A kind of doping Yb
3+vanadate upconverting fluorescent material and preparation method thereof
Technical field
The present invention relates to a kind of upconverting fluorescent material and preparation method thereof, particularly a kind of up-conversion that sends the visible blue green light under infrared ray excited, belong to the luminescent material technical field.
Background technology
Rare earth ion ytterbium Yb
3+be the active ions that a kind of luminescent properties is very good, its maximum characteristics are that level structure is very simple, only have
2f
7/2with
2f
5/2two isolated energy levels, Yb
3+it is within the wavelength region between the 0.1-1.0 micron that the characteristic light of ion absorbs, and has the Absorber Bandwidth of non-constant width, so Yb
3+the material of ion doping can effectively be coupled with InGaAs semi-conductor pump light source; In addition, doping Yb
3+there is not excited state absorption in the laserable material of ion, and fluorescence efficiency is very high usually, and the life-span of fluorescence is very long.Therefore Yb adulterates
3+the laserable material of ion always is the focus that people study.
Up-conversion luminescent material under infrared ray excited is a kind of at the infrared ray excited lower material that can send visible ray, and up-conversion luminescent material has good application background in the detection of antiforge, three-dimensional stereo display, short wavelength's all solid state laser and ir radiation etc. field.
Nakazawa E in 1970 and Shinonnya S are at YbPO
4in at first reported Yb
3+ion is at the cooperation up-conversion luminescence behavior of blue green light wave band, Yb
3+the up-conversion luminescence behavior of ion is unique, Yb
3+ion pair is not that the mode by excited state absorption realizes up-conversion luminescence, but by two close Yb of excited state
3+the ion colleague's de excitation that is coupled mutually is dealt into ground state and realizes luminous.The up-conversion luminescence of this uniqueness can be for the solid laser of developing optical bistability, high-speed computer and blue wave band etc. novel optics, wherein blue green light band laser material has huge potential application foreground in fields such as high density data storage, optical communication and demonstration, laser medicine, laser anti-counterfeit, induced with laser, so Yb
3+ion has caused people's research and concern in the up-conversion luminescence behavior of visible ray blue green light wave band.
Study at present more up-conversion luminescent material kind more, study more main mostly be to take the body material that fluorochemical or oxyfluoride be matrix, although the efficiency of its up-conversion luminescence is higher, but the preparation of fluorochemical is extremely complicated, the pollution of preparation process is quite serious, the environmental requirement of producing is very harsh, thereby production cost is also very high, and these have all seriously hindered the practical application of up-conversion luminescent material.The up-conversion luminescent material that the oxide compound of take is matrix has a lot of good characteristics, and for example the technique of preparation is very simple, also lower to the requirement of envrionment conditions, and luminous temperature performance, the thermal stability of material are fine.
Rare earth vanadic acid calcium substrate material has good physical and chemical performance, Yb
3+ion has quite wide absorption band among this substrate material near 980 nanometers, therefore can improve the pumping efficiency of infrared laser, and these characteristics all make it become a kind of good up-conversion luminescence substrate material.At present, with trivalent ytterbium, the up-conversion luminescence of ion-activated vanadate has no bibliographical information.
Summary of the invention
The purpose of this invention is to provide a kind of degree of crystallinity high, substrate material is thermally-stabilised good, prepares simple, free of contamination vanadate phosphor and preparation method thereof, passes through Yb
3+the doping of ion, realize obtaining bright blue-greenish colour up-conversion fluorescence under infrared ray excited.
For reaching above purpose, the technical solution used in the present invention is: a kind of doping Yb is provided
3+the vanadate upconverting fluorescent material, its active ions are ytterbium ion Yb
3+, under the exciting of 980 nanometer infrared lights, the emission wavelength of described fluorescent material is near the blue-greenish colour fluorescence 475 nanometers and 523 nanometers; The chemical formula of the matrix of described fluorescent material is Ca
9ln
1-xyb
x(VO
4)
7, wherein, Ln is rare-earth yttrium ion Y
3+, lanthanum ion La
3+, gadolinium ion Gd
3+, lutetium ion Lu
3+in a kind of, or their arbitrary combination;
xfor ytterbium ion Yb
3+the molar percentage coefficient of doping, 0.0001<x≤1.0.
A kind of doping Yb
3+the preparation method of vanadate upconverting fluorescent material, adopt high temperature solid phase synthesis, comprise the steps:
(1) to contain calcium ion Ca
2+, rare earth ion lutetium ion Ln, vanadium ion V
5+, ytterbium ion Yb
3+compound be raw material, press chemical formula Ca
9ln
1-xyb
x(VO
4)
7in the mol ratio of each element take each raw material, grind and mix, obtain mixture; Described rare earth ion Ln is rare-earth yttrium ion Y
3+, lanthanum ion La
3+, gadolinium ion Gd
3+, lutetium ion Lu
3+in a kind of, or their arbitrary combination;
(2) by the presintering 1~2 time under air atmosphere of the mixture that obtains, pre-sintering temperature is 250~700 ℃, and the presintering time each time is 1~10 hour;
(3) after naturally cooling, grind and mix, finally calcine in air atmosphere, calcining temperature is 900~1100 ℃, and the calcining soaking time is 3~10 hours, naturally cools to room temperature, obtains a kind of doping Yb
3+the vanadate upconverting fluorescent material.
Another kind of doping Yb
3+the preparation method of vanadate upconverting fluorescent material, it is characterized in that adopting the chemical solution synthesis method, comprise the steps:
(1) press chemical formula Ca
9ln
1-xyb
x(VO
4)
7in the Mol ratio of each element, wherein 0.0001<x≤1.0, take respectively reactant and contain calcium ion Ca
2+, rare earth ion Ln, ytterbium ion Yb
3+compound, described rare earth ion Ln is rare-earth yttrium ion Y
3+, lanthanum ion La
3+, gadolinium ion Gd
3+, lutetium ion Lu
3+in a kind of, or their arbitrary combination; They are dissolved in respectively in distilled water or nitric acid, obtain clear solution; 0.5~2.0 wt% by each reactant quality adds respectively complexing agent citric acid or oxalic acid in each clear solution again, is heated to 50~100 ℃, stirs 0.5~3 hour, obtains the transparent mixture liquid of various respective reaction things; The pH value of regulating them is 5~6;
(2) press chemical formula Ca
9ln
1-xyb
x(VO
4)
7in the Mol ratio of each element, take and contain vanadium ion V
5+compound, be dissolved in distilled water or nitric acid, obtain clear solution; 0.5~2.0 wt% that presses again the reactant quality adds complexing agent citric acid or oxalic acid complexing vanadium ion V
5+, be heated to 50~100 ℃, stir 0.5~3 hour, obtain corresponding transparent mixture liquid; Regulating the pH value is 7~8;
(3) the various mixture liquid that step (1) and (2) obtained mix, and stir, then stir 1~2 hour under the temperature condition of 50~100 ℃, standing, dry, and obtain fluffy presoma;
(4) presoma is placed in to retort furnace and is calcined, processing condition are: first be warming up to 400~700 ℃, insulation is greater than 2 hours; Then be warmed up to 850~1100 ℃ and finally calcine, calcination time 3~10 hours, naturally cool to room temperature, obtains a kind of doping Yb
3+the vanadate upconverting fluorescent material.
The described calcium ion Ca that contains
2+compound be a kind of in calcium oxide, calcium carbonate, nitrocalcite, calcium sulfate, caoxalate, or their arbitrary combination.
The described compound that contains rare earth ion Ln is rare-earth yttrium ion Y
3+, lanthanum ion La
3+, gadolinium ion Gd
3+, lutetium ion Lu
3+oxide compound, nitrate in a kind of, or their arbitrary combination.
The described rare earth ion ytterbium ion Yb that contains
3+compound be a kind of in rare-earth yttrium ionic oxide formation ytterbium, ytterbium nitrate, or their arbitrary combination.
The described vanadium ion V that contains
5+compound be a kind of in Vanadium Pentoxide in FLAKES, vanadic acid ammonia, or the combination of two kinds.
In the present invention, pre-burning is become 1 time, and pre-sintering temperature is 350~550 ℃, and the presintering time is 3~5 hours.The temperature of final calcining is 950~1050 ℃, and calcination time is 5~8 hours.
The accompanying drawing explanation
Fig. 1 is the comparison of X-ray powder diffraction collection of illustrative plates and the standard card PDF#46-0410 of sample in the embodiment of the present invention 1;
Fig. 2 is the Ca that the embodiment of the present invention 1 provides
9la
0.9yb
0.1(VO
4)
7luminescent spectrum figure under the excitation that sample is 0.7 watt at 980nm, power;
Fig. 3 is the Ca that the embodiment of the present invention 2 provides
9la
0.2yb
0.8(VO
4)
7luminescent spectrum figure under the excitation that sample is 0.7 watt at 980nm, power;
Fig. 4 is the Ca that the embodiment of the present invention 6 provides
9yb (VO
4)
7luminescent spectrum figure under the excitation that sample is 0.7 watt at 980nm, power;
Fig. 5 is the Ca that the embodiment of the present invention 7 provides
9yb (VO
4)
7luminescent spectrum figure under the excitation that sample is 0.7 watt at 980nm, power.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
Prepare up-conversion luminescent material Ca
9la
0.9yb
0.1(VO
4)
7
Take calcium carbonate CaCO
3: 4.5041 grams, lanthanum trioxide La
2o
3: 0.7331 gram, ytterbium oxide Yb
2o
3: 0.1 gram, and vanadic acid ammonia NH
4vO
3: 4.0943 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, calcination time 3 hours, then be chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 630 ℃, sintering time is 5 hours, the cooling room temperature that causes; Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 1000 ℃, sintering time is 6 hours, the cooling room temperature that causes; Obtain powder shaped Yb
3+rare earth doped vanadic acid calcium base upconverting fluorescent material.
Referring to accompanying drawing 1, prepare X-ray powder diffraction collection of illustrative plates and the demonstration of standard card PDF#46-0410 comparative result of sample by the present embodiment technical scheme, prepared material is monophase materials.
Referring to accompanying drawing 2, be the up-conversion luminescence spectrum of sample under 0.7 watt of 980 nanometer excites prepared by the present embodiment technical scheme, be presented on the blue-greenish colour fluorescence of 475 nanometers and 523 nanometers.
Embodiment 2
Prepare up-conversion luminescent material Ca
9la
0.2yb
0.8(VO
4)
7
Take calcium carbonate CaCO
3: 4.5041 grams, lanthanum trioxide La
2o
3: 0.163 gram, ytterbium oxide Yb
2o
3: 0.7882 gram, and vanadic acid ammonia NH
4vO
3: 4.0943 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 450 ℃, calcination time 5 hours, then be chilled to room temperature, takes out sample.After the raw material of calcining for the first time, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 950 ℃, sintering time is 10 hours, the cooling room temperature that causes; Obtain powder shaped Yb
3+rare earth doped vanadic acid calcium base upconverting fluorescent material.
Referring to accompanying drawing 3, it is the up-conversion luminescence spectrogram of sample under 0.7 watt of 980 nanometer excites prepared by the present embodiment technical scheme, is presented on the blue-greenish colour fluorescence of 475 nanometers and 523 nanometers.
Embodiment 3
Prepare up-conversion luminescent material Ca
9gd
0.2yb
0.8(VO
4)
7
Take calcium carbonate CaCO
3: 4.5041 grams, gadolinium sesquioxide Gd
2o
3: 0.1813 gram, ytterbium oxide Yb
2o
3: 0.7882 gram, and vanadic acid ammonia NH
4vO
3: 4.0943 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 500 ℃, calcination time 6 hours, then be chilled to room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 1050 ℃, sintering time is 7 hours, the cooling room temperature that causes; Obtain powder shaped Yb
3+rare earth doped vanadic acid calcium base upconverting fluorescent material.Up-conversion luminescence spectrum and legend 3 that the present embodiment technical scheme prepares sample are approximate.
Embodiment 4
Prepare up-conversion luminescent material 4 Ca
9y
0.2yb
0.8(VO
4)
7
Take calcium carbonate CaCO
3: 4.5041 grams, yttrium oxide Y
2o
3: 0.113 gram, ytterbium oxide Yb
2o
3: 0.7882 gram, and vanadic acid ammonia NH
4vO
3: 4.0943 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, calcination time 10 hours, then be chilled to room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 1100 ℃, sintering time is 4 hours, the cooling room temperature that causes; Obtain powder shaped Yb
3+rare earth doped vanadic acid calcium base upconverting fluorescent material.Up-conversion luminescence spectrum and legend 3 that the present embodiment technical scheme prepares sample are approximate.
Embodiment 5
Prepare up-conversion luminescent material Ca
9lu
0.1yb
0.9(VO
4)
7
Take calcium carbonate CaCO
3: 4.5041 grams, lutecium oxide Lu
2o
3: 0.1 gram, ytterbium oxide Yb
2o
3: 0.8867 gram, and vanadic acid ammonia NH
4vO
3: 4.0943 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, calcination time 8 hours, then be chilled to room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 800 ℃, sintering time is 3 hours, the cooling room temperature that causes; Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 1000 ℃, sintering time is 5 hours, the cooling room temperature that causes; Obtain powder shaped Yb
3+rare earth doped vanadic acid calcium base upconverting fluorescent material.Up-conversion luminescence spectrum and legend 3 that the embodiment technical scheme prepares sample are approximate.
Embodiment 6
Prepare up-conversion luminescent material Ca
9yb (VO
4)
7
Take calcium carbonate CaCO
3: 9.01 grams, ytterbium oxide Yb
2o
3: 1.971 grams, and vanadic acid ammonia NH
4vO
3: 8.1886 grams, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, calcination time 4 hours, then be chilled to room temperature, takes out sample.Again even the abundant mixed grinding of compound, among air atmosphere, sintering for the second time under 1000 ℃, sintering time is 8 hours, the cooling room temperature that causes; Obtain powder shaped vanadic acid ytterbium calcium upconverting fluorescent material.Fig. 4 is embodiment 6 Ca
9yb (VO
4)
7the up-conversion luminescence spectrum of sample under 980nm excites, exciting light is 0.7 watt.Be presented on the blue-greenish colour fluorescence of 475 nanometers and 523 nanometers.
Embodiment 7
Prepare up-conversion luminescent material Ca
9yb (VO
4)
7
Take four water-calcium nitrate Ca (NO
3)
2.4H
2the O:10.627 gram is dissolved in distilled water; Take ytterbium oxide Yb
2o
3: 0.9853 gram, heating 80-100 degree is dissolved in nitric acid, mixes two kinds of solution, adds citric acid 0.12 gram, regulates pH value to 5.5, obtains clear solution 1.Take vanadic acid ammonia NH
4vO
3: 4.0943 grams, be dissolved in distilled water, be heated to 80 ℃, stir 1.5 hours, obtain clear solution 2, regulate pH value to 7.5.Solution 1 and solution 2 are mixed, stir under the temperature condition of 50~100 ℃ after 2 hours, standing, among baking oven, dry, obtain presoma; The presoma obtained is placed in to retort furnace to be calcined: at first be warmed up to 650 degree, be incubated 5 hours; Then be warmed up to 1000 ℃, calcination time is 8 hours again.Obtain powder shaped vanadic acid ytterbium calcium upconverting fluorescent material.Legend 5 is embodiment 7 Ca
9yb (VO
4)
7the up-conversion luminescence spectrum of sample under 980nm excites, exciting light is 0.7 watt, and sample has bright up-conversion luminescence, and luminous main peak is in 475 nanometers and 523 nanometers.