A kind of realize near-infrared luminous material and preparation method under ultraviolet excitation
Technical field
The present invention relates to a kind of preparation method and applications of luminescent material, real under ultraviolet excitation particularly to one kind
Existing near-infrared luminous material and preparation method, belong to luminescent material technical field.
Background technology
Since 21 century, energy shortage and environmental pollution more and more govern the sustainable development of future society, for this
The mankind represent the developing direction of clean energy resource in the urgent need to development and application new forms of energy, the renewable energy technologies such as solar energy,
Cause the extensive concern of countries in the world, and the important component part of following basic energy resource will be become.
Solar cell is a kind of device that solar energy is converted into electric energy using photovoltaic effect, according to material
Battery can be divided into by the difference of material:Silicon solar cell, nano-crystalline solar battery, with inorganic salts such as GaAs, cadmium sulfide
The multi-element compounds such as CIS are the solar cell of material, organic solar batteries, the sun of functional high molecule material preparation
Energy battery, wherein Development Technology is the most ripe, and most widely used is exactly silica-based solar cell.Silicon solar cell is to incident light
Significant response spectral range be 400~1100 nanometers, this spatial distribution Incomplete matching with sunshine is so that account for sunshine
In the ultraviolet light of significant portion of short wavelength can not be fully absorbed utilization, how silicon solar cell is made by spectral modulation
More fully absorbing sunshine, thus improving the photoelectric transformation efficiency of silica-based solar cell, being that people presently the most pay close attention to
One of problem.
In order to solve this difficult problem, people change luminescent layer under the introducing of the upper surface of solar cell, by doping
Rare earth quantum-cutting, absorbs poor short wavelength photons of a battery spectral response, then it is preferable to launch spectral response
Two or more infrared photons, thus greatly eliminating spectral mismatch phenomenon, improving battery lighting spectrum response and reducing current-carrying
The heat energy loss of son, thus improve its phototranstormation efficiency.Therefore, what exploitation was new is applied to solar spectrum conversion and to environment
The friendly, down-conversion luminescent material of low manufacture cost has important Research Significance.
Yb3+The 4f electronics of ion has 13, and spectral transition can only be in ground state level2F7/2With unique excited level2F5/2
Between carry out, there is not Excited-state Absorption and upper conversion, thus have higher light conversion efficiency.But, single doping Yb3+Ion is very
Difficult absorb ultraviolet light and visible ray, therefore generally to be co-doped with trivalent rare earth ionses, to improve it as sensitizer visible in ultraviolet light
The absorption in light area, to improve the utilization rate of solar energy, the ion of these codopes is concentrated mainly on terbium ion Tb at present3+, thulium from
Sub- Tm3+, erbium ion Er3+, praseodymium ion Pr3+, neodymium ion Nd3+Deng trivalent rare earth ionses.Although these ions being co-doped with are in ultraviolet extremely
Visible region has absorption, but its absorption is all mostly wire, and the intensity of absorption is little, does not reach the effect making full use of, and
Existing lower conversion luminescent material preparation method is also more complicated, relatively costly.
Content of the invention
The problem existing for above-mentioned prior art, it is an object of the invention to provide a kind of stable luminescent property, absorption
Intensity is high, can efficiently realize the silica-based solar cell down-conversion luminescent material of ultraviolet light switching emission near infrared light, with
When, the present invention provides the preparation method of this kind of light-converting material simple to operation.
To achieve these goals, the technical solution used in the present invention is:One kind realizes near-infrared under ultraviolet excitation
Luminous material, chemical formula is MY4-4xYb4xMo3O16, M is divalent transition metal ion cadmium Cd2+Or zinc Zn2+, x is Yb3+Doping
Mole percent, 0.0001≤x≤0.8.
The preparation method realizing near-infrared luminous material under ultraviolet excitation as above, using high temperature solid-state
Method, comprises the steps:
(1) press chemical formula MY4-4xYb4xMo3O16The stoichiometric proportion of middle each element, wherein 0.0001≤x≤0.8, respectively
Weigh the compound containing ion M, contain ruthenium ion Y3+Compound, contain ytterbium ion Yb3+Compound, contain molybdenum ion
Mo6+Compound, grind and mix, obtain mixture, described ion M is divalent transition metal ion cadmium Cd2+Or zinc
Zn2+;
(2) the mixture precalcining in air atmosphere obtaining step (1), precalcining temperature is 400~900 DEG C, in advance
Calcination time is 1~15 hour;
(3) by the mixture obtaining natural cooling, grind after taking-up and mix, calcine in air atmosphere, calcining
Temperature is 900~1200 DEG C, and calcination time is 1~10 hour, naturally cools to room temperature, is fully ground and obtains in ultraviolet after taking-up
Light excites lower realizes near-infrared luminous material.
Preferably, in high temperature solid-state method of the present invention, the precalcining temperature of step (2) is 450~850 DEG C, and precalcination time is
2~14 hours.
Preferably, in high temperature solid-state method of the present invention step (3) calcining heat be 950~1150 DEG C, calcination time be 2~
9 hours.
The preparation method realizing near-infrared luminous material under ultraviolet excitation as above, using chemical synthesis
Method, comprises the steps:
(1) with the compound containing ion M, contain ruthenium ion Y3+Compound, contain ytterbium ion Yb3+Compound, contain
There is molybdenum ion Mo6+Compound be raw material, by chemical formula MY4-4xYb4xMo3O16The stoichiometric proportion of middle corresponding element weighs, its
In 0.0001≤x≤0.8, by the compound containing ion M, contain ruthenium ion Y3+Compound, contain ytterbium ion Yb3+Change
Compound is dissolved separately in dilute nitric acid solution, will be containing molybdenum ion Mo6+Compound be dissolved in deionized water or ethanol solution,
Obtain various clear solutions, then add complexing agent respectively by 0.5~2.0wt% of each reactant quality, in 50~80 DEG C of temperature
Stirring and dissolving under the conditions of degree, described ion M is divalent transition metal ion cadmium Cd2+Or zinc Zn2+;
(2) the various solution obtaining step (1) are slowly mixed together, and stir 1~2 hour under 50~80 DEG C of temperature conditionss
Afterwards, stand, dry, obtain bulk presoma;
(3) presoma obtaining step (2) is placed in calcining in Muffle furnace, and calcining heat is 700~1100 DEG C, during calcining
Between be 2~10 hours, naturally cool to room temperature, be fully ground after taking-up obtain realizing under ultraviolet excitation near-infrared luminous
Material.
Preferably, in chemical solution method of the present invention step (3) calcining heat be 750~1000 DEG C, calcination time be 3~
9 hours.
In chemical solution method of the present invention, described complexing agent is citric acid or oxalic acid.
Preferably, in high temperature solid-state method of the present invention and chemical solution method, the compound containing ion M is the oxide of M, chlorine
One of compound, nitrate;Containing ruthenium ion Y3+Compound be one of yittrium oxide, yttrium nitrate and yttrium carbonate;Contain
Ytterbium ion Yb3+Compound be one of ytterbium oxide, ytterbium nitrate and ytterbium carbonate;Containing molybdenum ion Mo6+Compound be oxidation
Molybdenum or ammonium molybdate.
The advantage of technical solution of the present invention is:
(1) what the present invention provided realizes near-infrared luminous material under ultraviolet excitation, can be by ultraviolet-black light
Effectively excite, launch 950~1100 nanometers of near infrared light, match with the absorption spectrum of silica-based solar cell, permissible
Improve silica-based solar cell light conversion efficiency, be preferable silica-based solar cell light-converting material.
(2) material that the present invention provides has good chemically and thermally stability, with MY4Mo3O16(M is Cd2+Or Zn2+) be
Matrix, adulterate active ions Yb3+It is used for replacing the Y among lattice3+Ion, by matrix in ultraviolet-near ultraviolet wide band absorption
Transmission energy is to active ions Yb3+, realize the wide band absorption in Uv and visible light area for its excitation spectrum, thus ultraviolet light is high
Imitate is converted near infrared light.
(3) what the present invention provided realizes near-infrared luminous material under ultraviolet excitation, and preparation is simple, right
Less demanding in equipment, prepared product thing is mutually pure, even particle size distribution, and low production cost is it is easy to industrialized production,
Special protection is not needed in preparation process, and environmentally friendly, not pollution.
Brief description
Fig. 1 is that the embodiment of the present invention 1 prepares sample CdY2Yb2Mo3O16X-ray powder diffraction pattern;
Fig. 2 is that the embodiment of the present invention 1 prepares sample CdY2Yb2Mo3O16Scanning electron microscope diagram spectrum;
Fig. 3 is that the embodiment of the present invention 1 prepares sample CdY2Yb2Mo3O16Excitation spectrum under 1000 nano wave length monitorings
Figure;
Fig. 4 is that the embodiment of the present invention 1 prepares sample CdY2Yb2Mo3O16Fluorescence spectra under 360 nano wave lengths excite;
Fig. 5 is that the embodiment of the present invention 1 prepares sample CdY2Yb2Mo3O16A length of 360 nanometers in excitation light wave, monitor optical wavelength
Decay of luminescence curve for 1000 nanometers;
Fig. 6 is that the embodiment of the present invention 2 prepares sample CdY3.6Yb0.4Mo3O16X-ray powder diffraction pattern;
Fig. 7 is that the embodiment of the present invention 2 prepares sample CdY3.6Yb0.4Mo3O16Scanning electron microscope diagram spectrum;
Fig. 8 is that the embodiment of the present invention 2 prepares sample CdY3.6Yb0.4Mo3O16Exciting light under 1000 nano wave length monitorings
Spectrogram;
Fig. 9 is that the embodiment of the present invention 2 prepares sample CdY3.6Yb0.4Mo3O16Fluorescence spectrum under 360 nano wave lengths excite
Figure;
Figure 10 is that the embodiment of the present invention 6 prepares sample ZnY2.4Yb1.6Mo3O16X-ray powder diffraction pattern;
Figure 11 is that the embodiment of the present invention 6 prepares sample ZnY2.4Yb1.6Mo3O16Scanning electron microscope diagram spectrum;
Figure 12 is that the embodiment of the present invention 6 prepares sample ZnY2.4Yb1.6Mo3O16Exciting light under 1000 nano wave length monitorings
Spectrogram;
Figure 13 is that the embodiment of the present invention 6 prepares sample ZnY2.4Yb1.6Mo3O16Fluorescence light under 330 nano wave lengths excite
Spectrogram;
Figure 14 is that the embodiment of the present invention 6 prepares sample ZnY2.4Yb1.6Mo3O16A length of 330 nanometers in excitation light wave, monitor light
Wavelength is 1000 nanometers of decay of luminescence curve.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1:
Preparation CdY2Yb2Mo3O16, according to chemical formula CdY2Yb2Mo3O16The stoichiometric proportion of middle each element, weighs oxygen respectively
Cadmium CdO:0.32 gram, yittrium oxide Y2O3:0.56 gram, ytterbium oxide Yb2O3:0.99 gram, molybdenum oxide MoO3:1.08 grams, grind in agate
After grinding in alms bowl and mixing, select air atmosphere precalcining 14 hours at 450 DEG C in Muffle furnace;Then natural cooling
To room temperature, it is sufficiently mixed grinding after taking-up again uniformly, calcines 2 hours at 1150 DEG C in air atmosphere, be cooled to room temperature,
It is fully ground after taking-up and obtain dusty material.
Referring to accompanying drawing 1, it is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample, XRD test result
Display, the no other miscellaneous peak of in figure occurs, the card ICSD-35093 contrast with standard, the position of diffraction maximum and relative intensity all and
Standard card is completely the same, illustrates that the sample obtained by this example is pure thing phase.
Referring to accompanying drawing 2, it is the scanning electron microscope diagram spectrum of sample as prepared by the present embodiment technical scheme;From in figure
As can be seen that gained sample crystallization is good, particle is uniformly dispersed, and its average grain diameter is 1.74 microns.
Referring to accompanying drawing 3, it is sample the exciting under 1000 nano wave lengths are monitored by the preparation of the present embodiment technical scheme
Spectrogram, this material emission excite the main ultraviolet between 250~400 nanometers-black light region in source, launch main peak
Positioned at 360 nanometers, the ultraviolet-black light in sunshine can be absorbed well, apply permissible in crystal silicon solar batteries
Significantly improve photoelectric transformation efficiency.
Referring to accompanying drawing 4, it is the fluorescence light under 360 nano wave lengths excite for the sample by the preparation of the present embodiment technical scheme
Spectrogram, as seen from the figure, the near-infrared luminous of 900~1100 nano wavebands in emission spectrum, and transmitting main peak is located at 1000 nanometers
Position, obtained material effectively converts ultraviolet light into near-infrared luminous.
Referring to accompanying drawing 5, it be by the preparation of the present embodiment technical scheme sample a length of 360 nanometers in excitation light wave, monitoring
The decay of luminescence curve of a length of 1000 nanometers of light wave, can obtain die-away time for 0.078 millisecond from figure.
Embodiment 2:
Preparation CdY3.6Yb0.4Mo3O16, according to chemical formula CdY3.6Yb0.4Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh caddy CdCl2:0.46 gram, yttrium carbonate Y2(CO3)3:1.38 grams, ytterbium carbonate Yb2(CO3)3:0.26 gram, ammonium molybdate (NH4)6MO7O24·4H2O:1.32 grams, after grinding and mix in agate mortar, select air atmosphere at 850 DEG C in Muffle furnace
Lower precalcining 2 hours;Then naturally cool to room temperature, be sufficiently mixed grinding after taking-up again uniformly, in 950 in air atmosphere
Calcine 9 hours at DEG C, be cooled to room temperature, be fully ground after taking-up and obtain dusty material.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 1.
Embodiment 3:
Preparation CdY1.2Yb2.8Mo3O16, according to chemical formula CdY0.8Yb3.2Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh cadmium nitrate Cd (NO3)2·4H2O:0.31 gram, yttrium nitrate Y (NO3)3·6H2O:0.46 gram, ytterbium nitrate Yb (NO3)3·5H2O:
1.26 grams, ammonium molybdate (NH4)6MO7O24·4H2O:0.53 gram, after grinding and mix in agate mortar, select air gas
Atmosphere precalcining 7 hours at 650 DEG C in Muffle furnace;Then naturally cool to room temperature, be sufficiently mixed grinding after taking-up again all
Even, calcine 9 hours in 950 DEG C in air atmosphere, be cooled to room temperature, be fully ground after taking-up and obtain dusty material.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 1.
Embodiment 4:
Preparation CdY2.8Yb1.2Mo3O16, according to chemical formula CdY2.8Yb1.2Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh cadmium oxide CdO:0.32 gram, yttrium carbonate Y2(CO3)3:1.06 grams, ytterbium carbonate Yb2(CO3)3:0.79 gram, ammonium molybdate (NH4)6MO7O24·4H2O:1.32 grams, by the cadmium oxide weighing CdO, yttrium carbonate Y2(CO3)3And ytterbium carbonate Yb2(CO3)3It is dissolved in respectively
In dilute nitric acid solution, by the ammonium molybdate weighing (NH4)6MO7O24·4H2O is dissolved in deionized water, obtains various clear solutions,
The citric acid weighing the 2.0wt% of each material quality more respectively is separately added in each solution, in 80 DEG C of stirrings until being completely dissolved;
Then above-mentioned each solution is slowly mixed together, stirs 1 hour at 80 DEG C;Standing, dries, obtains bulk presoma;By presoma
It is placed in calcining in Muffle furnace, calcining heat is 750 DEG C, and calcination time is 9 hours, is cooled to room temperature, is fully ground i.e. after taking-up
Obtain dusty material.
Referring to accompanying drawing 6, it is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample, XRD test result
Display, the no other miscellaneous peak of in figure occurs, and does not have impurity, the position of diffraction maximum and relative intensity all completely the same with standard card,
Illustrate that the sample obtained by this example is pure thing phase.
Referring to accompanying drawing 7, it is the scanning electron microscope diagram spectrum of sample as prepared by the present embodiment technical scheme, from figure
As can be seen that gained sample particle is uniformly dispersed, its average grain diameter is 3.53 microns.
Referring to accompanying drawing 8, it is sample the exciting under 1000 nano wave lengths are monitored by the preparation of the present embodiment technical scheme
Spectrogram, this material emission excite the main ultraviolet between 250~400 nanometers-black light region in source, launch main peak
Positioned at 360 nanometers, the ultraviolet-black light in sunshine can be absorbed well, apply permissible in crystal silicon solar batteries
Significantly improve photoelectric transformation efficiency.
Referring to accompanying drawing 9, it is the fluorescence light under 360 nano wave lengths excite for the sample by the preparation of the present embodiment technical scheme
Spectrogram, as seen from the figure, the near-infrared luminous of 900~1100 nano wavebands in emission spectrum, and obtained material is effectively by purple
Outer light is converted to near-infrared luminous;Its attenuation curve is similar to Example 1.
Embodiment 5:
Preparation CdY3.9996Yb0.0004Mo3O16, according to chemical formula CdY3.9996Yb0.0004Mo3O16The stoichiometry of middle each element
Ratio weighs cadmium oxide CdO respectively:0.26 gram, yittrium oxide Y2O3:0.91 gram, ytterbium oxide Yb2O3:0.0002 gram, ammonium molybdate (NH4)6MO7O24·4H2O:1.06 grams, by the cadmium oxide weighing CdO, yittrium oxide Y2O3And ytterbium oxide Yb2O3It is dissolved in dust technology respectively molten
In liquid, by the ammonium molybdate weighing (NH4)6MO7O24·4H2O is dissolved in deionized water, obtains various clear solutions, then claims respectively
The citric acid taking the 0.5wt% of each material quality is separately added in each solution, in 70 DEG C of stirrings until being completely dissolved;Then will be upper
State each solution to be slowly mixed together, stir 1.5 hours at 70 DEG C;Standing, dries, obtains bulk presoma;Presoma is placed in horse
Not calcine in stove, calcining heat is 700 DEG C, calcination time is 10 hours, is cooled to room temperature, is fully ground and obtains powder after taking-up
Last shape material.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 4.
Embodiment 6:
Preparation ZnY2.4Yb1.6Mo3O16, according to chemical formula ZnY2.4Yb1.6Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh zinc oxide ZnO:0.21 gram, yittrium oxide Y2O3:0.68 gram, ytterbium oxide Yb2O3:0.79 gram, molybdenum oxide MoO3:1.08 grams,
After grinding in agate mortar and mixing, select air atmosphere precalcining 1 hour at 900 DEG C in Muffle furnace;Then certainly
So it is cooled to room temperature, be sufficiently mixed grinding after taking-up again uniformly, calcine 10 hours at 900 DEG C in air atmosphere, cooling
To room temperature, it is fully ground after taking-up and obtains dusty material.
Referring to accompanying drawing 10, it is the X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample, XRD test knot
Fruit shows, the no other miscellaneous peak of in figure occurs, and does not have impurity, the position of diffraction maximum and relative intensity all complete with standard card one
Cause, illustrate that the sample obtained by this example is pure thing phase.
Referring to accompanying drawing 11, it is the scanning electron microscope diagram spectrum of sample as prepared by the present embodiment technical scheme, from figure
In as can be seen that gained sample particle be uniformly dispersed, its average grain diameter be 1.47 microns.
Referring to accompanying drawing 12, it is sample the exciting under 1000 nano wave lengths are monitored by the preparation of the present embodiment technical scheme
Spectrogram, this material emission excite the main ultraviolet between 250~400 nanometers-black light region in source, launch main peak
Positioned at 330 nanometers, the ultraviolet-black light in sunshine can be absorbed well, apply permissible in crystal silicon solar batteries
Significantly improve photoelectric transformation efficiency.
Referring to accompanying drawing 13, it is the fluorescence under 330 nano wave lengths excite for the sample by the preparation of the present embodiment technical scheme
Spectrogram, as seen from the figure, the near-infrared luminous of 950~1100 nano wavebands in emission spectrum, and obtained material effectively will
Ultraviolet light is converted to near-infrared luminous.
Referring to accompanying drawing 14, it be by the preparation of the present embodiment technical scheme sample a length of 330 nanometers in excitation light wave, monitoring
The decay of luminescence curve of a length of 1000 nanometers of light wave, can be calculated die-away time for 0.078 millisecond.
Embodiment 7:
Preparation ZnY1.6Yb2.4Mo3O16, according to chemical formula ZnY1.6Yb2.4Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh zinc nitrate Zn (NO3)2·6H2O:0.30 gram, yttrium nitrate Y (NO3)3·6H2O:0.61 gram, ytterbium nitrate Yb (NO3)3·5H2O:
1.08 grams, ammonium molybdate (NH4)6Mo7O24·4H2O:0.53 gram, after grinding and mix in agate mortar, select air gas
Atmosphere in 400 DEG C of precalcinings 15 hours, then naturally cools to room temperature in Muffle furnace, is sufficiently mixed grinding again all after taking-up
Even, calcine 1 hour in 1200 DEG C in air atmosphere, be cooled to room temperature, be fully ground after taking-up and obtain dusty material.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 6.
Embodiment 8:
Preparation ZnY0.8Yb3.2Mo3O16, according to chemical formula ZnY0.8Yb3.2Mo3O16The stoichiometric proportion of middle each element, respectively
Weigh zinc oxide ZnO:0.10 gram, yittrium oxide Y2O3:0.11 gram, ytterbium oxide Yb2O3:0.79 gram, ammonium molybdate (NH4)6Mo7O24·
4H2O:0.66 gram, by the zinc oxide weighing ZnO, yittrium oxide Y2O3And ytterbium oxide Yb2O3It is dissolved in respectively in dilute nitric acid solution, will
Ammonium molybdate (the NH weighing4)6MO7O24·4H2O is dissolved in ethanol solution, obtains various clear solutions, then weighs each former respectively
The oxalic acid of the 2.0wt% of material quality is separately added in each solution, in 50 DEG C of stirrings until being completely dissolved;Then by above-mentioned each solution
It is slowly mixed together, stir 2 hours at 50 DEG C;Standing, dries, obtains bulk presoma;Presoma is placed in calcining in Muffle furnace,
Calcining heat is 1000 DEG C, and calcination time is 3 hours, is cooled to room temperature, is fully ground and obtains dusty material after taking-up.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 6.
Embodiment 9:
Preparation ZnY3.96Yb0.04Mo3O16, according to chemical formula ZnY3.96Yb0.04Mo3O16The stoichiometric proportion of middle each element, point
Another name takes zinc oxide ZnO:0.10 gram, yittrium oxide Y2O3:0.56 gram, ytterbium oxide Yb2O3:0.01 gram, ammonium molybdate (NH4)6Mo7O24·
4H2O:0.66 gram, by the zinc oxide weighing ZnO, yittrium oxide Y2O3And ytterbium oxide Yb2O3It is dissolved in respectively in dilute nitric acid solution, will
Ammonium molybdate (the NH weighing4)6MO7O24·4H2O is dissolved in ethanol solution, obtains various clear solutions, then weighs each former respectively
The oxalic acid of the 2.0wt% of material quality is separately added in each solution, in 80 DEG C of stirrings until being completely dissolved;Then by above-mentioned each solution
It is slowly mixed together, stir 2 hours at 80 DEG C;Standing, dries, obtains bulk presoma;Presoma is placed in calcining in Muffle furnace,
Calcining heat is 1100 DEG C, and calcination time is 2 hours, is cooled to room temperature, is fully ground and obtains dusty material after taking-up.
Its primary structure pattern, excitation spectrum, emission spectrum and attenuation curve are similar to Example 6.