa at pressure, select air atmosphere first sintering, sintering temperature is 400 DEG C, and sintering time 5 hours, is then chilled to room temperature, take out sample, repeat this sintering operation, carry out second time sintering.
After second time sintering, again even for abundant for compound mixed grinding, be compressing tablet 10min in the pressure environment of 18MPa at pressure, be positioned among air atmosphere, third firing is carried out at 950 DEG C, calcination time is 8 hours, is cooled to room temperature, takes out sample and carry out grinding namely to obtain pulverous erbium ion-doped New Tungsten salt luminescent material.
See accompanying drawing 5, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 2.24 watts, as seen from Figure 5, this material launches main peak at 530 nm, is Green upconversion luminescent.
Embodiment 5
Preparation MgLa
0.2er
0.6yb
1.2(WO
4)
4
According to chemical formula MgLa
0.2er
0.6yb
1.2(WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.788 gram, Erbium trioxide Er
2o
3: 0.382 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams, then take citric acid respectively by 0.5 wt% of above each drug quality.First the above-mentioned each raw material taken is dissolved in appropriate salpeter solution respectively, magnetic agitation 0.5 hour, and dilutes with the deionization of 5 times of its volumes, stir.To be dissolved completely after, in each solution, add the citric acid taken respectively, and stir 1 hour under magnetic stirring.Finally, each solution obtained is mixed, to continue at 50 DEG C heated and stirred 2 hours, leave standstill, dry, obtain fluffy presoma; Precursor is placed in retort furnace calcine, calcining temperature is 450 DEG C for the first time, calcination time 4 hours; Second time calcining temperature is 550 DEG C, calcination time 8 hours; Then be chilled to room temperature, take out sample and fully grinding, carry out third firing, temperature is 1050 DEG C, calcination time 13 hours, is then cooled to 380 DEG C and is incubated 5 hours, carries out grinding namely obtaining pulverous erbium ion-doped New Tungsten salt luminescent material after cooling.
See accompanying drawing 6, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 2.41 watts, as seen from Figure 6, this material launches main peak at 525 nm, is Green upconversion luminescent.
Embodiment 6
Preparation MgLa
0.6er
0.4yb (WO
4)
4
According to chemical formula MgLa
0.6er
0.4yb (WO
4)
4in the stoichiometric ratio of each element, take respectively: magnesium basic carbonate C
4mg
4o
2-H
2mgO
2-5H
2o:0.32 gram, lanthanum trioxide La
2o
3: 0.87 gram, ytterbium oxide Yb
2o
3: 0.657 gram, Erbium trioxide Er
2o
3: 0.255 gram, ammonium tungstate (NH
4)
10w
12o
41: 3.38 grams, then take oxalic acid respectively by 2 wt% of above each drug quality.The above-mentioned each raw material taken is dissolved in appropriate salpeter solution respectively, magnetic agitation 1.5 hours, and dilutes with the deionization of 5 times of its volumes, stir.To be dissolved completely after, in each solution, add the oxalic acid taken respectively, and stir 1 hour under magnetic stirring.The each solution obtained is mixed, to continue at 50 DEG C heated and stirred 1 hour, leave standstill, dry, obtain fluffy presoma; Precursor is placed in retort furnace calcine, calcining temperature is 580 DEG C for the first time, calcination time 9 hours; Second time calcining temperature is 500 DEG C, calcination time 4 hours; Then be chilled to room temperature, take out sample and fully grinding, carry out third firing, temperature is 650 DEG C, and then calcination time 3 hours is cooled to 250 DEG C and is incubated 2 hours, carries out grinding namely obtaining the erbium ion-doped New Tungsten salt luminescent material of powder shaped after cooling.
See accompanying drawing 7, its to be the sample prepared by the present embodiment technical scheme in 975 nanometers, excitation energy intensity be infrared ray excited lower up-conversion luminescence spectrum of 2.66 watts, as seen from Figure 7, this material launches main peak at 525 nm, is Green upconversion luminescent.
Claims (10)
1. an erbium ion-doped tungstate up-conversion luminescent material, is characterized in that: its chemical general formula is MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4, wherein,
xfor Er
3+the molecular fraction of doping, y is Yb
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0.
2. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material as claimed in claim 1, is characterized in that adopting high temperature solid-state method, comprises the steps:
By chemical formula MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4in the stoichiometric ratio of each element, wherein,
xfor Er
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0, takes respectively containing magnesium ion Mg
2+compound, containing lanthanum ion La
3+compound, containing ytterbium ion Yb
3+compound, containing erbium ion Er
3+compound, containing tungsten ion W
6+compound, grind and mix, after compressing tablet, obtaining sheet precast body;
The precast body that step (1) is obtained presintering 1 ~ 2 time in air atmosphere, pre-sintering temperature is 300 ~ 700 DEG C, and sintering time is 1 ~ 12 hour, grinds and mix after naturally cooling, and compressing tablet obtains flap;
Calcined in air atmosphere by the flap that step (2) obtains, calcining temperature is 700 ~ 1300 DEG C, and calcination time is 2 ~ 15 hours, naturally cools to room temperature, grinds and mix namely to obtain Powdered erbium ion-doped tungstate up-conversion luminescent material.
3. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 2, is characterized in that: the sintering temperature of step (2) is 350 ~ 680 DEG C, and calcination time is 2 ~ 10 hours; The calcining temperature of step (3) is 750 ~ 1250 DEG C, and calcination time is 3 ~ 10 hours.
4. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 2, is characterized in that: described contains magnesium ion Mg
2+compound be one in magnesium oxide, magnesium basic carbonate, magnesium sulfate, magnesium nitrate; Described contains lanthanum ion La
3+compound be one in lanthanum trioxide, lanthanum nitrate; Described contains ytterbium ion Yb
3+compound be one in ytterbium oxide, ytterbium nitrate; Described contains erbium ion Er
3+compound be one in Erbium trioxide, Erbium trinitrate; Described contains tungsten ion W
6+compound be one in Tungsten oxide 99.999, ammonium tungstate.
5. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 2 or 4, is characterized in that: described contains magnesium ion Mg
2+compound be magnesium basic carbonate; Described contains lanthanum ion La
3+compound be lanthanum trioxide; Described contains ytterbium ion Yb
3+compound be ytterbium oxide; Described contains erbium ion Er
3+compound be Erbium trioxide; Described contains tungsten ion W
6+compound be ammonium tungstate.
6. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material as claimed in claim 1, is characterized in that adopting chemical synthesis, comprises the steps:
By chemical formula MgLa
2-2 (x+y)er
2xyb
2y(WO
4)
4in the stoichiometric ratio of each element, wherein,
xfor Er
3+the molecular fraction of doping, 0.0001≤
x<0.5,0.1≤y<1.0, and 0.1<
x+ y<1.0, takes respectively containing magnesium ion Mg
2+compound, containing lanthanum ion La
3+compound, containing ytterbium ion Yb
3+compound, containing erbium ion Er
3+compound, containing tungsten ion W
6+compound, they are dissolved in dust technology under magnetic stirring respectively, by volume, with the deionized waters of 2 ~ 4 times dilution;
Adding complexing agent respectively by 0.5 ~ 2.0 wt% of reactant quality in each raw material, under magnetic stirring to dissolving completely, obtaining the solution of each raw material; Described complexing agent is the one in citric acid or oxalic acid;
The solution of each raw material step (2) obtained slowly mixes, in temperature be under the condition of 50 ~ 100 DEG C stir 1 ~ 2 hour, leave standstill, dry after obtain fluffy presoma;
Presoma is placed in retort furnace, in air atmosphere presintering 1 ~ 2 time, sintering temperature is 400 ~ 600 DEG C, and sintering time is once 3 ~ 10 hours, after naturally cooling, grinds and mixes;
Calcined in air atmosphere by the mixture that step (4) obtains, calcining temperature is 600 ~ 1100 DEG C, and calcination time is 1 ~ 15 hour; Be cooled to 200 ~ 400 DEG C, be incubated and be cooled to room temperature after 1 ~ 6 hour, after grinding evenly, namely obtain Powdered erbium ion-doped tungstate luminescent material.
7. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 6, is characterized in that: described contains magnesium ion Mg
2+compound be one in magnesium oxide, magnesium basic carbonate, magnesium sulfate, magnesium nitrate; Described contains lanthanum ion La
3+compound be one in lanthanum trioxide, lanthanum nitrate; Described contains ytterbium ion Yb
3+compound be one in ytterbium oxide, ytterbium nitrate; Described contains erbium ion Er
3+compound be one in Erbium trioxide, Erbium trinitrate; Described contains tungsten ion W
6+compound be one in Tungsten oxide 99.999, ammonium tungstate.
8. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 6 or 7, is characterized in that: described contains magnesium ion Mg
2+compound be magnesium basic carbonate; Described contains lanthanum ion La
3+compound be lanthanum trioxide; Described contains ytterbium ion Yb
3+compound be ytterbium oxide; Described contains erbium ion Er
3+compound be Erbium trioxide; Described contains tungsten ion W
6+compound be ammonium tungstate.
9. the preparation method of a kind of erbium ion-doped tungstate up-conversion luminescent material according to claim 6, is characterized in that: the sintering temperature of step (4) is 450 ~ 580 DEG C, and calcination time is 4 ~ 9 hours; The calcining temperature of step (5) is 650 ~ 1050 DEG C, and calcination time is 3 ~ 13 hours, and holding temperature is 250 ~ 380 DEG C, and soaking time is 2 ~ 5 hours.
10. the application of a kind of erbium ion-doped tungstate up-conversion luminescent material as claimed in claim 1, is characterized in that: described luminescent material is used for anti-counterfeiting mark, biomolecules fluorescent mark, 3 D stereo display.
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| Synthesis and upconversion luminescence properties of Yb3+/Er3+ codoped;Haiyan Du等;《Materials Research Bulletin》;20090503;第44卷;全文 * |
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