Down-conversion luminescent material that a kind of broad band absorbs and preparation method thereof
Technical field
The invention belongs to luminescent material and its preparing technical field, and in particular to the lower conversion that a kind of broad band absorbs shines
Material and preparation method thereof.
Technical background
In face of petering out for current fossil energy, and damaging influence of the fossil energy to ecological environment is consumed, compeled
Be essential new energy to be developed and utilized or regenerative resource.Solar energy has the advantages that renewable, pollution-free, is a kind of great competing
Strive the green novel energy source of power.Silicon solar cell is the device that solar energy can be changed into electric energy.Sunlight is a distribution
Very wide continuous spectrum, the wavelength band for the solar radiation observed on the ground is about 300 ~ 2500nm, and silicon solar
Significant response wavelength band of the battery to incident light is 400 ~ 1100nm, and the spatial distribution Incomplete matching with sunlight, is caused
It is difficult to be absorbed by solar cell that significant portion of short wave ultraviolet light and blue light are accounted in sunlight, and this spectral mismatch phenomenon causes
The extreme loss of solar energy, the efficiency of opto-electronic conversion are low.How more fully, sunlight is more reasonably absorbed, improves silicon substrate
The photoelectric conversion efficiency of solar cell is one of focal issue of current extensive concern.
T.Trupke in 2002 etc. proposes to be shone with lower conversion and solar spectral is cut out, and is cut by lower transition material
Solar spectrum after sanction will focus on the most sensitive wave band of solar cell, response that can preferably with solar cell
Match somebody with somebody, the lattice thermal vibration loss of silicon solar cell can be effectively reduced, so as to improve the photoelectric conversion efficiency of solar cell.
More light conversion material is studied at present is concentrated mainly on M3+-Yb3+(M3+=Tb3+, Tm3+, Eu3+And Pr3+)The luminous material of doping
Material, due to trivalent rare earth M3+(M3+=Tb3+, Tm3+, Eu3+And Pr3+)4f-4f transition be a kind of parity prohibit eelctric dipole jump
Move, absorption cross-section very little, very low to the absorbability of purple light-blue region, this causes the Yb in these materials3+Ion it is near red
Outer light emitting intensity is weaker, the lifting unobvious of energy conversion efficiency.Therefore the near-infrared quantum-cutting that exploitation broad band absorbs
Luminescent material can be expected to improve absorption efficiency of the material near ultraviolet region, strong near infrared light transmitting be obtained, so as to improve
The photoelectric conversion efficiency of silicon solar.
The content of the invention
It is an object of the invention to provide a kind of stable luminescent property, absorption intensity is high, can efficiently realize ultraviolet light turn
Change the down-conversion luminescent material that the broad band of near infrared light absorbs.
Another purpose of the object of the invention, which is to provide, a kind of simple to operation described realizes that ultraviolet light changes near-infrared
The preparation method for the down-conversion luminescent material that the broad band of light absorbs.
The chemical general formula for the down-conversion luminescent material that broad band of the present invention absorbs is as follows:M1-x- y -zM’zA3(BO3)4:
xCe3+,yYb3+;Wherein M is at least one of Y or Gd, and M ' is one kind in Lu, La, Sc or Bi, and A is in Al or Ga
At least one, 0<x≤0.3, 0<y<1, 0≤z<1.
The down-conversion luminescent material that the broad band absorbs is preferably Y0.80Bi0.10Al2.7Ga0.3(BO3)4:0.05Ce3+,
0.05Yb3+。
The preparation method for the down-conversion luminescent material that above-mentioned broad band absorbs comprises the following steps:
1) with Lu, La, Y, Gd, Al, Ga, Sc, Bi oxides and boric acid are raw material, according to chemical general formula M1-x-y-zM’zA3(BO3)4:xCe3+,yYb3+Stoichiometric ratio weigh Lu, La, Y, Gd, Al, Ga, Sc, Bi, Ce, Yb oxides
And boric acid, boric acid stoichiometric excess is than 5 ~ 30%;
2) raw material of step 1) after mixing, when 600 ~ 800 DEG C of sintering 1 ~ 2 are small, take out after being cooled to room temperature and grinds
It is even, then under reducing atmosphere, when sintering 4 ~ 10 is small at 1100 ~ 1250 DEG C;Above-mentioned reducing atmosphere is nitrogen and hydrogen mixed gas,
Either carbon burns generated gas in atmosphere.
3) it is crushed into powder after sintering, after being washed with deionized water, crosses 400 mesh sieves, after pigment separation, dried at 100 ~ 200 DEG C,
Obtain the M of broad band absorption1-x-y-zM’zA3(BO3)4:xCe3+,yYb3+Down-conversion luminescent material.
Down-conversion luminescent material that the broad band of the present invention absorbs and preparation method thereof has the following advantages:
(1) down-conversion luminescent material of the invention has strong wide band absorption at UV light region (260 ~ 340nm), can effectively inhale
Receive solar energy;
(2) down-conversion luminescent material of the invention under ultraviolet excitation there is strong near infrared light to launch, and transmitting main peak is located at
925 ~ 1075nm, matches with the most sensitive response wave band of silicon solar cell;
(3) down-conversion luminescent material property of the invention is stablized, and manufacture method is simple, easily operated, and cost is low.
Brief description of the drawings
Fig. 1 is the XRD diagram of embodiment 1.
Fig. 2 is the excitation spectrum and near infrared spectroscopy figure (λ of embodiment 1em=980nm,λex=320nm)。
Fig. 3 is the XRD diagram of embodiment 18.
Fig. 4 is the excitation spectrum and near infrared spectroscopy figure (λ of embodiment 18em=980nm,λex=320nm)。
Embodiment
Analytically pure boric acid (H is weighed in the chemical composition ratio of table 13BO3), bismuth oxide (Bi2O3), 99.99% oxidation
Gadolinium (Gd2O3), 99.99% yittrium oxide (Y2O3), 99.99% lanthana (La2O3), 99.99% luteium oxide (Lu2O3)、99.99%
Scandium oxide (Sc2O3), 99.99% gallium oxide (Ga2O3), 99.99% aluminium oxide (Al2O3), 99.99% ytterbium oxide (Yb2O3) and
99.99% cerium oxide (CeO2), add stoichiometric excess boric acid (H purer than 5 ~ 30% analysis3BO3), after mixing, put
In corundum crucible, high temperature furnace is put into, first when 600 ~ 800 DEG C of sintering 1 ~ 2 are small, takes out and is ground uniformly after being cooled to room temperature,
Then under reducing atmosphere when 1100 ~ 1250 DEG C of sintering 4 ~ 10 are small, it is crushed into powder after sintering, after being washed with deionized water, crosses 400
Mesh sieve, after pigment separation, in 100 ~ 200 DEG C of drying, that is, obtains the M that broad band absorbs1-x-y-zM’zA3(BO3)4:xCe3+,yYb3+
Down-conversion luminescent material.
Embodiment 1
2.7210g boric acid, 1.6314g gadolinium oxides, 1.5294g aluminium oxide, 0.0985g ytterbium oxides and 0.0861g oxygen are weighed respectively
Change cerium, after being ground uniformly in agate mortar, be fitted into corundum crucible, be put into high temperature furnace, it is cold first when 600 DEG C of insulations 1 are small
But to taking out after room temperature and grind uniformly, then mixture is fitted into corundum crucible, be then placed in the crucible equipped with activated carbon
And lid is covered tightly, batch-type furnace is put into when 1250 DEG C of sintering 6 are small, is crushed into powder after sintering, after being washed with deionized water, is crossed 400 mesh
Sieve, after pigment separation, in 180 DEG C of drying, that is, obtains Gd0.9Al3.0(BO3)4:0.05Ce3+,0.05Yb3+Down-conversion luminescent material.
The XRD diagram of the down-conversion luminescent material is shown in Fig. 1, and excitation spectrum and near infrared spectroscopy at room temperature are shown in Fig. 2.
Embodiment 2
3.2157g boric acid, 1.5294g aluminium oxide, 1.8719g ytterbium oxides and 0.0861g cerium oxide are weighed respectively, in agate mortar
After middle grinding uniformly, it is fitted into corundum crucible, is put into high temperature furnace, first when 800 DEG C of insulations 2 are small, is taken out after being cooled to room temperature
And grind it is uniform, then again by mixture at 1250 DEG C, volume ratio 75%N2:25%H2Atmosphere under sintering 10 it is small when, powder after sintering
Powder is broken into, after being washed with deionized water, 400 mesh sieves is crossed, after pigment separation, in 200 DEG C of drying, that is, obtains Al3.0 (BO3)4:
0.05Ce3+,0.95Yb3+Down-conversion luminescent material.
Embodiment 3
2.7210g boric acid, 1.0513g gadolinium oxides, 1.4058g gallium oxides, 0.7647g aluminium oxide, 0.7882g oxidations are weighed respectively
Ytterbium and 0.0344g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1200 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 150
DEG C drying, that is, obtain Gd0.58Al1.5Ga1.5(BO3)4:0.02Ce3+,0.40Yb3+Down-conversion luminescent material.
Embodiment 4
2.5973g boric acid, 1.1600g gadolinium oxides, 2.8116g gallium oxides, 0.5911g ytterbium oxides and 0.1033g oxygen are weighed respectively
Change cerium, after being ground uniformly in agate mortar, be fitted into corundum crucible, be put into high temperature furnace, it is cold first when 600 DEG C of insulations 1 are small
But to taking out after room temperature and grinding uniformly, then again by mixture at 1150 DEG C, volume ratio 75%N2:25%H2Atmosphere under sinter 6
Hour, it is crushed into powder after sintering, after being washed with deionized water, crosses 400 mesh sieves, after pigment separation, in 100 DEG C of drying, that is, obtain
Gd0.64Ga3.0(BO3)4:0.06Ce3+,0.30Yb3+Down-conversion luminescent material.
Embodiment 5
2.7210g boric acid, 1.1781g gadolinium oxides, 0.1990g luteium oxides, 0.9372g gallium oxides, 1.0196g oxidations are weighed respectively
Aluminium, 0.4335g ytterbium oxides and 0.0516g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into height
In warm stove, first when 700 DEG C of insulations 1 are small, take out and ground uniformly after being cooled to room temperature, then again by mixture at 1200 DEG C,
Volume ratio 75%N2:25%H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, cross 400 mesh sieves, water
After powder separation, in 150 DEG C of drying, that is, Gd is obtained0.65Lu0.10Al2.0Ga(BO3)4:0.03Ce3+,0.22Yb3+The lower luminous material of conversion
Material.
Embodiment 6
2.7210g boric acid, 0.8156g gadolinium oxides, 0.1379g scandium oxides, 1.5294g aluminium oxide, 0.0985g oxidations are weighed respectively
Ytterbium and 0.5164g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 700
When DEG C insulation 2 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1250 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 8 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 180
DEG C drying, that is, obtain Gd0.45Sc0.2Al3.0(BO3)4:0.30Ce3+,0.05Yb3+Down-conversion luminescent material.
Embodiment 7
2.7210g boric acid, 0.5619g gadolinium oxides, 0.0815g lanthanas, 1.8744g gallium oxides, 0.5098g oxidations are weighed respectively
Aluminium, 1.1822g ytterbium oxides and 0.0688g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into height
In warm stove, first when 600 DEG C of insulations 1 are small, take out and ground uniformly after being cooled to room temperature, then again by mixture at 1150 DEG C,
Volume ratio 75%N2:25%H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, cross 400 mesh sieves, water
After powder separation, in 120 DEG C of drying, that is, Gd is obtained0.31La0.05AlGa2.0(BO3)4:0.04Ce3+,0.60Yb3+The lower luminous material of conversion
Material.
Embodiment 8
2.7210g boric acid, 0.8881g gadolinium oxides, 0.3387g yittrium oxide, 1.5294g aluminium oxide, 0.3941g oxidations are weighed respectively
Ytterbium and 0.0172g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 2 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1250 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 9 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 180
DEG C drying, that is, obtain Gd0.49Y0.30Al3.0(BO3)4:0.01Ce3+,0.20Yb3+Down-conversion luminescent material.
Embodiment 9
2.7210g boric acid, 0.7250g gadolinium oxides, 0.9319g bismuth oxides, 1.5294g aluminium oxide, 0.1970g oxidations are weighed respectively
Ytterbium and 0.1721g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then mixture is fitted into corundum crucible, is then placed in and is equipped with
In the crucible of activated carbon and lid is covered tightly, batch-type furnace is put into when 1200 DEG C of sintering 6 are small, is crushed into powder after sintering, uses deionization
After washing, 400 mesh sieves are crossed, after pigment separation, in 180 DEG C of drying, that is, obtain Gd0.40Bi0.40Al3.0(BO3)4:0.10Ce3+,
0.10Yb3+Down-conversion luminescent material.
Embodiment 10
2.7210g boric acid, 0.9597g yittrium oxide, 1.5294g aluminium oxide, 0.1970g ytterbium oxides and 0.0861g oxygen are weighed respectively
Change cerium, after being ground uniformly in agate mortar, be fitted into corundum crucible, be put into high temperature furnace, it is cold first when 600 DEG C of insulations 1 are small
But to taking out after room temperature and grind uniformly, then mixture is fitted into corundum crucible, be then placed in the crucible equipped with activated carbon
And lid is covered tightly, batch-type furnace is put into when 1250 DEG C of sintering 6 are small, is crushed into powder after sintering, after being washed with deionized water, is crossed 400 mesh
Sieve, after pigment separation, in 200 DEG C of drying, that is, obtains Y0.85Al3.0(BO3)4:0.05Ce3+,0.10Yb3+Down-conversion luminescent material.
Embodiment 11
2.5973g boric acid, 2.8116g gallium oxides, 1.9113g ytterbium oxides and 0.0516g cerium oxide are weighed respectively, in agate mortar
After middle grinding uniformly, it is fitted into corundum crucible, is put into high temperature furnace, first when 600 DEG C of insulations 1 are small, is taken after being cooled to room temperature
Go out and grind uniformly, then again by mixture at 1100 DEG C, volume ratio 75%N2:25%H2Atmosphere under sintering 6 it is small when, after sintering
It is crushed into powder, after being washed with deionized water, crosses 400 mesh sieves, after pigment separation, in 100 DEG C of drying, that is, obtain Ga3.0(BO3)4:
0.03Ce3+,0.97Yb3+Down-conversion luminescent material.
Embodiment 12
2.7210g boric acid, 0.8242g yittrium oxide, 1.4058g gallium oxides, 0.7647g aluminium oxide, 0.3941g oxidations are weighed respectively
Ytterbium and 0.1205g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1200 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 150
DEG C drying, that is, obtain Y0.73Al1.5Ga1.5(BO3)4:0.07Ce3+,0.20Yb3+Down-conversion luminescent material.
Embodiment 13
2.5973g boric acid, 0.8581g yittrium oxide, 2.8116g gallium oxides, 0.3941g ytterbium oxides and 0.0688g oxygen are weighed respectively
Change cerium, after being ground uniformly in agate mortar, be fitted into corundum crucible, be put into high temperature furnace, it is cold first when 600 DEG C of insulations 1 are small
But to taking out after room temperature and grinding uniformly, then again by mixture at 1150 DEG C, volume ratio 75%N2:25%H2Atmosphere under sinter 6
Hour, it is crushed into powder after sintering, after being washed with deionized water, crosses 400 mesh sieves, after pigment separation, in 100 DEG C of drying, that is, obtain
Y0.76Ga3.0(BO3)4:0.04Ce3+,0.20Yb3+Down-conversion luminescent material.
Embodiment 14
2.7210g boric acid, 0.6210g yittrium oxide, 0.3979g luteium oxides, 1.5294g aluminium oxide, 0.3941g oxidations are weighed respectively
Ytterbium and 0.0861g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1250 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 180
DEG C drying, that is, obtain Y0.55Lu0.20Al3.0(BO3)4:0.05Ce3+,0.20Yb3+Down-conversion luminescent material.
Embodiment 15
2.7210g boric acid, 0.9372g yittrium oxide, 0.0690g scandium oxides, 0.9372g gallium oxides, 1.0196g oxidations are weighed respectively
Aluminium, 0.0985g ytterbium oxides and 0.0344g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into height
In warm stove, first when 600 DEG C of insulations 1 are small, take out and ground uniformly after being cooled to room temperature, then again by mixture at 1200 DEG C,
Volume ratio 75%N2:25%H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, cross 400 mesh sieves, water
After powder separation, in 150 DEG C of drying, that is, Y is obtained0.83Sc0.10Al2.0Ga(BO3)4:0.02Ce3+,0.05Yb3+The lower luminous material of conversion
Material.
Embodiment 16
2.7210g boric acid, 0.5081g yittrium oxide, 0.2444g lanthanas, 1.5294g aluminium oxide, 0.7093g oxidations are weighed respectively
Ytterbium and 0.0688g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1250 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 150
DEG C drying, that is, obtain Y0.45La0.15Al3.0(BO3)4:0.04Ce3+,0.36Yb3+Down-conversion luminescent material.
Embodiment 17
2.7210g boric acid, 0.4531g gadolinium oxides, 0.5646g yittrium oxide, 2.8116g gallium oxides, 0.3941g oxidations are weighed respectively
Ytterbium and 0.0861g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into high temperature furnace, first 600
When DEG C insulation 1 is small, takes out and ground uniformly after being cooled to room temperature, then again by mixture at 1150 DEG C, volume ratio 75%N2:25%
H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, 400 mesh sieves crossed, after pigment separation, 100
DEG C drying, that is, obtain Gd0.25Y0.50Ga3.0(BO3)4:0.05Ce3+,0.20Yb3+Down-conversion luminescent material.
Embodiment 18
2.7210g boric acid, 0.9033g yittrium oxide, 0.2330g bismuth oxides, 1.3765g aluminium oxide, 0.2812g oxidations are weighed respectively
Gallium, 0.0985g ytterbium oxides and 0.0861g cerium oxide, after being ground uniformly in agate mortar, are fitted into corundum crucible, are put into height
In warm stove, first when 600 DEG C of insulations 1 are small, take out and ground uniformly after being cooled to room temperature, then again by mixture at 1150 DEG C,
Volume ratio 75%N2:25%H2Atmosphere under sintering 6 it is small when, be crushed into powder after sintering, after being washed with deionized water, cross 400 mesh sieves, water
After powder separation, in 120 DEG C of drying, that is, Y is obtained0.80Bi0.10Al2.7Ga0.3(BO3)4:0.05Ce3+,0.05Yb3+The lower luminous material of conversion
Material.The XRD diagram of the down-conversion luminescent material is shown in Fig. 3, and excitation spectrum and near infrared spectroscopy at room temperature are shown in Fig. 4.