Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide a kind of chemical purity high, luminous mass is good, and simple, the free of contamination boron tungstate up-conversion luminescent material of preparation technology and preparation method thereof.
For reaching above purpose, the technical solution used in the present invention provides a kind of ytterbium ion Yb
3+The boron tungstate up-conversion luminescent material that activates, its chemical formula is R
3-3xYb
3xBWO
9, wherein, R is rare earth erbium ion Er
3+, europium ion Eu
3+, lanthanum ion La
3+, ruthenium ion Y
3+, cerium ion Ce
3+, thulium ion Tm
3+, praseodymium ion Pr
3+, neodymium ion Nd
3+, samarium ion Sm
3+, gadolinium ion Gd
3+, terbium ion Tb
3+In a kind of, or their arbitrary combination;
xBe ytterbium ion Yb
3+The molecular fraction of mixing, 0.0001<x≤1.0; Described up-conversion luminescent material is under the infrared laser pumping of 975 nanometers, and obtaining wavelength is the green up-conversion luminescence of 530~560 nanometers.
A kind of aforesaid ytterbium ion Yb
3+The preparation method of the boron tungstate up-conversion luminescent material that activates adopts high temperature solid-state method, comprises the steps:
(1) presses chemical formula R
3-3xYb
3xBWO
9In the stoichiometric ratio of each element, take by weighing respectively and contain ytterbium ion Yb
3+Compound, contain rare earth ion R compound, contain boron ion B
3+Compound, contain tungsten ion W
6+Compound, grind and mix, obtain mixture; Wherein, R is rare earth erbium ion Er
3+, europium ion Eu
3+, lanthanum ion La
3+, ruthenium ion Y
3+, cerium ion Ce
3+, thulium ion Tm
3+, praseodymium ion Pr
3+, neodymium ion Nd
3+, samarium ion Sm
3+, gadolinium ion Gd
3+, terbium ion Tb
3+In a kind of, or their arbitrary combination;
xBe ytterbium ion Yb
3+The molecular fraction of mixing, 0.0001<x≤1.0;
(2) mixture is calcined under air atmosphere 1~2 time, calcining temperature is 200~600 ℃, and calcination time is 1~15 hour;
(3) the mixture naturally cooling that step (2) is obtained after grinding and mixing, is calcined in air atmosphere, and calcining temperature is 600~800 ℃, and calcination time is 1~15 hour;
(4) the mixture naturally cooling that step (3) is obtained after grinding and mixing, is calcined in air atmosphere, and calcining temperature is 800~1000 ℃, and calcination time is 1~15 hour;
(5) the mixture naturally cooling that step (4) is obtained after grinding and mixing, is calcined in air atmosphere, and calcining temperature is 1000~1300 ℃, and calcination time is 1~15 hour, naturally cools to room temperature, obtains a kind of ytterbium ion Yb
3+The boron tungstate up-conversion luminescent material that activates.
Adopt high temperature solid-state method to prepare ytterbium ion Yb
3+The preferred version of the boron tungstate up-conversion luminescent material that activates is: the calcining temperature of step (2) is 250~550 ℃, and calcination time is 2~12 hours; The calcining temperature of step (3) is 600~750 ℃, and calcination time is 2~12 hours; The calcining temperature of step (4) is 800~950 ℃, and calcination time is 2~12 hours; The calcining temperature of step (5) is 1000~1250 ℃, and calcination time is 2~12 hours.
Technical solution of the present invention also provides a kind of employing chemical synthesis to prepare described ytterbium ion Yb
3+The boron tungstate up-conversion luminescent material that activates comprises the steps:
(1) presses chemical formula R
3-3xYb
3xBWO
9In the stoichiometric ratio of each element, take by weighing and contain ytterbium ion Yb
3+Compound, contain rare earth ion R compound, contain tungsten ion W
6+Compound, they are dissolved in respectively in the dilute nitric acid solution, obtain the clear solution of various elements; Wherein, R is rare earth erbium ion Er
3+, europium ion Eu
3+, lanthanum ion La
3+, ruthenium ion Y
3+, cerium ion Ce
3+, thulium ion Tm
3+, praseodymium ion Pr
3+, neodymium ion Nd
3+, samarium ion Sm
3+, gadolinium ion Gd
3+, terbium ion Tb
3+In a kind of, or their arbitrary combination;
xBe ytterbium ion Yb
3+The molecular fraction of mixing, 0.0001<x≤1.0; 0.5~2.0wt% by each reactant quality adds respectively complexing agent citric acid or oxalic acid again, stirs under 50~100 ℃ temperature condition;
(2) press chemical formula R
3-3xYb
3xBWO
9Middle boron ion B
3+The stoichiometric ratio of element takes by weighing and contains boron ion B
3+Compound, it is dissolved in deionized water or the ethanolic soln, obtain solution; 0.5~the 2.0wt% that presses the reactant quality adds complexing agent citric acid or oxalic acid, stirs under 50~100 ℃ temperature condition;
(3) the various solution that step (1) and (2) obtained slowly mix, and after stirring 1~2 hour under 50~100 ℃ the temperature condition, leave standstill, and oven dry obtains fluffy presoma;
(4) place retort furnace to calcine presoma, calcining temperature is 1000~1300 ℃, and calcination time is 1~15 hour, naturally cools to room temperature, obtains a kind of ytterbium ion Yb
3+The boron tungstate up-conversion luminescent material that activates.
The ytterbium ion Yb that contains of the present invention
3+Compound be ytterbium oxide, fluoridize a kind of in ytterbium, the ytterbium nitrate or their arbitrary combination; The described boron ion B that contains
3+Compound be a kind of in boron oxide, boron nitride, sulfuration boron, the boric acid, or their arbitrary combination; The described tungsten ion W that contains
6+Compound be a kind of in Tungsten oxide 99.999, the ammonium tungstate, or their arbitrary combination.
Compared with prior art, the advantage of technical solution of the present invention is:
1, the present invention utilizes ytterbium ion Yb
3+Between unique upper conversion behavior, realized the preparation of up-conversion luminescent material, under the 975nm infrared laser light source, material can be realized green up-conversion luminescence, and luminosity is high, stable luminescent property has broad application prospects at aspects such as photoelectronics, laser technology, high-density storage, laser anti-counterfeits.
2, compare with other up-conversion luminescent material take fluorochemical as matrix, the preparation process of substrate material of the present invention is without any pollution, and preparation process is simple, and the product easily collecting is without the waste water and gas discharging, environmentally friendly.
3, because the present invention calcines to make, need not to provide reducing atmosphere, so operating process is simple in air atmosphere, lower to the requirement of equipment, can reduce production costs, and synthetic up-conversion luminescent material stable performance.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
According to chemical formula Yb
2.85Eu
0.15BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.404 grams, europium sesquioxide Eu
2O
3: 0.066 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 550 ℃, then calcination time 7 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 750 ℃ of lower for the second time sintering, sintering time is 10 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 950 ℃, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1250 ℃ of lower the 4th sintering, sintering time is 10 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.
Referring to accompanying drawing 1, be the X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme prepares sample, PDF#51-0101 is in full accord with standard card.
Referring to accompanying drawing 2, to be 0.998 watt infrared ray excited lower up-conversion luminescence spectrum in 975nm, excitation energy intensity by the sample of the present embodiment technical scheme preparation, as seen from Figure 2, this material emission main peak is green up-conversion luminescence near 540 nanometers.
Embodiment 2
According to chemical formula Yb
2.7Eu
0.3BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.33 grams, europium sesquioxide Eu
2O
3: 0.132 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 500 ℃, then calcination time 6 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 700 ℃ of lower for the second time sintering, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 900 ℃, sintering time is 10 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1200 ℃ of lower the 4th sintering, sintering time is 10 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 are approximate.
Referring to accompanying drawing 3, that sample by the present embodiment technical scheme preparation is 0.998 watt the infrared ray excited lower up-conversion luminescence spectrum that obtains in 975nm, excitation energy intensity, as seen from Figure 3, this material emission main peak is green up-conversion luminescence near 540 nanometers.
Embodiment 3
According to chemical formula Yb
2.55Y
0.45BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.256 grams, yttrium oxide Y
2O
3: 0.127 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, then calcination time 5 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 680 ℃ of lower for the second time sintering, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 860 ℃, sintering time is 9 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1150 ℃ of lower the 4th sintering, sintering time is 12 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 are approximate, and its excitation spectrum and accompanying drawing 3 are approximate.
Embodiment 4
According to chemical formula Yb
2.4Eu
0.6BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.182 grams, europium sesquioxide Eu
2O
3: 0.264 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, then calcination time 5 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 650 ℃ of lower for the second time sintering, sintering time is 7 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 850 ℃, sintering time is 9 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1100 ℃ of lower the 4th sintering, sintering time is 10 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 are approximate.
Referring to accompanying drawing 4, by the sample of the present embodiment technical scheme preparation infrared ray excited lower up-conversion luminescence spectrogram that obtains in 975nm, different excitation energy intensity, as seen from Figure 4, the luminous intensity of this material increases along with the enhancing of excitation diode energy intensity.
Embodiment 5
According to chemical formula Yb
2.1Eu
0.9BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.035 grams, europium sesquioxide Eu
2O
3: 0.396 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 320 ℃, then calcination time 4 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 630 ℃ of lower for the second time sintering, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 830 ℃, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1080 ℃ of lower the 4th sintering, sintering time is 12 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 are approximate.
Referring to accompanying drawing 5, by the sample of the present embodiment technical scheme preparation infrared ray excited lower up-conversion luminescence spectrogram that obtains in 975nm, different excitation energy intensity, as seen from Figure 5, the luminous intensity of this material increases along with the enhancing of excitation diode energy intensity.
Embodiment 6
According to chemical formula Yb
1.8Ga
1.2BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 1.035 grams, gadolinium sesquioxide Ga
2O
3: 0.489 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 310 ℃, then calcination time 3 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 630 ℃ of lower for the second time sintering, sintering time is 9 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 840 ℃, sintering time is 5 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1100 ℃ of lower the 4th sintering, sintering time is 11 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 is approximate, and the up-conversion luminescence spectrogram under its different excitation energy intensity infrared ray excited is similar to accompanying drawing 5.
Embodiment 7
According to chemical formula Yb
1.2Eu
1.8BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 0.591 gram, europium sesquioxide Eu
2O
3: 0.792 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, then calcination time 5 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 620 ℃ of lower for the second time sintering, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 810 ℃, sintering time is 10 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1050 ℃ of lower the 4th sintering, sintering time is 10 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 are approximate.
Referring to accompanying drawing 6, that sample by the present embodiment technical scheme preparation is 0.998 watt the infrared ray excited lower up-conversion luminescence spectrum that obtains in 975nm, excitation energy intensity, as seen from Figure 6, this material emission main peak is green up-conversion luminescence near 530 nanometers.
Embodiment 8
According to chemical formula Yb
0.9La
2.1BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 0.444 gram, lanthanum trioxide La
2O
3: 0.855 gram, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 280 ℃, then calcination time 6 hours is chilled to room temperature, takes out sample.After the raw material of for the first time calcining, again even the abundant mixed grinding of compound, among air atmosphere, 610 ℃ of lower for the second time sintering, sintering time is 8 hours, is cooled to room temperature, takes out sample.After the raw material of for the second time calcining, again even the abundant mixed grinding of compound, among air atmosphere, sintering for the third time under 825 ℃, sintering time is 9 hours, is cooled to room temperature, takes out sample.After the raw material of third firing, again even the abundant mixed grinding of compound, among air atmosphere, 1050 ℃ of lower the 4th sintering, sintering time is 12 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder.Its XRD diffraction spectrogram and accompanying drawing 1 is approximate, and the up-conversion luminescence spectrogram under its different excitation energy intensity infrared ray excited is similar to accompanying drawing 5.
Embodiment 9
According to chemical formula Yb
0.6Eu
2.4BWO
9The stoichiometric ratio of each element in 975nm takes by weighing respectively ytterbium oxide Yb
2O
3: 0.296 gram, europium sesquioxide Eu
2O
3: 1.056 grams, boric acid H
3BO
3: 0.1623 gram, Tungsten oxide 99.999 WO
3: 0.597 gram, and the citric acid of the 1.8wt% of above medicine total mass, with the ytterbium oxide Y that takes by weighing
2O
3, europium sesquioxide Eu
2O
3With Tungsten oxide 99.999 WO
3Be dissolved in an amount of dilute nitric acid solution, add an amount of deionized water and citric acid in 70 ℃ of stirrings; Then the boric acid that takes by weighing is dissolved in an amount of deionized water, adds again remaining citric acid, and constantly in 70 ℃ of lower stirrings; Above-mentioned two kinds of solution are slowly mixed and constantly stirred 1.5 hours; Leave standstill, oven dry obtains fluffy precursor; Place retort furnace to calcine precursor, sintering temperature is 1000 ℃, and calcination time is 10 hours, is cooled to room temperature, namely obtains pulverous upconversion fluorescent powder, and its XRD diffraction spectrogram and accompanying drawing 1 are approximate.
Referring to accompanying drawing 7, by the sample of the present embodiment technical scheme preparation infrared ray excited lower up-conversion luminescence spectrogram that obtains in 975nm, different excitation energy intensity, as seen from Figure 7, the luminous intensity of this material increases along with the enhancing of excitation diode energy intensity.