CN101348719B - Warm white LED and halogenide fluorescent powder thereof - Google Patents
Warm white LED and halogenide fluorescent powder thereof Download PDFInfo
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- CN101348719B CN101348719B CN2008102121749A CN200810212174A CN101348719B CN 101348719 B CN101348719 B CN 101348719B CN 2008102121749 A CN2008102121749 A CN 2008102121749A CN 200810212174 A CN200810212174 A CN 200810212174A CN 101348719 B CN101348719 B CN 101348719B
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- 239000000843 powder Substances 0.000 title claims abstract description 50
- -1 halide nitride Chemical class 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000002223 garnet Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 150000004767 nitrides Chemical class 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 239000012190 activator Substances 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 64
- 230000005855 radiation Effects 0.000 claims description 32
- 238000001228 spectrum Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 241001025261 Neoraja caerulea Species 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 1
- 150000004820 halides Chemical class 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 15
- 230000008859 change Effects 0.000 description 13
- 230000008901 benefit Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910017090 AlO 2 Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000005395 radioluminescence Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- UGTJLJZQQFGTJD-UHFFFAOYSA-N Carbonylcyanide-3-chlorophenylhydrazone Chemical compound ClC1=CC=CC(NN=C(C#N)C#N)=C1 UGTJLJZQQFGTJD-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 238000013499 data model Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to halide fluorescent powder, which is low color temperature halide nitride fluorescent powder on the basis of rare earth oxide garnet and adopts cerium as an activator. The halide fluorescent powder is characterized in that chlorine ions Cl-1 and nitrogen ions N-3 are added into compositions of the fluorescent powder; and the chemical formula formed is (SigmaLn+3)3Al2[(Al(O1-2pClpNp)4]3, wherein SigmaLn is equal to Y and/or Gd and/or Tb and/or Lu and/or Dy and/or Pr and/or Ce. Moreover, the invention also discloses a warm white light-emitting diode which uses the nitride fluorescent powder, and the weight ratio of the warm white light-emitting diode is between 8 and 75 percent. When the power of the light-emitting diode is 1 watt, the warm red luminescent color temperature T is less than or equal to 3,000 kelvins.
Description
[technical field]
The present invention relates to a kind of warm white light light-emitting diode (LED) and halogenide fluorescent powder thereof; Relate in particular to a kind of production technology of improving, create novel warm white light light-emitting diode (LED) and halogenide fluorescent powder thereof for different classes of indicating unit such as household, street lamp, railway station, tunnel, railway and course line.
[background technology]
Semiconductor light-emitting-diode develops into the heterojunction structure by nitride InGaN the development that improves in nearest 50 years by traditional G aAs (P) system structure, has ensured present stage luminous technical parameter, luminous intensity I and luminous efficiency ζ (lumens/watt).
Photodiode pioneer worker S by Japan; Nakanura creates (please with reference to S.Nakamura.Blue laser.Springer-Verlar.Berlin.1997); The nitride heterojunction InGaN that contains a large amount of quantum well structures with processing is the basis, improves this technology.The blue light of this work and ultraviolet light-emitting diodes output F >=10 lumens have 40% perhaps higher electronic power and change in photodiode.Adopt this effective blue light heterojunction photodiode, once in white-light emitting structure originally, proposed (please with reference to people such as S.Schimizu US20071149914 patent application case).
This photodiode in conjunction with two kinds of complementary color, creates white light according to famous newton's complementary color principle of the 17th century.Adopt in the white light emitting diode and have the stokes fluorescent material of emission wavelength greater than excitation wavelength; By Soviet Union slip-stick artist (please with reference to A б pa м о в B.C.Cy ш к о в B. ∏ .A в т о р с к о e с в и д e т e л ь с т в о CCCP № 630813 о т 09/12/1977) were proposed first at this item in 1977.
Adopt yttrium aluminum garnet Y for creating first
2Al
5O
12: Ce (please with reference to GBlasse et and.Luminescent material.Springer Verl, Amst.N-Y, 1994) is used in the CRT light-emitting device as the white light emitting diode of material.Radiation yellow wavelengths λ=560nm after blue ray radiation wavelength X=460nm of nitride heterojunction InGaN, this material are excited, at this moment the unabsorbed blue light of part combines with Yellow luminous, produces the radiation of intensive white light.First photodiode white light irradiation structure has high colour temperature T >=6500K mostly.
In above-mentioned known patent application case (please with reference to people such as S.S chimizu US20071149914 patent application case), adopt its major technology advantage of hi-tech solution that is proposed to reduce: 1. lack removable composition, node and parts, for the highly effective and safe property and the durability degree that ensure photodiode; 2. simple package structure, independently heterojunction semiconductor structure component; And 3. possibly obtain T >=6500K cold white light.
Above-mentioned advantage has been guaranteed the employing on the energy storage device of architectural lighting, Landscape Lighting field and battery of mobile telephone that known configurations is a large amount of.
In the data model of known patent, be proposed in first and adopt yttrium aluminum garnet Y in the fluorescent material
3Al
5O
12: Ce (YAG:Ce), however exist defective equally.Pointed out the radiation colour temperature T >=6500K of cold white light at first, before.
Point out that at work the yttrium aluminium garnet fluorescent powder radiation presents wild effect, combine that behind 1000 hours high light, radiant light has reduced 15～35% with the polymer phase that with epoxy resin is the master.Being similar to such situation is because the mutual relationship between fluorescent material top layer and the polymkeric substance is irreversible.Incident then is the disappearance of part transparence.
In known patent, there is light intensity radiating defective like this equally, for example sets up yttrogarnet fluorescent material and non-stoichiometric garnet phosphor powder (please with reference to people such as Sochchin N.P TW249567B5 patent case) and contain aluminium Al
+ 3Or silicon Si
+ 4Mixture garnet material (please with reference to people's such as Sochchin N.P TW.95117824 patent case, 19/05/2006) and (please with reference to Japan's 2007113487 patent application cases of people such as Sochchin N.P, 19/05/2006).
The solution that this is a part of makes the problem of many garnet phosphor powders and is well solved setting up on the advanced luminescent material.
Very the fluorescent material of high-parameters wherein is positioned at the tetrahedron oxonium ion around rare earths, but some of oxonium ion O
-2By fluorion F
-1And nitrogen ion N
-3Replacement, stoichiometric equation is: O
O+ O
O→ (N
o) °+(F
o) '.
Adopt and special like this have high heat-resisting and time stable fluorescence powder and reach the high-luminous-efficiency that power W=1 watt-hour luminous efficiency reaches 105 lumens/watt.
Aluminium and oxygen can be by other different ion F in the garnet structure
-1, Cl
-1, Si
+ 4, B
+ 3Replacement.The chemical equivalent formula (Y, Gd, Lu)
3Al
5O
12In, part A l
+ 3By Si
+ 4, B
+ 3, Ga
+ 3Replacement, the partial oxygen ion is by F
-1, Cl
-1, S
-2, P
-3Get and replace, the concrete quantity of mixture does not specify in patent, only points out to add fluorine, and the brightness that makes fluorescent material of success has promoted 20%.But at similar patent US6,400, point out among the 938B1/25.06.2002, according to fluorite garnet formula: (Y, Ce, Gd)
3Al
5(O, F)
12(please with reference to people's such as H.A.Co м anzo. US6409938B1 patent, 25/06/2002) can be found out the deficiency of above-mentioned patent, and the technical solution advantage is in this patent: 1. possibly change negatively charged ion in the fluorescent material component, same positively charged ion also can be like this; 2. adopt and add halogen ion F
-1, make the luminosity of fluorescent material promote 10～20%.
At Taiwan the 097123219th patent application case that this case applicant has applied for (please with reference to people's such as Sochchin N.P. 097123219; 25; 06,2008) middle finger comes from the global advantage in the oxyfluoride garnet series: 1. the garnet phosphor powder radiation spectrum that depends on fluorion is from λ=531～550 nanometers; 2. fluorescent material radiating high heat resistance is because with O
-2Replace to different valence state F
-1
In this patent, list fluorescent material garnet crystal lattice parameter a=11.951～11.99A equally.So detailed parameter in above-mentioned 097123219 patent application case inevitable dominance and special garnet phosphor powder combine.
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention provides a kind of warm white light light-emitting diode (LED) and halogenide fluorescent powder thereof, and it has the fluorescent material formula of special orange red radioluminescence.
For solving the shortcoming of above-mentioned known technology, main purpose of the present invention provides a kind of warm white light light-emitting diode (LED) and halogenide fluorescent powder thereof, and it adopts large batch of production, need draft reliable regulations for technical operation.Mainly be to improve its effective quantum efficiency and luminosity for setting up novel fluorescent material in addition.
For solving the shortcoming of above-mentioned known technology; Main purpose of the present invention provides a kind of warm white light light-emitting diode (LED) and halogenide fluorescent powder thereof; It can set up the establishment that the new technique solution is not limited to the novel inorganic phosphor material powder, also comprises creating the durable photodiode that has thermostability and have the luminous parameter.
For reaching above-mentioned purpose, a kind of halogenide fluorescent powder of the present invention, it is to be the low colour temperature halogen Nitride phosphor on the basis with the rare earth oxide garnet, adopts cerium as activator, is characterised in that: in this fluorescent material component, add cl ions Cl
-1, nitrogen ion N
-3, the stoichiometric equation of its composition is: (∑ Ln
+ 3)
3Al
2[Al (O
1-2pCl
pN
p)
4]
3, wherein ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or Dy and/or Pr and/or Ce.
For reaching above-mentioned purpose; A kind of warm white light light-emitting diode (LED) of the present invention; It is to become matrix and have the structure of a luminescent conversion layer with the InGaN heterogeneous semiconductor; It is characterized in that: this luminescent conversion layer is distributed in the light-emitting area and the side of this InGaN heterojunction semiconductor with the uniform form of thickness, directly contacts with faceted pebble with the plane of this InGaN heterojunction semiconductor.
Technical solution proposed by the invention is not limited to the prescription of inorganic fluorescent powder; Its direction is to set up in the invention course of processing to have high radiant light instrument and contain the luminous I of HS; And the optical throughput F of high numerical value and have the low color temperature value of T≤3000K, and the necessary colour system numerical value of drilling.Photodiode proposed by the invention should guarantee that high luminescence technology parameter generally is suitable for museum, showroom, and exhibition place.
[description of drawings]
Fig. 1 is a synoptic diagram, and it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 1 in the table 1.
Fig. 2 is a synoptic diagram, and it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 2 in the table 1.
Fig. 3 is a synoptic diagram, and it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 3 in the table 1.
Fig. 4 is a synoptic diagram, and it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 4 in the table 1.
Fig. 5 is a synoptic diagram, and it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 5 in the table 1.
[embodiment]
At first, the objective of the invention is to eliminate the shortcoming of above-mentioned fluorescent material.In order to reach this target; Halogenide fluorescent powder of the present invention is used for warm white light light-emitting diode (LED), and it is to be the low colour temperature halogen Nitride phosphor on the basis with the rare earth oxide garnet; Adopt cerium as activator, be characterised in that: in this fluorescent material component, add cl ions Cl
-1, nitrogen ion N
-3, the stoichiometric equation of its composition is: (∑ Ln
+ 3)
3Al
2[(Al (O
1-2pCl
pN
p)
4]
3, wherein ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or Dy and/or Pr and/or Ce.
Wherein, chemical parameters 0.001 ≦ p ≦ 0.2 in this stoichiometric equation.
Wherein, This halogenide fluorescent powder best rare earth ion composition in positively charged ion sublattice component is: 0.001 ≦ (Y/ ∑ Ln) ≦ 0.5,0.5 ≦ (Gd/ ∑ Ln) ≦ 0.95,0 ≦ (Tb/ ∑ Ln) ≦ 0.1; 0 ≦ (Lu/ ∑ Ln) ≦ 0.05; 0 ≦ (Dy/ ∑ Ln) ≦ 0.05,0.0001 ≦ (Pr/ ∑ Ln) ≦ 0.01,0.01 ≦ (Ce/ ∑ Ln) ≦ 0.1.
Wherein, lattice parameter a >=12.01A that this halogenide fluorescent powder is main, and increase along with the increase of chemical index in the formula " p ".
Wherein, the spectrum greatest irradiation of this halogenide fluorescent powder is λ=580 ± 3nm, and wavelength can be toward long wavelength shifted when increasing the chemical parameters " p " in the stoichiometric equation.
Wherein, this halogenide fluorescent powder is when the chemical index " P " in the increase fluorescent material matrix, and the wide meeting of spectrum half-wave becomes greatly λ
0.5=126+6nm.
Wherein, this halogenide fluorescent powder is when the chemical index " P " in the increase fluorescent material matrix, and the radiation chromaticity coordinates increases to ∑ (x+y)>0.88.
Wherein, in the matrix of this halogenide fluorescent powder under the increase of chemical parameters " p " quantum output increase to ζ=0.96 from ζ=0.92.
Wherein, the particle of this halogenide fluorescent powder becomes the prismatic shape, and the neutrality line diameter of this fluorescent powder grain is d
50≤4.0 microns, d
90≤16 microns.
The contrast of fluorescent material proposed by the invention and known fluorescent material, its difference is: simultaneously in anion lattice by the ion of two different oxidisabilities, such as cl ions Cl
-1With nitrogen ion N
-3Replace oxygen ion O
-2
Confirmable theory; Technical literature before the fluorescent material utilization proposed by the invention (please with reference to H.A.C о м а nz о. wait people's US6,409, the 938B1 patent; 25/06/2002); In fluorescent material proposed by the invention, note that the form of each three valence state atom, as at tetrahedron AlO
4In the aluminum ion Al that centers on
+ 3, can change over AlO
2Cl
-1N
-3
Change anionic component like this in essence, different valence state replacement takes place in outcome procedure, equation is:
O
O+Cl
-1→Cl
O +1+1/2O
2↑
gas
O
O+N
-3→N
O -1+1/2O
2↑
gas
2O
O+Cl
-1+N
-3→Cl
O +1+N
O -1+O
2↑
Cl wherein
O + 1Mean existing cl ions Cl
-1In anion lattice, replaced oxonium ion O
O, and N
O -1Expression nitrogen ion N
-3In anion lattice, replaced oxonium ion O
O
The positively charged ion lattice can change equally, traditional rare earth ion, Y
+ 3, Gd
+ 3, Lu
+ 3, Tb
+ 3Major portion at the positively charged ion lattice can be introduced Dy
+ 3And Pr
+ 3, contain Ce simultaneously
+ 3, fluorescent material can have two or more startup ion, for example Ce
+ 3And Pr
+ 3And Ce
+ 3And Dy
+ 3Perhaps the three has simultaneously.Similar multiple startup ion fluorescence powder obtains broader integrated red spectrum radiation, can change the illuminant colour section.
Also have important many activator and three valence state fluorescent material in addition.This fluorescent material belongs to rare-earth garnet fluorescent material, has cubic structure and O
n 10-Ia3d spatial group, but garnet type Y
3Al
5O
12, activator cerium Ce
+ 3Has very narrow excitation band, from λ=445～475nm.In this connects, excitation band mutual restriction Ce
+ 3-O
-2Transfer.Activation cerium ion Ce around this garnet phosphor powder
+ 3Can be in tetrahedron combines three valence states to fill AlO
2F
-1N
-3, so the increase on the excitation band substance.Can reduce the demand of demand and heterojunction semiconductor excitation wavelength like this, adopt quantity radiation wavelength λ=440nm of heterojunction InGaN originally in this case, have bigger led radiation wavelength X
Ext=400～485nm.
Has very important advantage like the above-mentioned fluorescent material that proposes with three valence states; It is characterized in that: for the rare earth ion composition that is based upon in the positively charged ion lattice: 0.001 ≦ (Y/ ∑ Ln) ≦ 0.5,0.5 ≦ (Gd/ ∑ Ln) ≦ 0.95,0 ≦ (Tb/ ∑ Ln) ≦ 0.1; 0 ≦ (Lu/ ∑ Ln) ≦ 0.05; 0 ≦ (Dy/ ∑ Ln) ≦ 0.05,0.0001 ≦ (Pr/ ∑ Ln) ≦ 0.01,0.01 ≦ (Ce/ ∑ Ln) ≦ 0.1.
Prescription in the positively charged ion lattice is with respect to ruthenium ion Y
+ 3, improve gadolinium ion Gd
+ 3During concentration, fluorescent material can increase the radiation of warm ruddiness.When in the structure of positively charged ion lattice, introducing other rare earth ion compositions simultaneously, effect is to change luminous intensity, for example adds like Lu
+ 3And Tb
+ 3At first quote the Tb of less ionic radius
+ 3(τ=0,85A) and Lu
+ 3(τ=0,81A), its interatomic distance shortens, and incident is the strong growth in the crystal inside static field of force, active ions Ce
+ 3, Pr
+ 3And Dy
+ 3During introduction, can make luminosity obtain increasing.
As fluorescent material of the present invention, the proposal that this is important is characterized in that: for the growth of " p " in stoichiometric equation of this fluorescent material, its lattice parameter can increase to a=12.01A.
As above-mentioned explanation of quoting, in the parameters in series of Y-Gd-Tb-Lu, the change of lattice parameter is from a
Y=12.00A to a
Gd=12.11A, a
Tb=11.912A to a
Lu=11.909A.In the positively charged ion lattice, quote 5% macrobead Ce
+ 3Ion and/or Pr
+ 3Ion can increase 3～4% with the lattice parameter value.
Different what replace with valence state with discovery in the garnet, the present invention turns to replacement oxonium ion O with attention
-2, oxonium ion a wherein
O-2=1.40A is by the less fluorion a of ionic radius
F-1=1.32A replacement will reduce its lattice parameter.
For component (Y
0.77Gd
0.2Ce
0.03)
3Al
2(AlO
3F
2)
3, applicant of the present invention once confirmed parameter value a=11.972A in the Republic of China's 097123219 patent application case, if use fluorion F
-1The O of replacement 25%
-2Then the parameter size reduces 1～1.2%, and through in the tetrahedral influence of fluorine alumina, the change of its scope is to result from a fluorion not change its main A1 at this
+ 3Framework.Cl according to same size
-1Replacement O
-2, its parameter value size has increased by 0.1%.On tetrahedron, use N
-3Ion is replaced oxonium ion for the second time, and lattice parameter should increase.But say that definitely it is very difficult that present stage increases on this value theory.
In fact, N
-3Ion and O
-2Ion is compared and is had large size (a
N-3=1.58A, a
O-2=1.4A).But long radius ion numerical value on tetrahedron that great majority increase diminishes.N
-3With O
-2Ionic radius is compared, and it is identical 1.5～2% that its parameter value possibly considered, as the O of integral body replacement 25%
-2When atom is replaced by nitrogen-atoms, exist (AlO
2F
-1N
-3)
3Lattice parameter must change identical direction: reduce F
-1Introducing, with N
-3Ionic increases.Such sample, parameter component a=11.979 (1.02-1+0.988) A=12.0748A that numeral changes.
Can use the spectral radiance analyser of " Sensing " company to measure in this colorimetric performance for fluorescent material proposed by the invention; (chromaticity coordinates is in xyz and uvw system to quote the fluorescent material of 5 different parameters; Greatest irradiation spectrum and radiation wavelength, color temperature value is drilled colour system and is counted the Ra value) in table 1; Adopted this five data, these all data referencings are at form 1.
Table 1 nitrogen muriate luminescent phosphor luminescence technology parameter
[0056]?
[0057]?
The present invention subsequently will set forth through the mode of graphic representation this piece 097123219 patent.The chart of being quoted in this patent is: please with reference to Fig. 1, it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 1 in the table 1; Please with reference to Fig. 2, it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 2 in the table 1; Please with reference to Fig. 3, it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 3 in the table 1; Please with reference to Fig. 4, it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 4 in the table 1; Please with reference to Fig. 5, it draws the fluorescent material integral radiation spectrum synoptic diagram of the sample 5 in the table 1.
In table 1, compare, in the negatively charged ion sublattice, do not introduce Cl for gadolinium-yttrium-aluminium garnet luminescence technology parameter value with standard
-1With N
-3Ion lacks Tb ion and Lu ion in cationic composition.
The chromaticity coordinates value of standard samples is little in table 1, and ∑ (x+y)≤0.85, greatest irradiation wavelength are λ=581nm.With best halogen nitride sample mutually brightness descended 12～15%.The colour temperature of sample and chromaticity coordinates also exist difference.For the sample colour temperature T=3200K of standard, surpass T=2780K for these parameters of sample 1～4.
The advantage of halogen Nitride phosphor of the present invention is characterized in that: its greatest irradiation spectrum lambda
Max=580 ± 3nm along with [Pr] main in the increase of chemical parameters " p " and the fluorescent material increases, has maximum wavelength shift in stoichiometric equation.All these are all set forth before requiring.Meanwhile, same Cl in increasing anion lattice
-1Ion and N
-3During ion, the maximum wavelength displacement is made a leapleap forward from λ=580nm to λ=610nm.
Two kinds of different like this emission wavelength mechanism before be not able to utilization on LED.Such a advantage is achieved in the 1st fluorescent material component that is proposed of claim of the present invention, it is characterized in that: increase " p " value in the stoichiometric equation, promptly in anion lattice, add suitable Cl
-1And N
-3Ionic weight, the wide change of maximum spectrographic half-wave is by λ
0.5=126nm to λ
0.5=132nm.
Point out the most important advantage of fluorescent material proposed by the invention simultaneously, it is characterized in that: ∑ (x+y)>=0.88 increases " p " value in the stoichiometric equation, the Cl that promptly in the negatively charged ion sublattice, suits
-1And N
-3Ionic weight makes that " x " value exceeds x in the sub-band radiation of orange red spectrum; 0.46, can obtain T<the low colour temperature that 3000K is such.
Just as the advantage of the existence that the invention described above proposed, it is characterized in that: under the situation that increases stoichiometry index " p ", increase the Cl in the anion lattice
-1And N
-3Content.The radiation of its quantum dot increases from ζ=0.92 to ζ=and 0.96.
What need supplementary notes is, for the output of effective quantum dot, many fluorescent material normally reduce the radiation wavelength displacement, and in the brightness value of described in the present invention fluorescent material L, the quantum radiation output valve that matches increases in table 1.
Fluorescent material proposed by the invention also has an important characteristic, the most ovalizes of fluorescent powder grain that applicant of the present invention disclosed before.We think must be by Cl
-1With N
-3Replacement O
-2The replacement of different in this case valency replaces, the growth of light-emitting particles, and the fluorescent powder grain of standard is and is similar to ellipse, and it has reduced granule geometric dimension in essence, and fluorescent material proposed by the invention has miniature particle size distribution.
The such a substantial advantage of fluorescent powder grain, it is characterized in that: the indication material is avette, particulate neutrality line diameter dimension d
50≤4.0 microns, and d
90≤10 microns.
In addition; The present invention also discloses a kind of warm white light light-emitting diode (LED); It is (to be that P-N connects face with InGaN (InGaN) heterojunction semiconductor; Figure does not show) for matrix and have the structure of a luminescent conversion layer (figure do not show), it is characterized in that: this luminescent conversion layer is distributed in the light-emitting area and the side of this InGaN heterojunction semiconductor with the uniform form of thickness, directly contacts with faceted pebble with the plane of this InGaN heterojunction semiconductor.
The faceted pebble of in our invention process, pointing out main radiating surface and luminescent conversion has identical thickness.If this luminescent conversion layer is in uneven thickness, then can constitute the luminous of different tones, this is unallowed, the photodiode proposed by the invention is characterized in that: its luminescent conversion layer has identical thickness.At first, adopt the polymkeric substance that contains high standard viscosity of specialty, the method that this is professional two form part be included in suspended particle fluorescent material and polymkeric substance interconnection.
This method can have been guaranteed the air bubble in the sufficient eliminating suspension-s, but does not hinder the luminous radiation output of heterojunction, and such method has guaranteed that the fluorescent powder grain that lacks viscosity is suspended in the suspension-s.
Point out the advantage that realizes that photodiode proposed by the invention has at this; It is characterized in that: the fluorescent material component of on its luminescent conversion layer, setting up as stated; In this luminescent conversion with mixed with polymers the time; Molecular mass from the M=12000 carbosilane unit to the M=20000 carbosilane unit, the chemical connection type between silicon and the oxygen
Parameter proposed by the invention selects main demand following: 1. its refraction parameter n>=1.45; 2. transmission region is 400-800nm fully; Thermal expansivity
4. preserve the bonding elastic temperature province be-40 ℃ to 120 ℃; And 5. photodiode optical stability of under long-time situation, having standard.
The advantage that photodiode proposed by the invention exists is the luminescence converter of self, and it is characterized in that: for polymkeric substance and the weight ratio of fluorescent powder grain in luminescence converter is 8～75%.
In our process of the test, also found a characteristic for photodiode proposed by the invention, the thickness on its luminescent conversion layer top layer is formed by 80～200 microns, and bad warm white radiation does not appear in luminescent conversion layer.
Following luminescence technology parameter is by obtaining in the warm white light light-emitting diode (LED) proposed by the invention, and is still as shown in table 2.
Table 2
| № | The voltage V that produces | Electric current mA through heterojunction | Colour temperature K | The optical throughput lumen | |
2 θ ° angle | Drill colour system and count |
| 1 | 3.61 | 350 | 2780 | 54.9 | 16.80 | 30 | 80 |
| 2 | 3.60 | 350 | 2760 | 56.2 | 17.05 | 30 | 81.5 |
| 3 | 3.62 | 350 | 2754 | 56.0 | 15.90 | 30 | 82 |
Its electric power is 1 watt a photodiode, luminous efficiency η >=50 lumens/watt.< 2800K did not disclose before for so low colour temperature T.
In sum, halogenide fluorescent powder of the present invention has the fluorescent material formula of special orange red radioluminescence.In addition, halogenide fluorescent powder of the present invention, it adopts large batch of production, need draft reliable regulations for technical operation, and halogenide fluorescent powder of the present invention can improve its effective quantum efficiency and luminosity, therefore, really can improve the shortcoming of known fluorescent material.
Though the present invention discloses as above with preferred embodiment; But it is not that any those skilled in the art are not breaking away from the spirit and scope of the present invention in order to qualification the present invention; A little change of Ying Kezuo and improvement, so protection scope of the present invention should be as the criterion with the accompanying Claim scope.
Claims (14)
1. a halogenide fluorescent powder is used for warm white light light-emitting diode (LED), and it is to be the low colour temperature halogen Nitride phosphor on the basis with the rare earth oxide garnet, adopts cerium as activator, is characterised in that: in this fluorescent material component, add cl ions Cl
-1, nitrogen ion N
-3, the stoichiometric equation of its composition is:
(∑Ln
+3)
3Al
2[Al(O
1-2pCl
pN
p)
4]
3，
0.001≤p≤0.2 wherein, ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or Dy and/or Pr and/or Ce, and 0.001≤(Y/ ∑ Ln)≤0.5; 0.5≤(Gd/ ∑ Ln)≤0.95; 0≤(Tb/ ∑ Ln)≤0.1,0≤(Lu/ ∑ Ln)≤0.05,0≤(Dy/ ∑ Ln)≤0.05; 0.0001≤(Pr/ ∑ Ln)≤0.01,0.01≤(Ce/ ∑ Ln)≤0.1.
2. like 1 described halogenide fluorescent powder of claim the, wherein main lattice parameter a >=12.01A, and increase along with the increase of chemical index in the formula " p ".
3. like 1 described halogenide fluorescent powder of claim the, its spectrum greatest irradiation is λ=580 ± 3nm, and wavelength can be toward long wavelength shifted when increasing the chemical parameters " p " in the stoichiometric equation.
4. like 1 described halogenide fluorescent powder of claim the, wherein when increasing the chemical index " p " of fluorescent material, the wide meeting of spectrum half-wave becomes greatly λ
0.5=126+6nm.
5. like 1 described halogenide fluorescent powder of claim the, wherein when the chemical index " p " in the increase fluorescent material matrix, the radiation chromaticity coordinates increases to ∑ (x+y)＞0.88.
6. like 1 described halogenide fluorescent powder of claim the, wherein in the matrix of this fluorescent material under the increase of chemical parameters " p " quantum output increase to ζ=0.96 from ζ=0.92.
7. like 1 described halogenide fluorescent powder of claim the, wherein the particle of this fluorescent material becomes the prismatic shape, and the neutrality line diameter of this fluorescent powder grain is d
50≤4.0 microns, d
90≤16 microns.
8. warm white light light-emitting diode (LED); It is to become matrix and have the structure of a luminescent conversion layer with the InGaN heterogeneous semiconductor; It is characterized in that: said luminescent conversion layer is through forming halogenide fluorescent powder according to claim 1 and polymer phase blended mode; This luminescent conversion layer is distributed in the light-emitting area and the side of this InGaN heterojunction semiconductor with the uniform form of thickness, directly contacts with faceted pebble with the plane of this InGaN heterojunction semiconductor.
9. like 8 described warm white light light-emitting diode (LED)s of claim the, wherein the interior fluorescent powder grain weight ratio of this luminescent conversion layer is from 8～75%.
10. like 8 described warm white light light-emitting diode (LED)s of claim the, wherein the thickness of the surface of this luminescent conversion layer and side is formed by 80～200 microns.
11. like 8 described warm white light light-emitting diode (LED)s of claim the, wherein this InGaN heterojunction semiconductor has first step heterojunction blue ray radiation.
12. like 8 described warm white light light-emitting diode (LED)s of claim the, wherein this radiation chromaticity coordinates is 2500K＜T≤4500K, drills colour index Ra＞80 units.
13. like 8 described warm white light light-emitting diode (LED)s of claim the, the light intensity radiation during wherein for ° angle, 2 θ=30 be 1＞15cd. under the exciting of 1W electric power, irradiation luminous flux is F＞55 lumens, light efficiency is η >=50 lumens/watt.
14. like 8 described warm white light light-emitting diode (LED)s of claim the, wherein according to made optical throughput F＞185 lumens of incandescent light on 3W power of this warm white light light-emitting diode (LED).
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