CN101475804B - Orthosilicate green phosphor for light emitting diode and preparation thereof - Google Patents
Orthosilicate green phosphor for light emitting diode and preparation thereof Download PDFInfo
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- CN101475804B CN101475804B CN 200810180160 CN200810180160A CN101475804B CN 101475804 B CN101475804 B CN 101475804B CN 200810180160 CN200810180160 CN 200810180160 CN 200810180160 A CN200810180160 A CN 200810180160A CN 101475804 B CN101475804 B CN 101475804B
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Abstract
The invention relates to the field of radiation materials, in particular to orthosilicate fluorescent powder. Part of O<-2> in a silanoxide tetrahedron is replaced, the orthosilicate fluorescent powder has a P2nn crystal structure and gives off green radiation under the strong shortwave radiation excitation of InGaN heterojunction, wherein the maximum spectrum depends on the interrelation between the amount of Me<+2> or Ln<+2, 3> in a cation crystal lattice, and the intensity is determined by the amount of the atom O<-2> in the component which is replaced in the V, the VI and the VII families and is taken from the series of F, Cl, Br, I, S, Se, N and P. The orthosilicate fluorescent powder has two excitation wave zones of which the range is between 360 and 400 nanometers and between 450 and 490 nanometers, and the materials are used for establishing a bright and effective green LED by using a nitride heterojunction as a substrate.
Description
Technical field
System of the present invention is relevant with the radiative material field, particularly, creates the heterogeneous semiconductor that is derived from InGaN and becomes the basis, and English is referred to as " solid state light emitter " (Solid State Light) or semiconductor lighting technology.
Background technology
This solid state light emitter or semiconductor lighting technology last decade are developed rapidly, and the advantage of this semiconductor light source be adopt brighter more effective luminous, this kind foundation contains the researcher S.Nakanura (S.Nakamura Blue Laser.Springer Verlag, Berlin1997) that the heterogeneous originator who becomes the novel structure light source of a large amount of quantum well InGaN is Japan.
Be arranged in the inorganic fluorescent powder that is derived from the yellow spectrum zone and the polymer phase that the blue spectrum zone of heterojunction InGaN radiation forms and connect, form the strong white light radiation of different tones in conjunction with the heterojunction blue ray radiation.
Can make the white light emitting diode that similarly has green emitting, but adopt the heterojunction semiconductor with ultraviolet radiation and green emitting inorganic fluorescent powder here.The United States Patent (USP) that the of this sort equipment that combines with green emitting is had this case contriver discloses in the US 2007/0267967A case once to be described.This instrument have evenly and very bright Green-Emission luminous, therefore such invention system belongs to green industry illumination system now.
Green-Emission luminescent phosphor quantity is very huge, and all various material types can be divided into two large classes:
-semiconductor fluorescence powder; And
-special fluorescent material.
The first kind mainly is to be combined with II AVIB (ZnS and CdS) by semi-conductor, and it is the active ions of volume not, for example Cu, Ag and Au.Change semi-conductive synthetic composition, for example sosoloid ZnS-CdS can arrange the luminous parameters of fluorescent material, spectral radiance, chromaticity coordinates, and persistence.
The main luminous parameters of special fluorescent material is:
The luminous position of-maximum spectrum;
The quantity of-radiation belt; And
-persistence.
When inorganic fluorescent powder interpolation active ions, different active ions have different luminous intensities and different greatest irradiation spectrum, and the particle diameter of fluorescent material and temperature effect are to light-emitting phosphor stability.For example be derived from semiconductor light emitting component ZnS:CuAl (green emitting) and ZnS:AgAl (blue-light-emitting) in the CRT electron tube technology, and the special fluorescent material Y described in the U.S. US 2007/0267967A number open case that is had this case contriver
2O
2S:Eu.
Describe special green light-emitting fluorescent powder in the open case of aforementioned United States Patent (USP), this case contriver once inquired into the relevant data document of knowing, for example description of special fluorescent material like the related genera in the document of W.YEN, and it is to highlight silicate synthesis type Ba
2SiO
4: Eu and SrAl
2O
4: Eu had announced in W.YENNeorganic Phosphors.CPS Press 2004 already.Be similar in this case contriver's the invention and be used.Although in the document of W.YEN, announce the green emitting phosphor of different quantities type, but still exist deficiency:
-special green emitting phosphor excitation wavelength mainly is the UV-light near wavelength 365nm.
In addition, must be pointed out that in the present stage level, UV-light nitride chip can not effectively use because of inefficiency.Aforementioned U.S. US 2007/0267967A number the luminous halogenide silicate fluorescent powder of mentioned different colours in the case is disclosed for example.
Recently the Novel silicate Huang-green emitting phosphor of essence in new invention comes from the disclosed U.S. US 2008/0116786A1 Patent Case on May 22nd, 2008.The overall formula A of relevant fluorescent material in this patent application case
2SiO
4: Eu
+ 2D wherein comes from the metal compound valency A and has at least one to select from Sr, Ca, and Ba, Mg, Zn and Gd, and D-replenishes and adds element and come from F, Cl, Br, I, P, S, N and B.
The contriver of this patent application case is [(Sr at the whole composition of describing the fluorescent material chemical formula
0.7Ba
0.3)
0.98Eu
0.02]
2SiO
3.9F
0.2, the radiation scope that has under the InGaN heterojunction is blue-light excited is λ=540nm.Fluorescent material [(Sr
0.9Ba
0.05Mg
0.05)
0.98Eu
0.02]
2SiO
3.9F
0.2Maximum luminous radiation range lambda=560nm.Although the element in broadness has entered in the mentioned fluorescent material, definite pointing out only is at F
-1Ion, Cl
-1The impact of ion on luminescent material.
The contriver of this patent application case mentioned green emitting phosphor in this patent has equally in the low deficiency of blue-light excited lower luminosity-account for 15% of all brightness, with the YAG:Ce (Y that knows
3Al
5O
12: be that main fluorescent material is compared Ce), Yellow luminous component is lower than 20%.
Summary of the invention
Main purpose of the present invention provides a kind of orthosilicate green phosphor for light emitting diode and method for making thereof, and it is the brightness of the special green silicate fluorescent powder of raising under the exciting of heterojunction blue light; Secondary objective is to be provided in to improve under the ultraviolet excitation usefulness of fluorescent material; And another purpose is to provide the mentioned luminescent material establishment of employing to have green, glaucous photodiode.
For reaching aforementioned purpose, it is the green emitting orthosilicate fluorescent material of matrix in conjunction with II family element that the technique means that this case is taked provides a kind of silicate, its be with europium as activator, wherein in described material, add to introduce composition, formed chemometric equation is shown below:
(∑Me
+2∑Ln
+2)
8-xSi
+4 4-x(∑Ln
+3∑Me
+3)
2x(O
1-y∑A
-1 p∑A
-2 q∑A
-3 r)
16
Wherein
∑ Me
+ 2=Ba
+ 2And/or Sr
+ 2And/or Ca
+ 2And/or Mg
+ 2And/or Zn
+ 2,
∑ Ln
+ 2=Eu
+ 2And/or Sm
+ 2And/or Yb
+ 2, replace part Me
+ 2,
∑ Ln
+ 3=Y
+ 3And/or Eu
+ 3And/or Gd
+ 3And/or Sm
+ 3And/or Tb
+ 3And/or La
+ 3And/or Nd
+ 3And/or Pr
+ 3And/or Ce
+ 3, replace part Si
+ 4And Me
+ 2Ion,
∑ Me
+ 3=Al
+ 3And/or Ga
+ 3And/or B
+ 3, replace part Si
+ 4And Me
+ 2Ion,
∑ A
-1=F
-1And/or Cl
-1And/or Br
-1And/or I
-1,
∑ A
-2=S
-2And/or Se
-2,
∑ A
-3=N
-3And/or P
-3,
y＝p/2+q+3r/2
Replace the O of part in silicon-oxygen tetrahedron
-2, having orthorhombic crystalline structure P2nn and under strong InGaN heterojunction short-wave radiation excites, discharge Green-Emission for described orthosilicate fluorescent material, its maximum spectrum depends on Me in the positively charged ion lattice
+ 2And Ln
+ 2.+3Mutual relationship between quantity, and at V, VI replaces O in the VII family
-2Quantity, come from F, Cl, Br, I, S, Se, N, P series.
Description of drawings
Fig. 1 a is that fluorescent material composition 1 is at excitation wavelength lambda=395nm in the table 1, and Fig. 1 b is the spectrogram of excitation wavelength lambda=464nm.
Fig. 2 a is that fluorescent material composition 2 is at excitation wavelength lambda=395nm in the table 1, and Fig. 2 b is the spectrogram of excitation wavelength lambda=464nm.
Fig. 3 a is that fluorescent material composition 3 is at excitation wavelength lambda=395nm in the table 1, and Fig. 3 b is the spectrogram of excitation wavelength lambda=464nm.
Fig. 4 a is that fluorescent material composition 4 is at excitation wavelength lambda=395nm in the table 1, and Fig. 4 b is the spectrogram of excitation wavelength lambda=464nm.
Fig. 5 is that the data of the present invention's fluorescent material are to have taken the special radiation synoptic diagram that has in E=45 kiloelectron-volt of the negative electrode quantity of radiant energy that has in specialty by an X-ray photographs.
Embodiment
The novel orthosilicate of mentioned employing is provided is that matrix combines with II family and the III family recycle system being positioned at, with Eu
+ 2As activator, wherein for the composition of indication Material Addition, formed chemometric equation is shown below:
(∑Me
+2∑Ln
+2)
8-xSi
+4 4-x(∑Ln
+3∑Me
+3)
2x(O
1-y∑A
-1 p∑A
-2 q∑A
-3 r)
16
Wherein
∑ Me
+ 2=Ba
+ 2And/or Sr
+ 2And/or Ca
+ 2And/or Mg
+ 2And/or Zn
+ 2,
∑ Ln
+ 2=Eu
+ 2And/or Sm
+ 2And/or Yb
+ 2, replace part Me
+ 2,
∑ Ln
+ 3=Y
+ 3And/or Eu
+ 3And/or Gd
+ 3And/or Sm
+ 3And/or Tb
+ 3And/or La
+ 3And/or Nd
+ 3And/or Pr
+ 3And/or Ce
+ 3, replace part Si
+ 4And Me
+ 2Ion,
∑ Me
+ 3=Al
+ 3And/or Ga
+ 3And/or B
+ 3, replace part Si
+ 4And Me
+ 2Ion,
∑ A
-1=F
-1And/or Cl
-1And/or Br
-1And/or I
-1,
∑ A
-2=S
-2And/or Se
-2,
∑ A=N
-3And/or P
-3,
y＝p/2+q+3r/2
Replace the O of part in silicon oxide
-2, exciting and discharge Green-Emission and the organosilicate of indication has rhomboidal crystal P2nn structure and strong short-wave radiation heterojunction InGaN, its spectrum maximum value depends on and Me in the positively charged ion lattice
+ 2And Ln
+ 2.+3Relevant ratio, take from V, VI, the F of VII family element, Cl, Br, I, S, Se, N, P.
Hereinafter will explain physics-chemical fundamentals that the present invention has proposed the patent solution.The first, mentioned orthosilicate fluorescent material has (∑ Me)
8Si
4O
16Form.Shown in the corresponding like this record system foundation Japanese Patent Publication P2008-24933A Patent Case on July 21st, 2006, the orthosilicate chemical structure that gears to actual circumstances.The second, in structure of the present invention, must mark the structure of matter of dividing two kinds of structures:
-have in the positively charged ion lattice Ln that replaces barium ion and strontium ion
+ 2.3Ion;
-at silicon oxide (SiO
4) replacement Si is arranged in the tetrahedron
+ 4Perhaps oxygen forms round silicon element on every side.
Another innovation then is, is located at the replacement of element in the positively charged ion lattice, main is its+divalent ion Ba
+ 2, part can be used Sr
+ 2And/or Ca
+ 2And/or Mg
+ 2And/or Zn
+ 2Replace.Equally have similar same valency and replace Ba
+ 2Ion, for example Eu
+ 2And/or Sm
+ 2And/or Yb
+ 2, this kind replacement does not need charge compensation.In addition, also (+3) rare earth ion of available different degree of oxidation is replaced Ba
+ 2, Y for example
+ 3And/or Eu
+ 3And/or Gd
+ 3And/or Sm
+ 3And/or Tb
+ 3And/or La
+ 3And/or Nd
+ 3And/or Pr
+ 3And/or Ce
+ 3Ions etc., the different valence state of this kind is replaced and is needed charge compensation, must introduce a charge compensation in lattice.
In the lattice of negatively charged ion, also have with valency and replace the phenomenon of replacing with different valency, for example use-the ion S of divalent
-2And/or Se
-2Replace O
-2The same valency of oxonium ion is replaced, and this kind replacement does not need charge compensation.Different valency is replaced then two kinds of phenomenons, and a kind of is the halide-ions F that uses-1 valency
-1And/or Cl
-1And/or Br
-1And/or I
-1Replace O
-2Oxonium ion, the different valence state of this kind is replaced and is needed charge compensation, must introduce a charge compensation in lattice; Another kind is with-3 valency ion N
-3And/or P
-3Replace O
-2Oxonium ion, the different valence state of this kind are replaced and can be produced a unbound electron, and this unbound electron just can be transferred to the place that needs charge compensation.
In addition, in the positively charged ion lattice+4 valency ion Si
+ 4Can be replaced by different valency, can be by+3 valence metal ion Al
+ 3And/or Ga
+ 3And/or B
+ 3And+3 valency rare earth element ies
+ 3And/or Eu
+ 3And/or Gd
+ 3And/or Sm
+ 2And/or Tb
+ 3And/or La
+ 3And/or Nd
+ 3And/or Pr
+ 3And/or Ce
+ 3Replace, the different valence state of this kind is replaced and can be produced a unbound electron, and this unbound electron just can be transferred to the place that needs charge compensation.
As mentioned above, for part Ba
+ 2Ion is by III family lanthanon such as Eu
+ 2And/or Sm
+ 2And/or Yb
+ 2When replacing with valency, these+the divalent rare earth ion is active ions, its inner electronic switch is 5d-4f
7
When rare earth element carried out different valency replacement with+3 valencys, except the needs charge compensation, its proper concn was 1～3% atomic fraction.
In addition, by the ion A l of IIIA family
+ 3And/or Ga
+ 3And/or B
+ 3Replace ion Si
+ 4, especially use B
+ 3Replace Si
+ 4, be very rare in the composition of fluorescent material, using.
Usually we can use boric acid H
3BO
3Obtain B
+ 3, in order to replace ion Si
+ 4, but this material can make it become the hardenability material for glass products, also can use NH in addition
4BF
4Obtain B
+ 3, but must just can finish at suitable pressures; We can Material Used AlF in addition
3Obtain Al
+ 3, in order to replace ion Si
+ 4We can also Material Used Ga
2O
3Obtain Ga
+ 3, in order to replace ion Si
+ 4
Replacing silicon oxide (SiO
4) during oxygen composition in the tetrahedron, can use easily the little F of ionic radius difference
-1Ion is replaced the O of part
-2Ion (τ
o=1.40A τ
F=1.32A).
But the ion Cl of heavy ion radius
-1(τ
Cl=1.8A), be to enter silicon oxide (SiO not having under the special situation
4) replace the oxygen composition in the tetrahedron, but the contriver has found suitable condition (temperature, vapor pressure, and halogenide), such reaction can be realized in industrial production.
Heavy ion radius Br more
+ 1(τ
Br=1.98A) and I
-1(τ
I=2.20A) application does not appear in the aforementioned U.S. US 2008/0116786A1 patent disclosure case; But now the contriver can use such replacement, that is adopts fine grain how meter level SiO in original reagent
2, the optimal S ≈ 100m that is of a size of in its surface
2/ gram), because have very high activity at the Surface Oxygen ion of this reagent, so these halide-ionss will enter in the lattice and only to need 1/2～1/3 times energy to get final product, and can get the chemical formula that replaces shown in following:
SiO
2+2HBr→H
2O+SiOBr
2
Secondly decompose:
SiO
2+2HI→H
2O+SiOI
2
At this hereinafter, will be set forth with concrete spectrogram in the table 1, oxide compound for example is for all F
-1, Cl
-1, Br
-1And I
-1Halid replacement.
For using ion S
-2And/or Se
-2Get for oxonium ion O
-2, should avoid using poisonous or explosive reagent class, for example H
2S and H
2Se etc., and adopt organic sulfide or selenide product; If quote ion F
-1Get for oxonium ion O
-2, the absorption that is accompanied by the fluorescent material radiation excitation increases, but introduces S
-2Reach particularly Se
-2What change in essence is not only the absorption of fluorescent powder grain, changes simultaneously hydrolysis intensity.Therefore, such material is not suitable for among the experiment.
The orthosilicate fluorescent material that the contriver is mentioned, it is luminous to have very strong blue-greenish colour under the InGaN of wavelength X=410～490nm heterojunction blue light short-wave radiation excites, and it is near UV-light zone (UVA or UVB) that such short-wave radiation excites.Traditional organosilicate Zn
2SiO
4: the main excitation area of Mn is at λ
3=254nm and λ
2=173nm (VUA field).Oxyhydroxide Y
2SiO
5: the main excitation area of Ce is at λ=330-360nm, but only is this banded exciting.
The advantage of above-mentioned fluorescent material is included in two excitation bands, and this point of novel photodiode is extremely important when setting up, shown in it is reported as follows.Important advantage is to be characterised in that at mentioned orthosilicate fluorescent material, for the concentration composition group in positively charged ion lattice II family:
0.3≤Ba
+2/∑Me
+2≤0.99， 0.01≤Sr
+2/∑Me
+2≤0.6，
0.01≤Ca
+2/∑Me
+2≤0.05，0.001≤Mg
+2/∑Me
+2≤0.05，
0.001≤Zn
+2/∑Me
+2≤0.05，
In addition, the composition component that all is had degree of oxidation+2: ∑ Me
+ 2+ ∑ Ln
+ 2=1 atomic fraction.
Physics-chemical property according to the present invention in the patent.The divalent cation of at first, all II families and bivalent rare earth ion ∑ Ln
+ 2=Eu
+ 2And/or Sm
+ 2And/or Yb
+ 2Consisted of and self sosoloid between, the stretching, extension that homogeneity gets is for negatively charged ion Ba
+ 2And Sr
+ 2But the enough high (0.01≤Sr of solubility
+ 2/ ∑ Me
+ 2≤ 0.6), but Sr
+ 2Excessive concentration the time, crystalline network (molecular structure) can change and should not select.
Orthosilicate Ba, Ca, the mutual fusibleness of Mg does not become, according to contriver's understanding, at the composition (Ca-Mg) of orthosilicate
8Si
4O
16At Ba
4Sr
4Si
4O
16In can obtain evenly single product during less than 10% mole.Different because of ionic radius in II family element, also exist different solubleness, at ion size Ba
+ 2(T
Ba=1.16A), Sr
+ 2(T
Sr=1.08A), Ca
+ 2(T
Ca=1.02A), Mg
+ 2(T
Mg=0.7A), Zn
+ 2(τ
Zn=0.7A), find it only is for Ba
+ 2And Sr
+ 2Can be unlimited mutually molten, other element only can melt during less than 10% mole in scope.
As for europium ion Eu
+ 2(τ
Eu=1.26A) at barium ion Ba
+ 2In melting degree be difficult to expect, at concentration range [Eu
+ 2]≤10% atomic fraction, its melting should be feasible.Similar phenomenon is Sm on other two bivalent rare earth family elements
+ 2And Yb
+ 2, its melting degree should be less than 5% mole.More than these data conform to experiment, more than these of equal value replacements do not need charge compensation.In the positively charged ion lattice, the different valency of+3 valency rare earths ions is replaced, and the rare earth ion composition is restriction mutually, so its total melting degree should be less than 5% mole.
As for the application of halogenide element ion, can adopt ion F
-1, Cl
-1, Br
-1And I
-1, replace the oxonium ion in the silicon oxide composition.
The rare earths ion Ln that adopts in test
+ 3=Y
+ 3, La
+ 3, Gd
+ 3, Sm
+ 3, Tb
+ 3, Nd
+ 3, Ce
+ 3, Pr
+ 3, Eu
+ 3, the effect of these ions is also non-uniform.For example, ion Y
+ 3, La
+ 3, Gd
+ 3Form colourless silicate compound, in the fluorescent material of made, be inevitable for halid charge compensation, have+divalent Eu
+ 2Can be with the fluorescent material stained yellow.At this moment add the interaction of fluorescent material and the semi-conductor InGaN heterojunction blue ray radiation of made; In addition, ion Pr
+ 3, Ce
+ 3, Eu
+ 3, Nd
+ 3Also silicate fluorescent powder can be dyeed, in suitable concentration range (0.5-5%), make the fluorescent material of made promote luminous efficiency.
Also to point out two important empirical factors relevant for mentioned silicate.The first, with Ca
+ 2Introduce Ba
4Sr
3Ca
0,75Eu
0,25Si
2O
12In the silicate fluorescent powder.The second, with Mg
+ 2Introduce in the silicate fluorescent powder, although that it allows to melt concentration is limited, will limit the growth of fluorescent powder grain, for example during concentration to 1% mole, fluorescent powder grain mean sizes d
Cp≤ 20 microns, do not introducing Mg
+ 2The time particle mean size may exceed d
Cp30 microns.
Mentioned orthosilicate fluorescent material is characterized in that, for from rare earth element ∑ Ln
+ 3And+3 valency metallic element ∑ Me
+ 3Composition add, its chemical index x is:
0.0001≤x≤0.5
The present invention formula only points out that Eu ion composition can be positioned at two degree of oxidations, does not exceed 4% of usual atom.
Higher composition [Eu
+ 2.+3] the extinguishing of the light-emitting phosphor brightness that causes of 0.04 concentration, the simultaneously [Eu in composition
+ 2.+3The substantial reduction of]＜0.01% luminosity of drawing.
Point out that in addition two have degree of oxidation+important effect of 2 rare earth elements and are: the firstth, Sm
+ 2, its concrete effect is to make the short-and-medium wavestrip of orthosilicate fluorescent material composition be excited to λ=415-420nm, it is extremely important that this has a photodiode that contains UV-light and green exciting light for foundation.The secondth, Yb
+ 2, it can promote yellow sub-band wavelength brightness in the fluorescent material component.
The present invention pointed out once that mentioned special fluorescent material was positioned at and adds ion composition Sm
+ 2, Yb
+ 2In its concentration be:
0.0001≤Sm
+2≤0.01，0.0001≤Yb
+2≤0.01，
The patent of institute of the present invention submit applications is in conjunction with following experimental data:
Fig. 1 a is that fluorescent material composition 1 is at excitation wavelength lambda=395nm in the table 1, and Fig. 1 b is the spectrogram of excitation wavelength lambda=464nm;
Fig. 2 a is that fluorescent material composition 2 is at excitation wavelength lambda=395nm in the table 1, and Fig. 2 b is the spectrogram of excitation wavelength lambda=464nm;
Fig. 3 a is that fluorescent material composition 3 is at excitation wavelength lambda=395nm in the table 1, and Fig. 3 b is the spectrogram of excitation wavelength lambda=464nm; And
Fig. 4 a is that fluorescent material composition 4 is at excitation wavelength lambda=395nm in the table 1, and Fig. 4 b is the spectrogram of excitation wavelength lambda=464nm.
The material that the present invention's experiment is obtained, its measure spectrum is when wavelength is λ=395nm and λ=464nm, the spectral radiance analyser of employing Zhejiang Province, China university's three looks (Sensing) Instr Ltd. is measured, the spacing of scanning optical spectrum is 5nm, and the measurement wavelength is λ=380nm to λ=800nm.
Obtained spectral absorption, in the parameter result who obtains:
-be positioned at greatest irradiation spectrum and half-wavelength at Nano grade;
The radiation of-chromaticity coordinates is on system xyz (MKO1931) and uvw (1965);
-luminosity energy;
-radiation wavelength advantage;
-chromaticity coordinates Ra;
The radiation colour temperature T.K. of-fluorescent material
-radiation colour purity α.
It must be noted that, all do not propose in previous any one piece of patent documentation in the parameter of dense like this optics quantity and silicate.
The data that are the present invention's fluorescent material in Fig. 5 are to have taken the special radiation that has in E=45 kiloelectron-volt of the negative electrode quantity of radiant energy that has in specialty by an X-ray photographs.Describedly exist double-colored mark, the below will be marked, and it must be noted that the crystalline network system for the present invention's fluorescent material belongs to the morphological structure of orthosilicate and approaches the mineral substance structure (Ca, Ba, Mg, Mn) of describing
2SiO
4
For the fluorescent material of relevant silicate pointed in the document of knowing, the academic paper of aforementioned W.Yen for example.For necessary excitation energy E ≈ 2.8-3 ev, its stimulated luminescence is in the ultraviolet radiation field, and therefore, similar material is of value to the short wave ultraviolet light heterojunction for the first time.
At traditional orthosilicate fluorescent material Me
2SiO
4: Eu or Me
8Si
4O
16: must introduce the method for making of specialty among the Eu, can be by shortwave blue-light excited and in long emission wavelength.All once expressions in a large amount of orthosilicate fluorescent material patents are by introducing mixture halide-ions F in the composition of fluorescent material
-1, Cl
-1, Br
-1, and phosphorus P
-3, fluorescent material is changed have the excited blue-green wavelength, for example the United States Patent (USP) on March 20th, 2008 discloses No. 2008/0667920 Patent Case of US.
Add halide-ions in fluorescent material, raw material can use hydrogen halide, HF for example, HCl, HBr, HI etc., or halogenation ammonia, for example NH
4F, NH
4Cl, NH
4Br, NH
4I etc., or more complicated compound, for example NH
4BF
4, can introduce simultaneously B
+ 3Come the ion Si in the different valency replacement fluorescent material
+ 4
In the process of invention, find, for ion O
-2Same valency replace ion S
-2And/or Se
-2The best material of introducing is (NH
4)
2C=S and/or (NH
4)
2C=Se, these materials not only can be with ion S
-2And/or Se
-2Introduce, also can be with ion N
-3As ion O
-2Different valency replace.
Within preamble is mentioned, hold, in the anion lattice of fluorescent material, introduce the halogen ion ∑ A that replaces the oxonium ion in the silicon tetrahedron
-1=F
-1And/or Cl
-1And/or Br
-1And/or I
-1, its preferred concentration is 0.001≤∑ A
-1≤ 0.15 atomic fraction.
When furnace temperature rose to 900～1400 ℃, the hydrogen halide in the gas will decompose and the halogen ion is discharged, and then entered in the phosphor material powder in synthetic.
Describing for the measuring result of special fluorescent material spectrogram is that professional surveying instrument from three look Instr Ltd. of Zhejiang Province, China university records.
During from T=1100-1350 ℃, the data procedures of contriver's gained needs 2-10 hour in temperature range, needs cost τ=1 hour promoting 10% for luminous intensity.The contriver in operating process at sosoloid Ba
2SiO
4-Sr
2SiO
4-Ca
2SiO
4Middle use method for sensitizing, luminous intensity is compared with master pattern, exceed 1.3, sensitization for fluorine is approximately 1.24～1.26, its halid proportion, this case contriver is also careful, is having longer short-wave long light-emitting (parameter value " x " less than 0.27) for the sample of fluoride ion sensibilized with the sample of fluorescent material in relatively.Ion Cl
-1(λ=525-528nm), ion Br
-1(λ=526-529nm) or ion I
-1(λ=527-530nm).This wavelength shift is written among the patent of the present invention first.Therefore, mentioned fluorescent material obviously has two and can control maximum spectrum:
--change the mutual ratios between [Ba]/[Sr]; And
--the ion of replacement has the wavelength region displacement from F
-1＜Cl
-1＜B
-1＜I
-1
So accurate concentration was not all carried in the disclosed correlation technique document of this case contriver from the radiation composition of orthosilicate spectrum.
In fluorescent material of the present invention, such advantage can clearly be presented in the radiation spectrum component, it is characterized in that, introduces being derived from Se for the component that adds
-2The sulfide ion of series is replaced the oxonium ion in the anion lattice in the silicon tetrahedron, and its concentration is [S
-2] 4 milligrams/to restrain be main fluorescent material.
Embodiment:
At first, the valence state that explicitly points out sulfonium ion is-2.The contriver is for the affirmation of introducing the sulfonium ion minimum concentration, and the concentration component is 4 milligrams/gram, and it changes the luminescent spectrum wavelength and luminosity has reduced 2-4%.
For Se
-2The quoting of ion needs for a long time processing (from 10-20 hour), institute to follow and makes Eu
+ 2The radiation wavelength displacement.
Introducing ion S
-2And/or Se
-2, can change active ions Eu
+ 2Characteristic, Eu originally
+ 2Standard time of persistence is τ
eHow second=160, with S
-2In the composition of introducing orthosilicate fluorescent material (to 0.002 atomic fraction), follow and reduce to τ time of persistence
eHow second=135.Be similar to such reduction, be used under photodiode (LED) high current loads, reducing the fluorescent material usage quantity.The change of fluorescent material numerical value advantage of the present invention in its composition is characterised in that, adds in anion lattice and introduces N
-3Ion and P
-3Ion contains-3 degree of oxidation, replaces oxonium ion in the silicon tetrahedron.
The second, import sensitizer ion N
-3Significant in the brightness of fluorescent material, surpass the F that is disclosed before the contriver
-10The data of ion.Main sensitized material discloses in the US 2008/0116786A1 case at United States Patent (USP) and describes to some extent.Therefore, add 2-4 milligram nitrogen/gram according to contriver's data presentation, yield of radiation increases to 14～16%, simultaneously the substantial maximum spectral radiance displacement=3-5nm that has widened fluorescent material.The contriver is the sensitization nitrogen ion N of fluorescent material in test
-3Interpolation, make that its usefulness is the highest to promote 45～55%, in any patent documentation now all less than relevant description.Introduce P
-3Ion produces more complicated, with N
-3Compare, needed more detailed radiation, but the spectrum of fluorescent material and brightness have obvious improvement.
The contriver has determined to have added the composition that comes from V or VII family among the lumen equivalent value Q of orthosilicate fluorescent material.If for equaling from 224 to 289 lumens/watt radiation without the fluorescent material Q value of adding, have introducing halogenide (F
-1, Cl
-1, Br
-1) ion and special N
-3, numerical value Q is near ≈ 500 lumens/watt, N.P.Soshchin ef and Phys ef Tech Semicon for example, and 2007 V, 41 No 9, shown in the 1143-1149, this very important records of values is in contriver's document.
Must compare the fluorescent material composition (Y, Gd, Ce) for standard
3Al
5O
12, wherein the Q=320-390 lumens/watt contains F for the orthosilicate fluorescent material that proposes, Cl, and Br, N etc., under identical power parameter InGaN nitride heterojunction, the efficient of its photodiode is 20-25%.
This result has shown that orthosilicate fluorescent material quality of the present invention is very high, it is characterized in that, for add the B that quotes in anion lattice
+ 3, Al
+ 3, Ga
+ 3The series ion is replaced part Si
+ 4Ion has Al in tetrahedron fluorescent material radiation displacement aspect the long wavelength
+ 3And Ga
+ 3Ion or aspect shortwave, B is arranged
+ 3Ion is quoted wavelength B in the spectral results in anion lattice
+ 3, Al
+ 3And Ga
+ 3At first change spectrum directions different in the lattice.
Ion B
+ 3(τ=0.22A) quotes the light emitting region that reduce lattice, obviously can increase brightness and shortwave displacement.
On the other hand, in lattice, introduce oarse-grained ion A l
+ 3(τ=0.62A) and Ga
+ 3(τ=0.86A) lattice parameter increases, and at this moment the stress field of intracell should reduce, and incident effective luminous energy reduces.Maximum emission wavelength displacement, thus luminous efficiency is increased.Therefore, the viewer finds not lose for brightness, but special spectrum is being introduced B
+ 3The time, chromaticity coordinates is changed into Δ x=-0.015 Δ y=-0.02, greatest irradiation spectrum has some atrophys, Δ λ=-2nm.
It is very important that such radiation spectrum changes for fluorescent material of the present invention, and general recommendations is used for traffic lights, traffic lights, and on the erecting device of semaphore.The control restriction that the color tool of these devices is very strict.
Then describe about in negatively charged ion and cationic lattice, noted before as the contriver on special fluorescent material spectrum, embodying simultaneously in the scope of non-equivalence with halid replacement of different valence state only is F
-1Ion has ionic radius less than the O that replaces
-2Ion.Al
+ 3With Ga
+ 3Ion is equally greater than Si
+ 4, B
+ 3Ion.Be similar to the ion that in different sizes, replaces like this and be in the composition of the synthetizing phosphor powder of indication.Orthosilicate fluorescent material has d under the condition of standard synthetizing phosphor powder particle
50≤ 16 microns, d
90≈ 25-30 micron.Shown in the present invention the contriver and to have pointed out to reduce to d for numerical value
50≤ 10-12 micron, d
90≤ 20 microns.
The granularity that is similar to fluorescent powder grain of the present invention can adopt and be not only manual manufacturing under luminescence converter, but the sign and mechanism in particularly importantly for the photodiode of obtaining the color parameter equilibrium.
Fluorescent material of the present invention is characterised in that its particle shape is ellipse, and the diameier size is 8 microns≤d
90≤ 12 microns.
The contriver finds that the granularity size finally depends on concentration of element main in the lattice, at such high concentration ion Br
-1, I
-1And N
-3Synthetic under probably divide few thin and mean value reduces.
The present invention obtains the method for making of high quality green silicate fluorescent powder, and is described as the 1st of claim, is characterised in that, the heat treatment in two pointed stages, its composition II, III, IV, V, VI, VII family, after this, be the heat treatment that is located in the oxygen in the fs, the Atmospheric composition of subordinate phase comes from 2NH
3→ 3H
2+ N
2Contain and add to introduce halogenide and/or chlorion component, in temperature T first
1=900-1300 ℃, the secondary temperature T
2=750-1200 ℃, whole process is 5-20 hour.
Illustrated and introduced fluorescent material of the present invention, at the generation of the quality reagent oxygen for utilize employing, calcium oxide, and/or the composition of chlorine.Second family series Mg, Ca, Sr, Ba, Zn.The series B of three races and/or Al and/or Ga and rare earth element are with SiO
2Mix, this reagent has top layer S〉50m
2/ gram.All chemical reagent fully mix in the crucible that is placed on 300 milliliters, crucible are put into begin above-mentioned heat treatment process after high temperature reaction stove is settled.
Cooled product carries out aftertreatment, adopts hydrochloric acid HCL (1:5) pickling after diluting.The surface of fluorescent material forms thin film layer ZnOSiO
2, thickness is δ=100nm.After this phosphor powder after the processing is carried out drying treatment, temperature is T=105 ℃, and the time length is 2 hours.And sieve by 600 purpose screen clothes, afterwards its gained is measured.
It is as follows now to enumerate one of fluorescent material embodiment and preparation method thereof:
Weigh first following raw material
BaCO
3:87.62g Eu
2O
3:2.82g
SrCO
3:44.29g SiO
2:24g
CaCO
3:40g
Put into the alumina crucible of 300ml after above raw material is fully mixed, crucible is put into stove, be warming up to 1280 ℃ with 5 ℃/minute heat-up rates and kept 2～4 hours, and then lower the temperature with 5 ℃/minute speed, add reducing gas ammonia NH this moment
3Protected, be cooled to 1050 ℃ and kept 3～6 hours, then naturally cooled to room temperature, take out product and be ground to Powdered.
Cooled product carries out aftertreatment, adopts hydrochloric acid HCL (1:5) pickling after diluting.The surface of fluorescent material forms thin film layer ZnOSiO
2, thickness is δ=100nm.After this phosphor powder after the processing is carried out drying treatment, temperature is T=105 ℃, and the time length is 2 hours.And sieve by 600 purpose screen clothes, afterwards its gained is measured.
The chemical formula of the fluorescent material that forms is Ba
4.44Sr
3.0Ca
0.4Eu
0.16Si
4O
16, its feature is shown in table 1 and Fig. 1 a and 1b.
4 parameter data of silicate fluorescent powder of the present invention in table 1, have been quoted.
Table 1
| No | The composition of fluorescent material | λ max，nm | λ 0.5nm | Luminosity L, |
| 1 | Ba 4.44Sr 3.0Ca 0.4Eu 0.16Si 4O 16 | 521.7 | 63.8 | 17957 |
| 2 | Ba 4.44Sr 3.0Ca 0.3Mg 0.1Eu 0.16Si 4O 15.25F 1Cl 0.5 | 525.6 | 65.4 | 23241 |
| 3 | Ba 4.27Sr 3.0Ca 0.4Mg 0.14Eu 0.16Si 3.97B 0.06O 15.94N 0.04 | 529.1 | 68.2 | 19212 |
| 4 | Ba 4.28Sr 3.0Ca 0.3Mg 0.24Eu 0.6Si 3.98B 0.04O 15.97P 0.02 | 531.3 | 72 | 20125 |
Below be the concise and to the point conclusion of relevant form 1:
In the invention process of preparation orthosilicate fluorescent material:
-sensitizing ion F
-1, Cl
-1, Br
-1, I
-1, S
-2, Se
-2, N
-3, P
-3Have concentration from 0.002 to 0.18 atomic fraction for the O that replaces in the silicon tetrahedron
-2Ion;
The composition B of-ion
+ 3, Al
+ 3, Ga
+ 3Replace the Si in the tetrahedron
+ 4Ion;
The position of-maximum spectrum changes from λ=531nm to λ=521nm;
-maximum spectrum half-wave is wide from λ
0,5=63.58nm to λ
0,5=72nm;
-radiation chromaticity coordinates value is from (x+y)=0.88 to (x+y)=0.93; And
-radiance is from L=17957 to L=23802 relative unit.
All synthetizing phosphor powders have the orthosilicate lattice parameter, and the change of its main fluorescent material lattice parameter is from [Ba]/[Sr].The meta particle size consist of d
50=5-9 micron, the feature of synthetizing phosphor powder are positioned on two excitation bands:
-have λ at the excitation band of UV-light
1=395nm; And
-have λ=464nm at the radiation excitation band of shortwave blue light;
Its most important advantage of fluorescent material of the present invention is, its composition as claimed in claim 1, can set up the luminous photodiode of shortwave take heterojunction semiconductor InGaN as matrix, the feature of radiative transition coating is, described luminescence converter is have same thickness fluorescent powder coated, overlay and heterojunction surface side, described polymkeric substance cladding thickness is from 80 to 200 microns.
Luminescence converter can contact a radiating surface, and for example, two heterojunction combine with electrode.
Important condition is positioned at the UV-light luminous that heterojunction greatest irradiation spectrum contains λ=395nm, is the shortwave blue light emitting secondly.Photodiode can have two heterojunction parameters, between electrode is connected, at two group position its stimulated luminescence (the photodiode Y of satisfactory stability that are located at shown in the patent of Nichia company in the photodiode
3AL
5O
12: it only is blue-light excited near the UV-light part that Ce (YAG) excites.
Similarly point out, be higher than δ=200 micron for luminescence converter thickness range of the present invention.Allow exciting light to extend to all converter range, such fluorescent powder grain sample simultaneously can be under UV-light and blue spectrum stimulated luminescence, can say for certain that incident is that diode usefulness is increased.
Photodiode of the present invention is characterised in that in essence the conversion composition organosilicon polymer parameter of this photodiode has:
-Si-O-Si-
The M=10000-20000 carbosilane unit, described orthosilicate fluorescent material composition tissue is described as the 1st of claim, and the mutual ratio between the polymerizable organosilicon amount from 8% to 38%.
According to known for inventor, the fluorescent powder grain the best in connecting polymkeric substance is 22～32%, the green emitting that can reach capacity, and high brightness radiation.
The structure of photodiode forms, and comes from two different heterojunction at it, it is characterized in that described photodiode is in the field of UV-light and blue-light excited yellow spectrum part, and its special maximum spectral value has λ
1=360～405nm, λ
2=410～490nm, λ
3520nm, the half-wave of radiation spectrum is wide, and to have greatest irradiation be 100nm, light intensity is 1〉20cd.Be 2 Θ=60 ° for half angle of release.And the W=1 watt-hour, surpass 50 lumens/watt at luminous power.
The application is disclosed, is a kind of of preferred embodiment, and the patent right category of this case is not all taken off in such as partial alteration or modification and come from the technological thought of this case and be easy to the person of knowing by inference by those skilled in the art.
Claims (5)
1. orthosilicate green emitting phosphor, its chemical formula are selected from any in the following chemical formula:
Ba
4.44Sr
3.0Ca
0.4Eu
0.16Si
4O
16；
Ba
4.44Sr
3.0Ca
0.3Mg
0.1Eu
0.16Si
4O
15.25F
1Cl
0.5；
Ba
4.27Sr
3.0Ca
0.4Mg
0.14Eu
0.16Si
3.97B
0.06O
15.94N
0.04With
Ba
4.28Sr
3.0Ca
0.3Mg
0.24Eu
0.6Si
3.98B
0.04O
15.97P
0.02。
One kind with heterojunction semiconductor InGaN as the luminous photodiode of the shortwave of matrix, it has orthosilicate green emitting phosphor as claimed in claim 1, it has realized polymer encapsulated with same thickness with luminescence converter, and the heterojunction package thickness of surface and side is at the 80-200 micron.
3. photodiode as claimed in claim 2, wherein this photodiode is in conjunction with the principle of luminescence converter-contain the light conversion composition that organosilicon polymer is sent out, and it consists of:
-Si-O-Si-
The M=10000-20000 carbosilane unit, in addition, this orthosilicate green emitting phosphor and the polymerizable organosilicon amount between mutual ratio from 8% to 38%.
4. photodiode as claimed in claim 2, wherein this photodiode is positioned at UV-light, and the photodiode of blue-greenish colour spectrum sub-band scope has three special spectrum, is respectively λ
1=360～405nm, λ
2=410～490nm and λ
3＞520nm, the wide Δ λ 〉=100nm of spectrum intense radiation half-wave, light intensity I＞10cd, 2 θ=60 ° and luminous efficiency η＞50 lumens/watt.
5. photodiode as claimed in claim 2, wherein this photodiode is to contain λ in two heterojunction semiconductors
1=360-405nm, λ
2=410-490nm, the luminescence converter of fluorescent material as claimed in claim 1, in addition, this fluorescent material surpasses 50 lumens/watt in the luminous efficiency that blue and green visible spectrum have.
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| US20080116786A1 (en) * | 2004-08-04 | 2008-05-22 | Intematix Corporation | Novel silicate-based yellow-green phosphors |
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