CN103450900B - Fluorescent material, white-light light-emitting device and solar battery - Google Patents
Fluorescent material, white-light light-emitting device and solar battery Download PDFInfo
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- CN103450900B CN103450900B CN201310333243.2A CN201310333243A CN103450900B CN 103450900 B CN103450900 B CN 103450900B CN 201310333243 A CN201310333243 A CN 201310333243A CN 103450900 B CN103450900 B CN 103450900B
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- fluorescent material
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- emitting device
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 9
- 229910052745 lead Inorganic materials 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 230000005284 excitation Effects 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000005855 radiation Effects 0.000 description 28
- 238000010586 diagram Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 10
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 230000001443 photoexcitation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Abstract
The invention provides a fluorescent material. The fluorescent material has a structural formula shown as Eu(1-p-q)MdpMeqMg(1-y)MnyAl(10-z)MczO17, wherein the Md is one of or the combination of Sn, Yb, Pb, Tb, Ce, Dy and Pr; the p is more than 0 and less than or equal to 0.5; the Me is one of or the combination of Ca, Sr and Ba and the q is more than or equal to 0 and less than or equal to 0.9; the sum of the p and the q is more than 0 and less than or equal to 0.9; the y is more than 0 and less than or equal to 0.7; the Mc is one of or the combination of Ga, In and B and the z is more than or equal to 0 and less than or equal to 5. The invention further relates to a white-light light-emitting device and a solar battery which use the fluorescent material. The fluorescent material can irradiate visible light after being excited by ultraviolet light or blue light and is combined with other applicable fluorescent materials of various colors to form the white-light light-emitting device. Furthermore, the fluorescent material can be used for enhancing the light use rate of the solar battery.
Description
The application is the application number submitted on November 5th, 2009 is 200910208735.2, and denomination of invention is the divisional application of the application for a patent for invention of " fluorescent material, white light emitting device and solar cell ".
Technical field
The present invention relates to a kind of fluorescent material, relates more specifically to this kind of material in the application of white light emitting device and solar cell.
Background technology
Utilize power saving, low stain, be the modern Main Trends of The Development that throws light on life-span long white light emitting diode as lighting source.Lighting source is except LED intrinsic brightness, and its fluorescent material selected also is the key factor of the total luminous efficiency of impact.
Common white light LEDs is that blue led (emission wavelength is 460nm to 480nm) coordinates yellow fluorescent powder on the market at present, and its color rendering is poor.In addition, because the blue-light excited yellow fluorescent powder of blue-light LED chip is to produce gold-tinted, blue light strength can change with the change of received current amount, makes photochromic partially blue or partially yellow.In addition, blue-ray LED can be damaged in time gradually, also can cause photochromic irregular phenomenon.For improving color rendering and luminous efficiency, red, blue, the green three-color phosphor of general employing ultraviolet light-emitting diode collocation.Because excitaton source is invisible light, even if excitation intensity weakens, do not affect powder issued light look yet.
In known technology United States Patent (USP) the 7064480th and No. 7239082, No. 0211211st, world patent, a kind of thioaluminate phosphor material EuMgAl of the green glow that turns blue is disclosed
10o
17.The main peak that excites of above-mentioned fluorescent material is 396nm, and light emitting main peak is the blue green light of 477nm, and its strongest luminous intensity is not good.
In sum, still need the composition adjusting those fluorescent materials further to improve the strongest luminous intensity at present, and make emission wavelength more pure red, the pure green of convergence or pure blue.
Summary of the invention
The object of the present invention is to provide one can effectively improve launching efficiency and intensity of radioactivity, and make the fluorescent material of emission wavelength more convergence pure color.
The present invention also aims to provide the white light emitting device and solar cell that use above-mentioned fluorescent material.
The invention provides a kind of fluorescent material, there is structural formula as Eu
(1-x)ma
xmg
(1-y)mb
yal
(10-z)mc
zo
17; Wherein Ma is Yb, Sn, Pb, Ce, Tb, Dy, Pr, Ca, Sr, Ba or above-mentioned combination, and 0≤x≤0.9; Mb is Mn, Zn or above-mentioned combination, and 0<y≤0.7; And Mc is Ga, In, B or above-mentioned combination, and 0≤z≤5.
The present invention also provides a kind of white light emitting device, comprises above-mentioned fluorescent material and an excitation light source, and the wavelength of this excitation light source is the UV-light of 200nm to 400nm or the blue light of 400nm to 420nm.
The present invention also provides a kind of solar cell, comprises transparency carrier; Anode and negative electrode, be positioned at the lower surface of transparency carrier; And semiconductor layer, between anode and this negative electrode; Wherein the upper surface of transparency carrier has above-mentioned fluorescent material.
The wavelength region that can utilize compared to semiconductor layer most is at present visible region, the ultraviolet region that energy is stronger cannot be utilized, the invention has the advantages that: one aspect of the present invention can improve launching efficiency and the intensity of radioactivity of fluorescent material by the multiple hotchpotch of doping.Fluorescent material of the present invention can be sent green glow by the ultraviolet excitation of sunlight on the other hand, increases semiconductor layer to the rate of utilization of sunlight.Further, fluorescent material of the present invention via UV-light or blue-light excited after can radiate visible ray, with other be suitable for assorted fluorescence material combine and can be made white light emitting device, fluorescent material of the present invention also can in order to promote the light rate of utilization of solar cell.
Accompanying drawing explanation
Fig. 1 is solar cell schematic diagram of the present invention;
Fig. 2 is fluorescent material EuMg of the present invention
1-ymn
yal
10o
17with known fluorescent material EuMgAl
10o
17photic radiation comparison diagram;
Fig. 3 is fluorescent material EuMg of the present invention
0.9mn
0.1al
10o
17cIE figure;
Fig. 4 is the EuMg of different ratios
1-ymn
yal
10o
17photoluminescence intensity figure;
Fig. 5 is fluorescent material EuMg of the present invention
0.8mn
0.2al
(10-z)ga
zo
17photoexcitation radiation comparison diagram;
Fig. 6 is fluorescent material Eu of the present invention
1-xyb
xmg
0.7mn
0.3al
10o
17with fluorescent material EuMg
0.7mn
0.3al
10o
17photoexcitation radiation comparison diagram;
Fig. 7 is fluorescent material Eu of the present invention
1-xsn
xmg
0.7mn
0.3al
10o
17with fluorescent material EuMg
0.7mn
0.3al
10o
17photoexcitation radiation comparison diagram;
Fig. 8 is fluorescent material Eu of the present invention
1-xpb
xmg
0.7mn
0.3al
10o
17with fluorescent material EuMg
0.7mn
0.3al
10o
17photoexcitation radiation comparison diagram;
Fig. 9 is fluorescent material Eu of the present invention
1-xtb
xmg
0.7mn
0.3al
10o
17with fluorescent material EuMg
0.7mn
0.3al
10o
17photic radiation comparison diagram; And
Figure 10 is fluorescent material Eu of the present invention
0.98-xsr
xtb
0.02mg
0.7mn
0.3al
10o
17photoexcitation radiation comparison diagram;
Wherein, primary clustering nomenclature
11 ~ transparency carrier; 13 ~ anode; 15 ~ semiconductor layer;
17 ~ negative electrode; 19 ~ transparency carrier upper surface.
Embodiment
The invention provides a kind of fluorescent material and there is structural formula as Eu
(1-x)ma
xmg
(1-y)mb
yal
(10-z)mc
zo
17; Wherein Ma is Yb, Sn, Pb, Ce, Tb, Dy, Pr, Ca, Sr, Ba or above-mentioned combination, and 0≤x≤0.9; Mb is Mn, Zn or above-mentioned combination, and 0<y≤0.7; Mc is Ga, In, B or above-mentioned combination, 0≤z≤5.
In an embodiment of the present invention, the composition of fluorescent material can be EuMg
(1-y)mn
yal
10o
17.
In an alternative embodiment of the invention, the composition of fluorescent material can be EuMg
0.8mn
0.2al
(10-z)ga
zo
17, wherein 0<z≤5.
In an embodiment of the present invention, Mb is Mn, and Ma
xmd
pme
q.Md is Sn, Yb, Pb, Tb, Ce, Dy, Pr or above-mentioned combination, and 0<p≤0.5.Me is Ca, Sr, Ba or above-mentioned combination, and 0≤q≤0.9.In above-mentioned composition, 0<p+q≤0.9.
In still another embodiment of the process, Mb is Mn, and Ma
xmd
pme
q.Md is Sn, Pb, Tb, Ce, Dy, Pr or above-mentioned combination, and 0<p≤0.5.Me is Ca, Sr, Ba or above-mentioned combination, and 0≤q≤0.9.In above-mentioned composition, 0<p+q≤0.9.
In an alternative embodiment of the invention, Mb is Mn, and Ma is Sn, Yb, Pb, Tb, Ce, Dy, Pr or above-mentioned combination, and 0<x≤0.5.
Above-mentioned fluorescent material can radiate the green glow that main peak is similar to 517nm after exciting via blue light (400nm to 420nm) or UV-light (200nm to 400nm).The above-mentioned excitation light source in order to send blue light or UV-light can be can photodiode or laser diode.
The forming method of above-mentioned fluorescent material is solid state reaction, first weighs the reagent of suitable mol ratio according to stoichiometry.Reagent containing Eu, Mn, Zn, Yb, Sn, Pb, Ce, Tb, Dy, Pr, Ca, Sr, Ba can be muriate as EuCl
2, oxide compound is as Mn
3o
4, ZnO or MnO, carbonic acid thing is as MnCO
3, acetic acid thing is as Mn (CH
3cOO)
2, nitric acid thing is as Tb (NO
3)
3.Reagent containing Mg can be oxide compound as MgO, and carbonic acid thing is as MgCO
3, or muriate is as MgCl
2.Reagent containing Al, Ga or In can be oxide compound as γ-Al
2o
3, Ga
2o
3, or In
2o
3.Boron source can be containing borane reagent as boron oxide (B
2o
3) or boric acid (H
3bO
3).Grind after getting the mentioned reagent Homogeneous phase mixing of equivalence ratio, after then putting into crucible, insert High Temperature Furnaces Heating Apparatus, after 1400-1700 DEG C of sintering a few hours, above-mentioned fluorescent material.
In an embodiment of the present invention, fluorescent material radiates green glow after blue light or ultraviolet excitation.In this embodiment, can by above-mentioned fluorescent material, the red light flourescent material that the combination ultraviolet blue-light fluorescent material that can excite and ultraviolet or blue light can excite, and collocation can send photodiode or the laser diode equal excitation source of near-ultraviolet ray, to make white light emitting diode or white light laser diode light source.Wherein blue-light fluorescent material comprises BaMgAl
10o
17: Eu
2+, (Ba, Sr, Ca)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, 2SrO*0.84P
2o
5* 0.16B
2o
3: Eu
2+, Sr
2si
3o
8* 2SrCl
2: Eu
2+(Mg, Ca, Sr, Ba, Zn)
3b
2o
6: Eu
2+, or other suitable blue-light fluorescent material.Red light flourescent material can be (Sr, Ca) S:Eu
2+, (Y, La, Gd, Lu)
2o
3: Eu
3+, Bi
3+, (Y, La, Gd, Lu)
2o
2s:Eu
3+, Bi
3+, Ca
2si
5n
8: Eu
2+, ZnCdS:AgCl or other suitable red light material.If the blue light using ultraviolet to excite and red light flourescent material are the application mode of " directly the exciting " in ultraviolet photodiode or laser diode equal excitation source; If use the red light flourescent material that blue light can excite, then belong to blue-light fluorescent material send the application mode of " indirectly exciting " of blue light.And ruddiness, blue light, with the combination of green-emitting fluorescent material, also respectively have its different optimum formulas or ratio.
The white light devices such as aforesaid photodiode or white light laser diode, can by above-mentioned various indigo plant/green/red fluor that waits according to optimum formula or ratio, after Homogeneous phase mixing is scattered in transparent optical cement, is packaged in the chip of the photodiode or laser diode etc. that can send near-ultraviolet ray and makes.But it should be noted that and do excitation light source with UV-light, uv filter should be set in white light emitting device outermost or utilize other UV-light to completely cut off mode, to avoid damaging human body or eyes.
Except white light emitting diode, ultraviolet excited fluorescence material of the present invention can be applied to solar cell further.The diagram of general solar cell as shown in Figure 1, transparency carrier 11 is sequentially formed with anode 13, semiconductor layer 15 and negative electrode 17.In general, the material of transparency carrier 11 is glass, plastics or synthetic resins.Anode 13 is that transparency conducting layer is as indium tin oxide, zinc oxide, fluorinated tin oxide or above-mentioned combination.Semiconductor layer 15 can be single one layer or more PIN structural, be sequentially p-type doping, do not adulterate (i.e. so-called I layer) and N-shaped adulterate semiconductor material, semiconductor material can be amorphous silicon hydride or microcrystalline hydrogenated silicon.Negative electrode 17 is the metals such as aluminium, silver, molybdenum, platinum, copper, gold, iron, niobium, titanium, chromium, bismuth, antimony.The wavelength region that the semiconductor layer of current major part can utilize is visible region, cannot utilize the ultraviolet region that energy is stronger.Fluorescent material of the present invention can be formed at the upper surface 19 of transparency carrier 11.Thus, the UV-light of sunlight will excite fluorescent material of the present invention to send green glow, increase the rate of utilization of semiconductor layer 15 pairs of sunlights.
In order to above and other objects of the present invention, feature and advantage can be become apparent, several embodiment cited below particularly coordinates appended accompanying drawing, is described in detail below:
Embodiment 1
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.9mn
0.1al
10o
17, EuMg
0.8mn
0.2al
10o
17, EuMg
0.7mn
0.3al
10o
17, and EuMg
0.6mn
0.4al
10o
17.Above-mentioned product and known fluorescent material EuMgAl
10o
17photic radiation trace analysis as shown in Figure 2.Fluorescent material of the present invention excite that main peak is 396nm, radiation main peak be the CIE coordinate of 515-517nm and radiation main peak for (0.157,0.667), as shown in Figure 3.With unadulterated fluorescent material EuMgAl
10o
17compare, the radiation wavelength of fluorescent material of the present invention is longer.With EuMg
0.7mn
0.3al
10o
17for example, its strongest luminous intensity 1*10
7count. also than EuMgAl
10o
17the strongest luminous intensity 5*10
6count. 100% is increased.Fig. 4 is EuMg
(1-y)mn
yal
10o
17in, the impact of Mn content (y) photoluminescence intensity (photoluminescence intensity).Mn at the beginning
2+doping ratio higher time, photoluminescence intensity can along with increase, has a preferably intensity when y=0.3.But Mn
2+doping ratio when increasing again, then photoluminescence intensity can reduce.It should be noted that the suitable strength of Fig. 4 is by being obtained so that 1600 degree of 8 hours conditions are lower.And other EuMg
(1-y)mn
yal
10o
17the sintering temperature of doping ratio when looking closely preparation and sintering time and determining, be not limited to the optimum proportion shown in Fig. 4.
Embodiment 2
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%), Al
2o
3(FW=101.96, ALDRICH>99.9%) and Ga
2o
3(FW=187.44, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.8mn
0.2al
9.5ga
0.5o
17, EuMg
0.8mn
0.2al
9gaO
17, EuMg
0.8mn
0.2al
7ga
3o
17, and EuMg
0.8mn
0.2al
5ga
5o
17.As shown in Figure 5, the CIE coordinate that it excites main peak between 380nm to 396nm, radiation main peak is 515nm and radiation main peak is (0.155,0.615) to the photoexcitation radiation comparison diagram of above-mentioned product.From the above, Al of the present invention can adulterate all the other 3A races element (Mc) as Ga.
Embodiment 3
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), Yb
2o
3(FW=394, PRO CHEM INC99.9%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.7mn
0.3al
10o
17, Eu
0.98yb
0.02mg
0.7mn
0.3al
10o
17, Eu
0.93yb
0.07mg
0.7mn
0.3al
10o
17, Eu
0.77yb
0.23mg
0.7mn
0.3al
10o
17, and Eu
0.5yb
0.5mg
0.7mn
0.3al
10o
17.As shown in Figure 6, it excites main peak between 380nm to 396nm to the photoexcitation radiation comparison diagram of above-mentioned product, radiation main peak is between 516nm to 517nm and radiate the CIE coordinate of main peak for (0.163,0.673).From the above, the present invention can adulterate a small amount of Yb to improve launching efficiency and the intensity of radioactivity of fluorescent material.
Embodiment 4
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), SnO (FW=134.69, PRO CHEM INC99.9%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.7mn
0.3al
10o
17and Eu
0.98sn
0.02mg
0.7mn
0.3al
10o
17.As shown in Figure 7, the CIE coordinate that it excites, and main peak is between 396nm, radiation main peak is 517nm and radiation main peak is (0.152,0.665) to the photoexcitation radiation comparison diagram of above-mentioned product.From the above, the present invention can adulterate a small amount of Sn to improve launching efficiency and the intensity of radioactivity of fluorescent material.
Embodiment 5
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), Pb
3o
4(FW=685.6, SHOWA CHEMICAL99.9%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.7mn
0.3al1
0o
17and Eu
0.98pb
0.02mg
0.7mn
0.3al
10o
17.As shown in Figure 8, the CIE coordinate that it excites, and main peak is 396nm, radiation main peak is 517nm and radiation main peak is (0.153,0.686) to the photoexcitation radiation comparison diagram of above-mentioned product.From the above, the present invention can adulterate a small amount of Pb to improve launching efficiency and the intensity of radioactivity of fluorescent material.
Embodiment 6
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), Tb (NO
3)
35H
2o (FW=453.04, STREM CHEMICAL99.9%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains EuMg after taking-up
0.7mn
0.3al
10o
17and Eu
0.98tb
0.02mg
0.7mn
0.3al
10o
17.As shown in Figure 9, the CIE coordinate that it excites, and main peak is between 396nm, radiation main peak is 517nm and radiation main peak is (0.153,0.677) to the photoexcitation radiation comparison diagram of above-mentioned product.From the above, the present invention can adulterate a small amount of Tb to improve launching efficiency and the intensity of radioactivity of fluorescent material.
Embodiment 7
Eu is weighed respectively according to stoichiometry
2o
3(FW=351.92, ALDRICH99.99%), SrCO
3(FW=147.6, PRO CHEM INC99.9%), Tb (NO
3)
35H
2o (FW=453.04, STREMCHEMICAL99.9%), MgO (FW=40.3, ALDRICH99.99%), MnCO
3(FW=114.93, ALDRICH99.99%) and Al
2o
3(FW=101.96, ALDRICH>99.9%), grinds after Homogeneous phase mixing, inserts High Temperature Furnaces Heating Apparatus, in the 5%H of 1600 DEG C
2/ N
2lower sintering about 8 hours, namely obtains Eu after taking-up
0.98tb
0.02mg
0.7mn
0.3al
10o
17, Eu
0.73sr
0.25tb
0.02mg
0.7mn
0.3al
10o
17, Eu
0.48sr
0.5tb
0.02mg
0.7mn
0.3al
10o
17, and Eu
0.23sr
0.75tb
0.02mg
0.7mn
0.3al
10o
17.As shown in Figure 10, the CIE coordinate that it excites main peak between 370 to 396nm, radiation main peak is 516nm and radiation main peak is (0.146,0.673) to the photoexcitation radiation comparison diagram of above-mentioned product.From the above, the present invention can adulterate multiple hotchpotch if Sr and Tb is to improve launching efficiency and the intensity of radioactivity of fluorescent material.
Although the present invention discloses as above with several preferred embodiment; so itself and be not used to limit the present invention; anyly have the knack of this those skilled in the art; without departing from the spirit and scope of the present invention; when doing arbitrary change and retouching, therefore protection scope of the present invention is as the criterion when the scope defined depending on accompanying claims.
Claims (8)
1. a fluorescent material, has structural formula as follows:
Eu
(1-p)Md
pMg
(1-y)Mn
yAl
(10-z)Mc
zO
17；
Wherein, 0<y≤0.7; And
Mc is Ga, In, B or above-mentioned combination, and 0≤z≤5;
When Md is Yb, 0<p≤0.23,
When Md is Sn, Pb or Tb, 0<p≤0.02.
2. fluorescent material according to claim 1, wherein z=0.
3. a white light emitting device, comprises fluorescent material according to claim 1 and an excitation light source, and the wavelength of described excitation light source is the UV-light of 200nm to 400nm or the blue light of 400nm to 420nm.
4. white light emitting device according to claim 3, wherein said excitation light source is photodiode or laser diode.
5. white light emitting device according to claim 3, also comprises a blue-light fluorescent material and red light flourescent material.
6. white light emitting device according to claim 5, wherein said blue-light fluorescent material is BaMgAl
10o
17: Eu
2+, (Ba, Sr, Ca)
5(PO
4)
3(F, Cl, Br, OH): Eu
2+, 2SrO*0.84P
2o
5* 0.16B
2o
3: Eu
2+, or Sr
2si
3o
8* 2SrCl
2: Eu
2+(Mg, Ca, Sr, Ba, Zn)
3b
2o
6: Eu
2+.
7. white light emitting device according to claim 5, wherein said red light flourescent material is (Sr, Ca) S:Eu
2+, (Y, La, Gd, Lu)
2o
3: Eu
3+, Bi
3+, (Y, La, Gd, Lu)
2o
2s:Eu
3+, Bi
3+, Ca
2si
5n
8: Eu
2+, or ZnCdS:AgCl.
8. a solar cell, comprising:
One transparency carrier;
One anode and a negative electrode, be positioned at the lower surface of described transparency carrier; And
Semi-conductor layer, between described anode and described negative electrode;
The upper surface of wherein said transparency carrier has fluorescent material according to claim 1.
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| CN201310333243.2A CN103450900B (en) | 2008-12-11 | 2009-11-05 | Fluorescent material, white-light light-emitting device and solar battery |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1498405A (en) * | 1974-03-05 | 1978-01-18 | Thorn Electrical Ind Ltd | Phosphors |
| CN101142296A (en) * | 2005-01-14 | 2008-03-12 | 英特曼帝克司公司 | Novel aluminate-based green phosphors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2846647B1 (en) * | 2002-11-05 | 2005-01-21 | Rhodia Elect & Catalysis | PRESSODYM DOPED BARIUM AND MAGNESIUM SILICATE, USE THEREOF IN LUMINESCENCE AND AS ANTI-UV ADDITIVE AND IN LIGHT-EMITTING MATERIALS |
| JP2008195807A (en) * | 2007-02-13 | 2008-08-28 | Nichia Chem Ind Ltd | Vacuum ultraviolet light-excited aluminate phosphor and device for emitting vacuum ultraviolet light-excited light by using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1498405A (en) * | 1974-03-05 | 1978-01-18 | Thorn Electrical Ind Ltd | Phosphors |
| CN101142296A (en) * | 2005-01-14 | 2008-03-12 | 英特曼帝克司公司 | Novel aluminate-based green phosphors |
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