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CN101570688B - A red luminescent luminescent material and a luminescent device using the same - Google Patents

A red luminescent luminescent material and a luminescent device using the same Download PDF

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CN101570688B
CN101570688B CN 200810011201 CN200810011201A CN101570688B CN 101570688 B CN101570688 B CN 101570688B CN 200810011201 CN200810011201 CN 200810011201 CN 200810011201 A CN200810011201 A CN 200810011201A CN 101570688 B CN101570688 B CN 101570688B
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light
luminescent material
emitting
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luminescent
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CN101570688A (en
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王细凤
夏威
肖志国
辛易
温嘉琪
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Dalian Luminglight Co Ltd
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Dalian Luminglight Co Ltd
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Abstract

A red luminous material with the composition formula Ma+b(Al1-βAβ)γO1.5γ+aD2b: xEu. yMn. zLn.delta Lm, wherein M is one or the combination of more elements of Mg, Ca, Sr, Ba and Zn; a is Y, Gd one or two elements; d is one or the combination of two element ions of Cl and F; ln is the combination of one or more element ions of Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sn, Lu, Sb, Tb and Pb; lm is one or the combination of multiple element ions in Li, Na, K and Ag; a. b, beta, gamma, x, y, z and delta are molar coefficients. The composite aluminate luminescent material can be excited by an excitation light source from ultraviolet to green light and can be used as a light conversion material for manufacturing white-series and red-series luminescent devices comprising LEDs.

Description

A kind of luminescent material of emitting red light and the light-emitting device that uses it
Technical field
The present invention relates to a kind of luminescent material of emitting red light, be particularly related to for making and comprise the white light system of semiconductor light-emitting elements (LED) and the luminescent material that the red colour system light-emitting device is used, it can be used as the emmission spectrum of excitation light source in the ultraviolet of 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, belong to photoelectron and lighting technical field.
Background technology
Since 1996, occurred with blue led and YAG fluorescent material ((Y, Gd) 3Al 5O 12: Ce 3+) white light LEDs that combines, this lighting source is compared with luminescent lamp with traditional white flag lamp, have the advantages such as less energy-consumption, long lifetime, volume be little, lightweight, and can eliminate the problem of environmental pollution that the objectionable impuritiess such as mercury in luminescent lamp cause, more and more receive people's concern.
This technology is by updating, and development realizes that with luminescent material the mode of white light has two kinds so far, namely can realize white light LEDs by the method for purple light chip or blue chip excitation light-emitting material.But all there is certain limitation in these methods, colour rendering index (R a) lower, colour temperature is higher, can't realize warm white.Expect the white light LEDs of high-color rendering, low colour temperature, must add the red fluorescence powder of a kind of emission wavelength more than 590nm.Red fluorescence powder can be obtained widespread use seldom at present, all has the problem that luminous efficiency is not high or aging property is bad.The fluorescent material that has been found that at present has:
(1) sulfide rouge and powder: contaminate environment, aging decay is fast, luminous efficiency is low;
(2) molybdate rouge and powder: luminous efficiency is higher, but excitation and emission spectra is line spectrum, and is larger for the selectivity of LED chip;
(3) tungstate rouge and powder: luminous efficiency is higher, but excitation and emission spectra is line spectrum, and is larger for the selectivity of LED chip;
(4) nitrogenous compound rouge and powder: this rouge and powder is to stablize the most at present and luminous efficiency rouge and powder preferably, but complex manufacturing technology is only done cost higher, is unfavorable for promoting and producing on a large scale.
(5) aluminate rouge and powder: some relevant document or patent reports are arranged, and it is ripe that is that all right at present.
Luminescent material of the present invention is a kind of compound aluminate red luminescent material, and some document and patent that approaches has at present:
(1) document " Flouorescence properrities of Mn 4+In CaAl 12O 19Compounds asred-emmiting phosphor for white LED ", be published in " Journal of Lumingescence ", 114 (2005) 207-212.The main excitation wavelength of this material is positioned at 400nm, and main emission wavelength is positioned at 656nm.Technical scheme in document, the CaAl of made 12O 19: Mn material glow color is red, and glow color is single, and its main emission peak positions is fixed, and is 656nm.Luminous intensity is low, and luminous efficiency can not satisfy the requirement of making white light LEDs.And because luminous efficiency is lower, can the light efficiency of the yellow fluorescent powder of common use be exerted an influence, for the colour rendering index that improves white light LEDs with reduce the DeGrain of colour rendering index.
(2) document of BLASS.G " FLUORESCENCE OF Eu 2+-ACTIVATED ALKALINE-EARTHALUMINATES ", be published in " Philips Res. ", Repts23,201-206,1968, introduced (Sr, Ba, Ca) Al 12O 19: Eu 2+Luminescent material, this material is synthetic under reducing atmosphere, the luminous energy level transition that comes from divalent europium, synthetic under the tangible reducing atmosphere of this material, the luminous energy level transition that comes from divalent europium, and luminous for UV-light to royal purple light district, can not produce emitting red light, can't realize the effect of warm white.
(3) application number is the patent of KR20020063395, relates to BaAl 12O 19: Mn, SrAl 13O 19: Mn, CaAl 12O 19: Mn is as the green emitting phosphor of making the flat display apparatus use, and the main emission wavelength of its emmission spectrum is positioned at green range.Can not realize emitting red light.
(4) application number is that the patent of 200510078430.6 (publication number is CN1880404A) is the early patent of application of applicant, wherein relates to aluminate fluorescent powder.Its principal right requires a content to be: a kind ofly can be excited the fluorescent material that glows by UV-light, blue-ray LED, its spy main chemical expression formula just is AM aO b: Mn x, R y, fluorescent material medium particle diameter D 50Be 2～6 μ m; Wherein A is Mg, Ca, Sr, Ba, the combination of 1～3 kind of element in Zn; M is Al, Ga, Y, the combination of 1～3 kind of element in Gd; R is Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, the combination of 1～3 kind of element in Tm and Cu; 0.9＜a＜25,3＜b＜40,0.0001＜x＜1,0≤y＜0.5.Its goal of the invention of contrast patent (4) technical scheme is similar to the technical program, but the luminosity of red illuminating material differs greatly.
(5) application number be provide in the patent of 200710105748.8 (publication number is CN:101054520A) a kind of take Sm as dominant activator the coactivated red illuminating material of other rare earth ion, the matrix of its material is aluminate or borate or phosphoric acid salt or silicate or mixed phase.Its goal of the invention of contrast patent (5) technical scheme is similar to the technical program.But the composition of material and the technical program have obvious difference.When its main body is aluminate, its luminous ion transition that mainly stems from Sm, its Sm is the element that must contain, phototranstormation efficiency is not high.
From the above mentioned, a kind of luminous intensity of present urgent need searching is high, the red illuminating material of stable chemical performance, can effectively be applied to the making of LED, particularly has the LED of warm-white light-emitting and the LED of emitting red light.
Summary of the invention
An object of the present invention is to provide a kind of clad aluminum salt luminescent material, (240～510nm), (590～660nm), light conversion efficiency is high, the luminescent material of ageing-resistant performance excellence for red-emitting to have the wide ranges of exciting; Another object of the present invention is to provide a kind of light-emitting device that contains clad aluminum salt luminescent material of the present invention, particularly comprises the light-emitting device of white light LEDs and red-light LED.
The main chemical constitution of clad aluminum salt luminescent material of the present invention can be used formula (1) expression:
M a+b(Al 1-βA β) γO 1.5γ+aD 2b:xEu·yMn·zLn·δLm(1)
Wherein: M is the combination of one or more elements in Mg, Ca, Sr, Ba, Zn; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn, Pb; Lm is the combination of one or more element ions in Li, Na, K, Ag; A, b, β, γ, x, y, z are mole coefficient, 0≤a≤2,0＜b≤2, and 1≤(a+b)≤3; 0.001≤β＜0.3,10＜γ＜14; 0≤x＜0.25,0≤y＜0.25,0＜z＜0.1,0.001≤δ＜0.2, and x and y can not be zero simultaneously; This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1), M is Mg, Ca, Sr, Ba, the combination of one or more elements in Zn; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, Mn; Lm is the combination of one or more element ions in Li, Na, K, Ag; 0≤a≤2,0＜b≤2, and 1≤(a+b)≤3; 0.001≤β＜0.3,10＜γ＜14; 0≤x＜0.25, y=0,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1), M is Mg, Ca, Sr, Ba, the combination of one or more elements in Zn; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, Mn; Lm is the combination of one or more element ions in Li, Na, K, Ag; 0≤a≤2,0＜b≤2, and 1≤(a+b)≤3; 0.001≤β＜0.3,10＜γ＜14; 0≤y＜0.25, x=0,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1), M is Mg, Ca, Sr, Ba, the combination of one or more elements in Zn; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, Mn; Lm is the combination of one or more element ions in Li, Na, K, Ag; 0≤a≤2,0＜b≤2, and 1≤(a+b)≤3; 0.001≤β＜0.3,10＜γ＜14; 0＜x＜0.25,0＜y＜0.25,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1) when 0≤x＜0.25,0≤y＜0.25 o'clock; Perhaps 0≤x＜0.25 is during y=0; Perhaps 0≤y＜0.25 is during x=0; Perhaps 0＜x＜0.25,0＜y＜0.25 o'clock, in the chemical constitution expression, M is Mg, Ca, Sr, Ba, the combination of one or more elements in Zn; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, Mn; Lm is the combination of one or both element ions in Li, Ag; Mole coefficient 0.8≤a≤2,0.001＜b≤1, and 1≤(a+b)≤2; 0.001≤β＜0.2,11≤γ≤13,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1) when 0≤x＜0.25,0≤y＜0.25 o'clock; Perhaps 0≤x＜0.25 is during y=0; Perhaps 0≤y＜0.25 is during x=0; Perhaps 0＜x＜0.25,0＜y＜0.25 o'clock, in the chemical constitution expression, M is Mg, Ca, Sr, Ba, the combination of one or more elements in Zn; A is the combination of one or both elements in Y, Gd; D is that the combination Ln of one or both element ions in Cl, F is that the combination Lm of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, Mn is the combination of one or both element ions in Li, Ag; Mole coefficient 0≤a≤1,0.5＜b≤2, and 1≤(a+b)≤2; 0.001≤β＜0.2,11≤γ≤13,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1) when 0≤x＜0.25,0≤y＜0.25 o'clock; Perhaps 0≤x＜0.25 is during y=0; Perhaps 0≤y＜0.25 is during x=0; Perhaps 0＜x＜0.25,0＜y＜0.25 o'clock, in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; A is the combination of one or both elements in Y, Gd; D is that the combination Ln of one or both element ions in Cl, F is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr, Bi; Lm is the combination of one or both element ions in Li, Ag; Mole coefficient a=1,0.001＜b≤1; 0.001≤β＜0.2, γ=12,0＜z＜0.1,0.001≤5＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1) when 0≤x＜0.25,0≤y＜0.25 o'clock; Perhaps 0≤x＜0.25 is during y=0; Perhaps 0≤y＜0.25 is during x=0; Perhaps 0＜x＜0.25,0＜y＜0.25 o'clock, in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; A is the combination of one or both elements in Y, Gd; D is that the combination Ln of one or both element ions in Cl, F is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr, Bi; Lm is the combination of one or both element ions in Li, Ag; Mole coefficient a=0,0.8≤b≤2; 0.001≤β＜0.2, γ=12,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
According to the clad aluminum salt luminescent material of a preferred embodiment of the present invention, in chemical constitution expression (1) when 0≤x＜0.25,0≤y＜0.25 o'clock; Perhaps 0≤x＜0.25 is during y=0; Perhaps 0≤y＜0.25 is during x=0; Perhaps 0＜x＜0.25,0＜y＜0.25 o'clock, in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; A is the combination of one or both elements in Y, Gd; D is the combination of one or both element ions in Cl, F; Ln is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr, Bi; Lm is the combination of one or both element ions in Li, Ag; Mole coefficient a=1, b=1; 0.001≤β＜0.2, γ=12,0＜z＜0.1,0.001≤δ＜0.2.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
Clad aluminum salt luminescent material according to a preferred embodiment of the present invention, wherein said luminescent material is by the UV-light at 240～510nm---the optical excitation of the excitation light source with emission peak in green range, be issued to rare one with upward peak the red emission spectrum in 590～660nm scope.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
Clad aluminum salt luminescent material according to a preferred embodiment of the present invention, wherein said luminescent material is by the UV-light at 240～510nm---the optical excitation of the excitation light source with emission peak in green range, and the emission peak wavelength of luminescent material is greater than the wavelength of the long wave side emission peak of excitation light source.This material can be by as the emmission spectrum of the excitation light source ultraviolet at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion utilizing emitted light of excitation light source, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope, can present the luminous of red color, also can mix with other one or more fluorescent material use realize white luminous.
In the present invention, the kind of the metallic element M of clad aluminum salt luminescent material and A affects wavelength and the luminous intensity of the emission peak of luminescent material.Also can affect it by the contamination of regulating its activator in addition and excite wavelength and luminous intensity with emmission spectrum.
In the present invention, introducing element D, Ln and Lm are also important discovery and the innovations in the present invention, formed clad aluminum silicate material has no relevant bibliographical information and patent application at present, and its purpose and effect are the luminous intensities that can improve widely luminescent material.
Be the patent of 200510078430.6 (publication number is CN1880404A) for application number, pass through to introduce halide-ions D and monovalent base metal ion Lm, the luminous intensity of the fluorescent material that can significantly be enhanced in technical scheme of the present invention.In the technical program, reduce phonon energy by introducing halide-ions; Alkalimetal ion Lm makees charge compensation, effectively plays the effect that fluorescence strengthens.
Be the patent of 200710105748.8 (publication number is CN:101054520A) for application number, the technical program is activator by Eu and/or Mn, and Ln realizes that fluorescence strengthens, and has higher phototranstormation efficiency.In the technical program, except by alkaline-earth metal, also realize the adjustable of spectrum by introducing transition metal Y, Yb, Ga, Gd.
The invention still further relates to a kind of light-emitting device, is the luminous element that has as excitation light source, and the light-emitting device that comprises LED of the luminescent material that at least a portion light of excitation light source can be changed, wherein:
The Emission Spectrum Peals of luminous element is in the UV-light of 240～510nm---in the green glow regional extent, and the wavelength Conversion of the first luminescent spectrum of the described luminous element of at least a portion is become to have at least more than one peak wavelength to be in the light-emitting device of the luminescent material of the second emmission spectrum in 590～660nm wavelength region, it is any clad aluminum salt luminescent material of the present invention that luminescent material wherein has more than one at least.
According to the light-emitting device of a preferred embodiment of the present invention, absorb the UV-light of 240～510nm of luminous element as the luminous element of excitation light source at luminescent material---have at least the emission peak wavelength more than 1 in the green glow regional extent.
According to the light-emitting device of a preferred embodiment of the present invention, the luminescent layer of luminous element is nitride-based semiconductor or has the nitride-based semiconductor that contains In.
According to the light-emitting device of a preferred embodiment of the present invention, it is any clad aluminum salt luminescent material of the present invention that the luminescent material that uses has more than one at least.
Light-emitting device according to a preferred embodiment of the present invention, as the Emission Spectrum Peals of the luminous element of the excitation light source UV-light at 240～510nm---in green range, it is any clad aluminum salt luminescent material of the present invention that the luminescent material that uses has more than one at least; At least a portion illuminating rotary that luminescent material absorbs non-other fluorescent material of the present invention in the luminous and/or combination of at least a portion of excitation light source changes into different has at least more than one peak wavelength to be in emmission spectrum in 590～660nm wavelength region, and with luminous mixing of luminous and/or non-other one or more the fluorescent material of the present invention of luminous element after obtain mixed white luminous.Obtain white luminously can be: chip light emitting and material of the present invention are luminous compound; Chip light emitting, the light-emitting phosphor that material of the present invention is luminous and the present invention is outer are compound.
Light-emitting device according to a preferred embodiment of the present invention, as the Emission Spectrum Peals of the luminous element of the excitation light source UV-light at 240～510nm---in green range, it is any clad aluminum salt luminescent material of the present invention that the luminescent material that uses has more than one at least; It is luminous that luminescent material absorbs at least a portion of non-other fluorescent material of the present invention in the luminous and/or combination of at least a portion of excitation light source, convert to and different have at least more than one peak wavelength to be in emmission spectrum in 590～660nm wavelength region, and with acquisition emitting red light after luminous and/or non-other one or more the light-emitting phosphor of the present invention of luminous element mixes.Obtaining emitting red light can be: different and non-light-emitting phosphor intensity of the present invention by situations such as material of the present invention absorb, all can obtain emitting red light lower than material luminous intensity of the present invention or non-light-emitting phosphor intensity of the present invention when the luminous wave band of the chip of choosing.
Emitting red light described in the present invention comprises pink, pigment look, pale pinkish purple, the nearly emitting red light such as amber.
According to the light-emitting device of a preferred embodiment of the present invention, the luminescent material that uses also contains the second luminescent material that together uses with more than one clad aluminum salt luminescent material of the present invention, and/or the 3rd luminescent material, and/or the 4th luminescent material; This second luminescent material, and/or the 3rd luminescent material, and/or the 4th luminescent material part of the light of self-excitation light source in the future, and/or from least a portion wavelength Conversion of the light of clad aluminum salt luminescent material of the present invention, and compoundly go out white light.
According to the light-emitting device of a preferred embodiment of the present invention, the luminescent material that uses also contains the second luminescent material that together uses with more than one clad aluminum salt luminescent material of the present invention, and/or the 3rd luminescent material, and/or the 4th luminescent material; This second luminescent material, and/or the 3rd luminescent material, and/or the 4th luminescent material part of the light of self-excitation light source in the future, and/or from least a portion wavelength Conversion of the light of clad aluminum salt luminescent material of the present invention, and compoundly go out ruddiness.
according to the light-emitting device of a preferred embodiment of the present invention, the second luminescent material wherein and/or the 3rd luminescent material and/or the 4th luminescent material are: the nitric oxide fluorescent powder of rare earth doped activation, and/or the Nitride phosphor of rare earth doped activation, and/or the halogen silicate phosphor powder of rare earth doped activation, and/or the silicate fluorescent powder of rare earth doped activation, and/or the aluminate fluorescent powder of rare earth doped activation, and/or the fluorescent material of the garnet structure of rare earth doped activation, and/or the sulphide fluorescent material of rare earth doped activation, and/or the oxide fluorescent powder of rare earth doped activation, and/or the oxysulfide phosphor of rare earth doped activation, and/or the sour magnesium fluorescent material of fluorine arsenic (germanium) of doped with Mn activation, and/or the borate fluorescent powder of rare earth doped activation, and/or the phosphate phosphor of rare earth doped activation, and/or the halogen-phosphate fluorescent material of rare earth doped activation, and/or the titanate fluorescent powder of rare earth doped activation, and/or the thiogallate fluorescent material of rare earth doped activation.
According to the light-emitting device of a preferred embodiment of the present invention, light-emitting device is the LED that a kind of luminescent material directly or indirectly contacts with chip.
According to the light-emitting device of a preferred embodiment of the present invention, light-emitting device is to comprise the means of illumination that at least one uses the LED of luminescent material of the present invention.
Clad aluminum salt luminescent material of the present invention also can be excited by the chip in ultraviolet～green range and emitting red light is arranged, and can be used for making the LED of emitting red light, also can be used for making white luminous LED.
When making silicate luminescent material of the present invention, raw materials used is the compound of each element in expression (1), generally select in raw material, the compound of M, A, Ln, Lm, Eu is carbonate, vitriol, nitrate, phosphoric acid salt, borate, acetate, oxalate, Citrate trianion or its oxide compound, oxyhydroxide, the halogenide of using respectively their representative elements; The compound of D is halogenide, halate, sulfide, oxysulfide, the vitriol of using respectively their representative elements; The compound of Al is to use oxide compound, oxyhydroxide, halogenide, carbonate, vitriol, nitrate.A raw materials used middle element mole proportioning is followed mole coefficient: 0≤a≤2,0＜b≤2, and 1≤(a+b)≤3; 0.001≤β＜0.2,10＜γ＜14; 0≤x＜0.25,0≤y＜0.25,0＜z＜0.1,0.001≤δ＜0.2, and x and y can not be zero simultaneously.
Manufacture craft can be liquid phase method or high-temperature solid phase reaction method.Wherein liquid phase method is: adopt sol-gel method or coprecipitation method to prepare presoma; with presoma through calcination 3～20 hours under oxidation or protection of inert gas or weakly reducing atmosphere after drying, grinding, sieve; wherein the scope of calcination temperature is 1300～1600 ℃; after cooling; pulverize, sieving forms.
High-temperature solid phase reaction method is: with the various starting material that planetary/Quick ball grinder is dry mixed or wet mixing is appropriate; then with the powder that mixes through oven dry after calcination 3～20 hours under oxidation or protection of inert gas or weakly reducing atmosphere; wherein the scope of calcination temperature is 1300～1600 ℃; after cooling; pulverize, sieving forms.
High-temperature solid phase reaction method also can adopt the method for twice firing: with the various starting material that planetary/Quick ball grinder is dry mixed or wet mixing is appropriate, then the powder that mixes is taked the method for secondary calcination, wherein calcination condition for the first time is: in oxidation or weakly reducing atmosphere, calcination time is 2-10 hour, and temperature is 1000-1300 ℃; Calcination condition for the second time is: in oxidation or weakly reducing atmosphere, calcination time is 2-20 hour, and calcination temperature is 1000-1600 ℃, cooling after, pulverize, sieving forms.
In the present invention, adopt high temperature solid-state method to prepare this redness aluminate luminescent material, fully mix in order to make each starting material, can adopt wet ball grinding to mix, ball-milling medium can be the organic solvents such as alcohol, acetone, Virahol, can be also deionized water; Also can adopt dry ball milling to mix, ball mill can use high speed ball mill, also can adopt planetary Quick ball grinder.
In the present invention, adopt high temperature solid-state method to prepare this redness aluminate luminescent material, in order to improve the quality of material, can add other compounds of a small amount of (0%～30%) in raw material, as NH 4Cl, NH 4F, (NH 4) 2HPO 4, BaF 2, CaF 2, SrF 2, ZnF 2, BaCl 2, MgCl 2, ZnS, SrS, CaS, SrSO 4, SrHPO 4Or CaHPO 4, Li 2CO 3, NaF, K 2CO 3Participate in solid state reaction as fusing assistant.
In the present invention, the excitation spectrum of luminescent material and emmission spectrum adopt the test of F-4500 fluorescence spectrophotometer.
The optical parametric index of LED adopts the test of PMS-50 type ultraviolet-visible-near-infrared spectrum analytical system.
Description of drawings
Fig. 1 is the excitation and emission spectra of the luminescent material of embodiment 1;
Fig. 2 is the emmission spectrum of the luminescent material of embodiment 2;
Fig. 3 is the emmission spectrum of the luminescent material of embodiment 3;
The excitation and emission spectra figure of Fig. 4 embodiment 4.
The excitation and emission spectra figure of Fig. 5 embodiment 5.
Fig. 6 comprises semiconductor luminous chip 1, negative electrode 2, positive electrode 3, pin 4, luminescent material 5, packaged material 6, lead-in wire 7, reflection cup 8, pad pasting 9 for using the LED structural representation of luminescent material; The figure a mode that to be luminescent material directly contact with semiconductor luminous chip, luminescent material with evenly be coated on semiconductor luminous chip, among reflector after transparent resin mixes.Figure b is the mode of luminescent material and semiconductor luminous chip indirect contact, and luminescent material is evenly distributed on epoxy skins.Figure c is the mode of luminescent material semiconductor luminous chip indirect contact, and luminescent material is evenly distributed among epoxy resin, on semiconductor luminous chip.Figure d is the mode of luminescent material semiconductor luminous chip indirect contact, and after luminescent material mixes with transparent medium, the form of preparation film forming is covered on semiconductor luminous chip again.
Embodiment
Below the present invention is described further with embodiment.
Embodiment 1:Ca (Al 0.995Gd 0.005) 12O 18F 2: the preparation method of 0.02Eu0.03Mn0.001Ce0.02Li luminescent material
Take various raw materials of Ca CO by stoichiometric composition 3, Al 2O 3, Gd 2O 3, Eu 2O 3, MnCO 3, NH 4F, Li 2CO 3, CeO 2Adding 0.2% boric acid is fusing assistant, after fully ball milling mixes, fill in 99 porcelain crucibles, 1000 ℃ are incubated 6 hours under oxidizing atmosphere, be incubated 4 hours in lower 1580 ℃ of oxygen atmosphere after cooling grinding, the chemical constitution that after sintered compact is cooling, pulverize, sieve, classification namely obtains in the present invention is Ca (Al 0.095Gd 0.005) 12O 18F 2: the luminescent material of 0.02Eu0.03Mn0.001Ce0.02Li.The excitation spectrum of this material is in 250～510nm scope; At 380nm and 470nm place, strong excitation wavelength is arranged, emmission spectrum has emission peak in 620～670nm scope, and its strongest emission wavelength is positioned at 656nm, its excite with emmission spectrum as shown in Figure 1.
Embodiment 2:
Make according to the preparation process of embodiment 1 and consist of Ca 1.2(Al 0.96Gd 0.04) 12O 18.9F 0.6: the luminescent material of 0.05Mn0.004Ce0.005Li, its strongest emission wavelength is positioned at 655nm, and its emmission spectrum is as shown in Figure 2.
Embodiment 3:
Make according to the preparation process of embodiment 1 and consist of Ca 1.05Sr 0.05(Al 0.97Y 0.03) 10.2O 15.4F 2: the luminescent material of 0.2Eu0.002Pr0.05Li, its strongest emission wavelength is positioned at 654nm, and its emmission spectrum is as shown in Figure 3.
Embodiment 4:
Make according to the preparation process of embodiment 1 and consist of Sr 2.5(Al 0.9Y 0.1) 11O 17Cl 4: the luminescent material of 0.2Mn0.08Li0.001Ag, its strongest emission wavelength is positioned at 590nm, its excite with emmission spectrum as shown in Figure 4.
Embodiment 5:
Make according to the preparation process of embodiment 1 and consist of Sr 1Ca 2(Al 0.9Gd 0.1) 13O 22The luminescent material of F:0.1Eu0.02Mn0.01Ce0.01Li, its strongest emission wavelength is positioned at 610nm, its excite with emmission spectrum as shown in Figure 5.
Embodiment 6:
Make according to the preparation process of embodiment 1 and consist of Ca 0.85Sr 0.05Ba 0.13Mg 0.02(Al 0.8Gd 0.2) 12.3O 19.3Cl 0.4: the luminescent material of 0.15Eu0.002Nd0.001K, its strongest emission wavelength is positioned at 628nm.
Embodiment 7:
Make according to the preparation process of embodiment 1 and consist of:
Ca 0.85Ba 0.25Mg 0.14Zn 0.07(Al 0.85Gd 0.15) 10.40O 15.96Cl 1.90: the luminescent material of 0.1Eu0.03Dy0.01Ce0.001Li, its strongest emission wavelength is positioned at 603nm.
Embodiment 8
Take Ca (NO by stoichiometric composition 3) 2, Mn (NO 3) 2, Y 2O 3, Eu (NO 3) 3, Li 2CO 3, CeO 2Be dissolved in certain density nitric acid, with the preparation solution A, then the aluminum nitrate with respective amount is dissolved in deionized water, with the preparation solution B; Again with solution A together with solution B is stirred in, and add appropriate ammoniacal liquor, regulate its pH value to 9 left and right, then at 70 ℃ of about 3-8 of this solution of lower continuously stirring hours; In order to make mixing solutions generate gel; With the resulting gel drying of aforesaid method, then 900 ℃ of lower calcinations 60 minutes, make the desiccant gel that obtains be decomposed to form oxide products, namely obtain presoma.Then add CaF in presoma 2, grind and evenly to be placed in crucible, calcination 6 hours at 1400 ℃ of temperature under weakly reducing atmosphere; Block after calcination is ground classification, the Ca that just can be evenly distributed, median size is less 2(Al 0.95Y 0.05) 12O 19F 2: the 0.05Eu0.04Mn0.001Ce0.05Li luminescent material.
The invention still further relates to the means of illumination that uses any above luminescent material in the present invention, particularly use the semiconductor LED of emission main peak in 250～510nm scope of the luminous element that uses as excitation light source to be packaged into warm white and red LED.In the present invention, what packaged type can be in Fig. 6 is several: wherein scheme a and be the mode that luminescent material and semiconductor luminous chip directly contact, luminescent material with evenly be coated on semiconductor luminous chip, among reflector after transparent resin mixes.Figure b is the mode of luminescent material and semiconductor luminous chip indirect contact, and luminescent material is evenly distributed on epoxy skins.Figure c is the mode of luminescent material semiconductor luminous chip indirect contact, and luminescent material is evenly distributed among epoxy resin, on semiconductor luminous chip.Figure d is the mode of luminescent material semiconductor luminous chip indirect contact, and after luminescent material mixes with transparent medium, the form of preparation film forming is covered on semiconductor luminous chip again.
The below is explained with specific embodiment.
Embodiment 9: one of manufacturing of white light LEDs
SrS:Eu with proper ratio 2+Orange fluorescent powder, (Ca, Sr, Ba, Zn) 2SiO 4: Eu 2+Green emitting phosphor, (Ca, Sr, Ba) MgAl 10O 17: Eu 2+Blue colour fluorescent powder mixes with the compound aluminate red luminescent material of the embodiment of the present invention 2, is dispersed in epoxy resin, evenly is coated on purple light (emission wavelength is 390-395nm) chip.To put the lead-in wire cup of glue, after putting into vacuum drying oven curing, inserting to fill with has in the mould of epoxy resin, then solidifies finally demould through vacuum drying oven.Its encapsulation is (semiconductor luminous chip 1, negative electrode 2, positive electrode 3, pin 4, luminescent material 5, packaged material 6, lead-in wire 7, reflection cup 8) as shown in a in Fig. 6.Various powder send after the ultraviolet chip excites red, green, rotten compoundly goes out white light, and its chromaticity coordinate is X=0.3267, Y=0.3337, colour temperature 5782K, colour rendering index 92.
Embodiment 10: two of the manufacturing of white light LEDs
Adopt the LED packaged type of b in Fig. 6 to prepare white light LEDs, the red clad aluminum salt luminescent material of the embodiment of the present invention 1 is mixed according to the ratio of 93: 7 with the Yellow luminous material of YAG, select blue light (emission wavelength is 457.5-460nm) chip as source of radiation.Packaging process is with embodiment 10, but luminescent material is evenly distributed on epoxy skins, and the emission spectrum of this white light LEDs is blue-light excited rear redness of launching respectively, the Yellow luminous white light that is composited that launched by blue chip by above-mentioned luminescent material.After its encapsulation, the chromaticity coordinate of LED is X=0.3655, Y=0.3275, colour temperature 4060K, colour rendering index 88.1.
Embodiment 11: three of the manufacturing of white light LEDs
Adopt the LED packaged type of c in Fig. 6 to prepare red LED, the red illuminating material of the appropriate embodiment of the present invention 3 is dispersed in epoxy resin, evenly be coated on purple light (emission wavelength is 390-395nm) chip.Packaging process is with embodiment 30, and after its encapsulation, chromaticity coordinate of LED is X=0.7232, Y=0.2731, for scarlet luminous.
Embodiment 12: four of the manufacturing of white light LEDs
Adopt the LED packaged type of d in Fig. 6 to prepare red LED, with appropriate green luminescent material (Ca, Sr, Ba) Al 2O 4: Eu 2+The red illuminating material that reaches the embodiment of the present invention 5 is dispersed in epoxy resin, evenly is coated on purple light (emission wavelength is 390-395nm) chip.Packaging process is with embodiment 10, and after its encapsulation, the chromaticity coordinate of LED is X=0.6402, Y=0.3105, is emitting red light.
Embodiment 13: five of the manufacturing of white light LEDs
Adopt the LED packaged type of a in Fig. 6 to prepare pink LED, the red illuminating material of the appropriate embodiment of the present invention 1 is dispersed in epoxy resin, evenly be coated on green glow (emission wavelength is 500-505nm) chip.Packaging process is with embodiment 10, and after its encapsulation, the chromaticity coordinate of LED is X=0.4612, Y=0.3203, is pink light emitting.
Embodiment 14: six of the manufacturing of white light LEDs
Adopt the LED packaged type of a in Fig. 6 to prepare amber LED, with appropriate green luminescent material (Ca, Sr, Ba, Zn) 2SiO 4: Eu 2+The red illuminating material that reaches the embodiment of the present invention 1 is dispersed in epoxy resin, evenly is coated on blue light (emission wavelength is 455-457.5nm) chip.Packaging process is with embodiment 10, and after its encapsulation, the chromaticity coordinate of LED is X=0.4502, Y=0.2213, for amber luminous.
Clad aluminum salt luminescent material stable chemical performance of the present invention, anti-aging property are excellent, the luminous efficiency of emitting red light and all be better than existing technical scheme for the characteristics such as adaptability of chip.

Claims (19)

1.一种红色发光的发光材料，其特征为含有卤素和激活剂离子的复合铝酸盐发光材料，其主要的化学组成表示式为：Ma＋b(Al1－βAβ)γO1.5γ+aD2b：xEu·yMn·zLn·δLm，其中：M为Mg、Ca、Sr、Ba、Zn中的一种或多种元素的组合；A为 Y、Gd中的一种或两种元素的组合；D为Cl、F中的一种或两种元素离子的组合；Ln为Nd、Dy、Ho、Tm、La、Ce、Er、Pr、Lu、Tb中一种或多种元素离子的组合；Lm为Li、Na、K、Ag中的一种或多种元素离子的组合；a、b、β、γ、x、y、z、δ为摩尔系数，0≤a≤2，0＜b≤2，且1≤（a＋b）≤3； 0.001≤β＜0.3，10＜γ＜14；0≤x＜0.25， 0≤y＜0.25，0＜z＜0.1，0.001≤δ＜0.2，且x和y不能同时为零；该材料可以被做为激发光源的发射光谱在240～510nm的紫外——绿光区域的发光元件激发，吸收激发光源的至少一部分发射光，发出至少有一个以上峰值在590～660nm范围内的发射光谱，可呈现红颜色的发光，也可与其它一种或一种以上的荧光粉混合使用实现白色发光。1. A red luminescent luminescent material, characterized in that it is a composite aluminate luminescent material containing halogen and activator ions, and its main chemical composition expression is: M a+b (Al 1－β A β ) γ O 1.5γ +a D 2b : xEu·yMn·zLn·δLm, wherein: M is a combination of one or more elements of Mg, Ca, Sr, Ba, Zn; A is one or two elements of Y, Gd D is the combination of one or two element ions in Cl and F; Ln is the combination of one or more element ions in Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Lu, Tb Combination; Lm is a combination of one or more element ions in Li, Na, K, Ag; a, b, β, γ, x, y, z, δ are molar coefficients, 0≤a≤2, 0< b≤2, and 1≤(a+b)≤3; 0.001≤β<0.3, 10<γ<14;0≤x<0.25,0≤y<0.25,0<z<0.1,0.001≤δ<0.2, and x and y cannot be zero at the same time; the material can be excited by a light-emitting element in the ultraviolet-green light region with an emission spectrum of 240-510nm as an excitation light source, absorb at least part of the emission light of the excitation light source, and emit at least one peak The emission spectrum in the range of 590-660nm can show red light emission, and can also be mixed with one or more than one other phosphor powder to achieve white light emission. 2.根据权利要求1所述的一种红色发光的发光材料，其特征在于化学组成表示式中的摩尔系数y＝0 。2. A red luminescent luminescent material according to claim 1, characterized in that the molar coefficient y=0 in the chemical composition expression. 3.根据权利要求1所述的一种红色发光的发光材料，其特征在于化学组成表示式中的摩尔系数x＝0。3. A red luminescent luminescent material according to claim 1, characterized in that the molar coefficient x=0 in the chemical composition expression. 4.根据权利要求1所述的一种红色发光的发光材料，其特征在于化学组成表示式中的摩尔系数0＜x＜0.25， 0＜y＜0.25。4. A red luminescent luminescent material according to claim 1, characterized in that the molar coefficients in the chemical composition expression are 0<x<0.25, 0<y<0.25. 5.根据权利要求1、2、3或4所述的一种红色发光的发光材料，其特征在于化学组成表示式中Lm为Li、Ag中的一种或两种元素离子的组合；摩尔系数0.8≤a≤2，0.001＜b≤1，且1≤（a＋b）≤2；0.001≤β＜0.2，11≤γ≤13。5. A kind of red luminescent luminescent material according to claim 1, 2, 3 or 4, characterized in that in the chemical composition expression, Lm is a combination of one or two element ions in Li and Ag; molar coefficient 0.8≤a≤2, 0.001<b≤1, and 1≤(a+b)≤2; 0.001≤β<0.2, 11≤γ≤13. 6.根据权利要求1、2、3或4所述的一种红色发光的发光材料，其特征在于化学组成表示式中Lm为Li、Ag中的一种或两种元素离子的组合；摩尔系数0≤a≤1，0.5＜b≤2，且1≤（a＋b）≤2；0.001≤β＜0.2，11≤γ≤13。6. A kind of red luminescent luminescent material according to claim 1, 2, 3 or 4, characterized in that in the chemical composition expression, Lm is a combination of one or two element ions in Li and Ag; molar coefficient 0≤a≤1, 0.5<b≤2, and 1≤(a+b)≤2; 0.001≤β<0.2, 11≤γ≤13. 7.根据权利要求1、2、3或4所述的一种红色发光的发光材料，其特征在于化学组成表示式中M为Mg，Ca，Sr中的一种或多种元素的组合； Ln为Nd、Dy、Ho、La、Ce、Er、Pr中一种或多种元素离子的组合；Lm为Li、Ag中的一种或两种元素离子的组合；摩尔系数a=1，0.001＜b≤1；0.001≤β＜0.2，γ=12。7. A kind of red luminous luminescent material according to claim 1, 2, 3 or 4, characterized in that in the chemical composition expression, M is Mg, Ca, a combination of one or more elements in Sr; Ln It is a combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; Lm is a combination of one or two element ions in Li, Ag; molar coefficient a=1, 0.001< b≤1; 0.001≤β<0.2, γ=12. 8.根据权利要求1、2、3或4所述的一种红色发光的发光材料，其特征在于化学组成表示式中M为Mg，Ca，Sr中的一种或多种元素的组合； Ln为Nd、Dy、Ho、La、Ce、Er、Pr中一种或多种元素离子的组合；Lm为Li、Ag中的一种或两种元素离子的组合；摩尔系数a=0，0.8≤b≤2；0.001≤β＜0.2，γ=12。8. A kind of red luminescent luminescent material according to claim 1, 2, 3 or 4, characterized in that in the chemical composition expression, M is Mg, Ca, a combination of one or more elements in Sr; Ln It is a combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; Lm is a combination of one or two element ions in Li, Ag; molar coefficient a=0, 0.8≤ b≤2; 0.001≤β<0.2, γ=12. 9.根据权利要求1、2、3或4所述的一种红色发光的发光材料，其特征在于化学组成表示式中M为Mg，Ca，Sr中的一种或多种元素的组合；Ln为Nd、Dy、Ho、La、Ce、Er、Pr中一种或多种元素离子的组合；Lm为Li、Ag中的一种或两种元素离子的组合；摩尔系数a＝1，b＝1；0.001≤β＜0.2，γ=12。9. A red luminous luminescent material according to claim 1, 2, 3 or 4, characterized in that in the chemical composition expression, M is a combination of one or more elements in Mg, Ca, Sr; Ln is a combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; Lm is a combination of one or two element ions in Li and Ag; molar coefficient a=1, b= 1; 0.001≤β<0.2, γ=12. 10.一种发光装置，是具有做为激发光源的发光元件，及能够将激发光源的至少一部分光转换的发光材料的包括LED在内的发光装置，其特征在于：10. A light-emitting device, which is a light-emitting device including an LED with a light-emitting element as an excitation light source and a light-emitting material capable of converting at least a part of the light from the excitation light source, characterized in that: 发光元件的发射光谱峰值在240～510nm的紫外光——绿光区域范围内，以及将至少一部分所述的发光元件的第一发光光谱的波长转换成至少有一个以上的峰值波长处于590～660nm波长范围内的第二发射光谱的发光材料的发光装置，所述的发光材料至少有一种以上为权利要求1～9中任何一项所述的复合铝酸盐发光材料。The emission spectrum peak of the light-emitting element is within the ultraviolet light-green light range of 240-510nm, and at least one of the wavelengths of the first light-emitting spectrum of the light-emitting element is converted into at least one peak wavelength in the range of 590-660nm A light-emitting device of light-emitting materials with a second emission spectrum in the wavelength range, at least one of the light-emitting materials is the composite aluminate light-emitting material described in any one of claims 1-9. 11.如权利要求10所述的发光装置，其特征在于所述的做为激发光源的发光元件在发光材料吸收发光元件的240～510nm的紫外光——绿光区域范围内至少具有1个以上的发射峰波长。11. The light-emitting device according to claim 10, characterized in that the light-emitting element used as the excitation light source has at least one or more within the range of the 240-510nm ultraviolet light of the light-emitting element absorbed by the light-emitting material - the green light region emission peak wavelength. 12.如权利要求10或11所述的发光装置，其特征在于所述的发光元件的发光层是氮化物半导体。12. The light-emitting device according to claim 10 or 11, characterized in that the light-emitting layer of the light-emitting element is a nitride semiconductor. 13.如权利要求10所述的发光装置，其特征在于做为激发光源的发光元件的发射光谱峰值在240～510nm的紫外光——绿光范围内，所使用的发光材料至少有一种以上为权利要求1～9中任何一项所述的复合铝酸盐发光材料；发光材料吸收激发光源的至少一部分发光和/或组合中其他荧光粉的至少一部分发光转换成不同的至少有一个以上的峰值波长处于590～660nm波长范围内的发射光谱，并与发光元件的发光和/或其它一种或一种以上的荧光粉的发光混合后获得混合后的白色发光。13. The light-emitting device according to claim 10, characterized in that the emission spectrum peak of the light-emitting element used as the excitation light source is in the range of ultraviolet light-green light from 240 to 510 nm, and at least one of the light-emitting materials used is The composite aluminate luminescent material according to any one of claims 1 to 9; the luminescent material absorbs at least a part of the luminescence of the excitation light source and/or converts at least a part of the luminescence of other phosphors in the combination into different peaks with at least one or more The emission spectrum with a wavelength in the wavelength range of 590-660nm is mixed with the luminescence of the light-emitting element and/or the luminescence of one or more phosphor powders to obtain mixed white luminescence. 14.如权利要求10所述的发光装置，其特征在于做为激发光源的发光元件的发射光谱峰值在240～510nm的紫外光——绿光范围内，所使用的发光材料至少有一种以上为权利要求1～9中任何一项所述的复合铝酸盐发光材料；发光材料吸收激发光源的至少一部分发光和/或组合中其它荧光粉的至少一部分发光，转换成不同的至少有一个以上的峰值波长处于590～660nm波长范围内的发射光谱，并与发光元件的发光和/或其它一种或一种以上的荧光粉的发光混合后获得红色发光。14. The light-emitting device according to claim 10, characterized in that the emission spectrum peak of the light-emitting element used as the excitation light source is in the range of ultraviolet light-green light from 240 to 510 nm, and at least one of the light-emitting materials used is The composite aluminate luminescent material according to any one of claims 1 to 9; the luminescent material absorbs at least a part of the luminescence of the excitation light source and/or at least a part of the luminescence of other fluorescent powders in the combination, and converts it into at least one of different The emission spectrum whose peak wavelength is within the wavelength range of 590-660nm is mixed with the emission of the light-emitting element and/or the emission of one or more fluorescent powders to obtain red emission. 15.如权利要求10、11或13 所述的发光装置，所述的发光材料，还含有同权利要求1～9中任何一项所述的一种以上的复合铝酸盐发光材料一同使用的第二发光材料，和/或第三发光材料，和/或第四发光材料；该第二发光材料，和/或第三发光材料，和/或第四发光材料将来自所述的激发光源的光的一部分转换，与来自所述权利要求1～9中任何一项所述的复合铝酸盐发光材料的光以及发光元件的发光的至少一部分复合出白色发光。15. The light-emitting device as claimed in claim 10, 11 or 13, wherein said light-emitting material also contains one or more composite aluminate light-emitting materials used together with any one of claims 1-9. The second luminescent material, and/or the third luminescent material, and/or the fourth luminescent material; the second luminescent material, and/or the third luminescent material, and/or the fourth luminescent material will come from the excitation light source A part of the light is converted, and combined with at least a part of the light from the composite aluminate luminescent material and the luminescence of the light-emitting element in any one of claims 1 to 9 to produce white luminescence. 16.如权利要求10、11或14所述的发光装置，所述的发光材料，还含有同权利要求1～9中任何一项所述的一种以上的复合铝酸盐发光材料一同使用的第二发光材料，和/或第三发光材料，和/或第四发光材料；该第二发光材料，和/或第三发光材料，和/或第四发光材料将来自所述的激发光源的光的一部分转换，与来自所述权利要求1～9中任何一项所述的复合铝酸盐发光材料的光以及发光元件的发光的至少一部分复合出红色发光。16. The light-emitting device as claimed in claim 10, 11 or 14, said light-emitting material also contains one or more composite aluminate light-emitting materials used together with any one of claims 1-9. The second luminescent material, and/or the third luminescent material, and/or the fourth luminescent material; the second luminescent material, and/or the third luminescent material, and/or the fourth luminescent material will come from the excitation light source Part of the light is converted, and combined with at least a part of the light from the composite aluminate luminescent material and the luminescent element according to any one of claims 1 to 9 to produce red luminescence. 17.如权利要求10、11、13或14所述的发光装置，其特征在于，所述的第二发光材料和/或第三发光材料和/或第四发光材料为：掺杂稀土激活的氮氧化物荧光粉、和/或掺杂稀土激活的氮化物荧光粉、和/或掺杂稀土激活的卤硅酸盐荧光粉、和/或掺杂稀土激活的硅酸盐荧光粉、和/或掺杂稀土激活的铝酸盐荧光粉、和/或掺杂稀土激活的石榴石结构的荧光粉、和/或掺杂稀土激活的硫化物荧光粉、和/或掺杂稀土激活的氧化物荧光粉、和/或掺杂稀土激活的硫氧化物荧光粉、和/或掺杂Mn激活的氟砷酸镁荧光粉、和/或掺杂Mn激活的氟锗酸镁荧光粉、和/或掺杂稀土激活的硼酸盐荧光粉、和/或掺杂稀土激活的磷酸盐荧光粉、和/或掺杂稀土激活的卤磷酸盐荧光粉、和/或掺杂稀土激活的钛酸盐荧光粉。17. The light-emitting device according to claim 10, 11, 13 or 14, characterized in that, the second light-emitting material and/or the third light-emitting material and/or the fourth light-emitting material are: doped rare earth activated Oxynitride phosphor, and/or doped rare earth activated nitride phosphor, and/or doped rare earth activated halosilicate phosphor, and/or doped rare earth activated silicate phosphor, and/or Or doped rare earth activated aluminate phosphor, and/or doped rare earth activated garnet structure phosphor, and/or doped rare earth activated sulfide phosphor, and/or doped rare earth activated oxide Phosphor powder, and/or doped rare earth activated sulfur oxide phosphor, and/or doped Mn activated magnesium fluoroarsenate phosphor, and/or doped Mn activated magnesium fluorogermanate phosphor, and/or Doped rare earth activated borate phosphor, and/or doped rare earth activated phosphate phosphor, and/or doped rare earth activated halophosphate phosphor, and/or doped rare earth activated titanate phosphor pink. 18.如权利要求10、11、13或14所述的发光装置，其特征在于，所述的发光装置是一种所述的发光材料直接或间接与芯片接触的LED。18. The light emitting device according to claim 10, 11, 13 or 14, characterized in that the light emitting device is an LED in which the light emitting material is in direct or indirect contact with the chip. 19.如权利要求10、11、13或14所述的发光装置，其特征在于，所述的发光装置是包含至少一个使用所述的发光材料的LED的照明装置。19. The light emitting device according to claim 10, 11, 13 or 14, wherein the light emitting device is a lighting device comprising at least one LED using the light emitting material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1880404A (en) * 2005-06-14 2006-12-20 大连路明发光科技股份有限公司 A phosphor that can be excited by ultraviolet light and blue light LED to emit red light
WO2007107915A1 (en) * 2006-03-23 2007-09-27 Philips Intellectual Property & Standards Gmbh Light emitting device with a ceramic garnet material
CN101054520A (en) * 2007-05-29 2007-10-17 王海容 Red luminescence phosphor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1880404A (en) * 2005-06-14 2006-12-20 大连路明发光科技股份有限公司 A phosphor that can be excited by ultraviolet light and blue light LED to emit red light
WO2007107915A1 (en) * 2006-03-23 2007-09-27 Philips Intellectual Property & Standards Gmbh Light emitting device with a ceramic garnet material
CN101054520A (en) * 2007-05-29 2007-10-17 王海容 Red luminescence phosphor

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