CN101570688B - Red light-emitting material and light emitting device using same - Google Patents
Red light-emitting material and light emitting device using same Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- light
- luminous
- combination
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a red light-emitting material. The constitution formula of the light-emitting material is M[a+b](Al[1-beta]Abeta)gammaO[1.5gamma+a]D2b:xEu.yMn.zLn.deltaLm, wherein M is one ormore of elements including Mg, Ca, Sr, Ba and Zn; A is one or more of elements including Y and Gd; D is Cl or/and F which are element irons; Ln is one or more of various element ions including Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sn, Lu, Sb, Tb and Pb; Lm is one or more of various element ions including Li, Na, K and Ag; and a, b, beta, gamma, x, y, z and delta are mole coefficients. The invention is a composite aluminate light-emitting material which can be excited by a excitation light source from ultraviolet to green light and can be taken as the light conversion material used for manufacturing the white series and the red series of light emitting devices including an LED.
Description
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. the luminescent material of an emitting red light, is characterized by the clad aluminum salt luminescent material that contains halogen and activator ion, and its main chemical constitution expression is: M
A+b(Al
1-βA
β)
γO
1.5 γ+aD
2b: xEuyMnzLn δ Lm, 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, Lu, Tb; Lm is the combination of one or more element ions in Li, Na, K, Ag; A, b, β, γ, x, y, z, δ 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.
2. the luminescent material of a kind of emitting red light according to claim 1, is characterized in that the mole coefficient y=0 in the chemical constitution expression.
3. the luminescent material of a kind of emitting red light according to claim 1, is characterized in that the mole coefficient x=0 in the chemical constitution expression.
4. the luminescent material of a kind of emitting red light according to claim 1 is characterized in that the mole coefficient 0＜x＜0.25,0＜y＜0.25 in the chemical constitution expression.
5. according to claim 1, the luminescent material of 2,3 or 4 described a kind of emitting red lights, it is characterized in that in the chemical constitution expression, 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.
6. according to claim 1, the luminescent material of 2,3 or 4 described a kind of emitting red lights, it is characterized in that in the chemical constitution expression, Lm 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.
7. according to claim 1, the luminescent material of 2,3 or 4 described a kind of emitting red lights, it is characterized in that in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; Ln is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; 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.
8. according to claim 1, the luminescent material of 2,3 or 4 described a kind of emitting red lights, it is characterized in that in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; Ln is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; 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.
9. according to claim 1, the luminescent material of 2,3 or 4 described a kind of emitting red lights, it is characterized in that in the chemical constitution expression, M is Mg, Ca, the combination of one or more elements in Sr; Ln is the combination of one or more element ions in Nd, Dy, Ho, La, Ce, Er, Pr; 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.
10. a light-emitting device, be 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, it is characterized in that:
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 one described clad aluminum salt luminescent material in claim 1～9 that described luminescent material has more than one at least.
11. light-emitting device as claimed in claim 10 is characterized in that described luminous element as excitation light source absorbs the UV-light of 240～510nm of luminous element at luminescent material---have at least the emission peak wavelength more than 1 in the green glow regional extent.
12. light-emitting device as described in claim 10 or 11, the luminescent layer that it is characterized in that described luminous element is nitride-based semiconductor.
13. light-emitting device as claimed in claim 10, it is characterized in that as the Emission Spectrum Peals of the luminous element of the excitation light source UV-light at 240～510nm---in green range, the luminescent material that uses has at least more than one to be any one described clad aluminum salt luminescent material in claim 1～9; At least a portion illuminating rotary that luminescent material absorbs other fluorescent material 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 obtains mixed white luminous after one or more luminous mixing of fluorescent material with the luminous of luminous element and/or other.
14. light-emitting device as claimed in claim 10, it is characterized in that as the Emission Spectrum Peals of the luminous element of the excitation light source UV-light at 240～510nm---in green range, the luminescent material that uses has at least more than one to be any one described clad aluminum salt luminescent material in claim 1～9; It is luminous that luminescent material absorbs at least a portion of other fluorescent material 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 obtain emitting red light with the luminous of luminous element and/or other after one or more luminous mixing of fluorescent material.
15. as claim 10,11 or 13 described light-emitting devices, described luminescent material, also contain the second luminescent material that together uses with any one described more than one clad aluminum salt luminescent material in claim 1～9, 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 will be from the part conversion of the light of described excitation light source, with from luminous at least a portion of the light of any one described clad aluminum salt luminescent material in described claim 1～9 and luminous element compound go out white luminous.
16. as claim 10,11 or 14 described light-emitting devices, described luminescent material, also contain the second luminescent material that together uses with any one described more than one clad aluminum salt luminescent material in claim 1～9, 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 will be from the part conversion of the light of described excitation light source, and go out emitting red light from luminous at least a portion of the light of any one described clad aluminum salt luminescent material in described claim 1～9 and luminous element is compound.
17. as claim 10, 11, 13 or 14 described light-emitting devices is characterized in that, described the second luminescent material 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 fluorine magnesium arsenate fluorescent material of doped with Mn activation, and/or the fluogermanic acid magnesium fluorescent material 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.
18. as claim 10,11,13 or 14 described light-emitting devices, it is characterized in that, described light-emitting device is the LED that a kind of described luminescent material directly or indirectly contacts with chip.
19. as claim 10,11,13 or 14 described light-emitting devices, it is characterized in that, described light-emitting device is to comprise the means of illumination that at least one uses the LED of described luminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810011201 CN101570688B (en) | 2008-04-28 | 2008-04-28 | Red light-emitting material and light emitting device using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810011201 CN101570688B (en) | 2008-04-28 | 2008-04-28 | Red light-emitting material and light emitting device using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101570688A CN101570688A (en) | 2009-11-04 |
| CN101570688B true CN101570688B (en) | 2013-05-15 |
Family
ID=41230174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810011201 Active CN101570688B (en) | 2008-04-28 | 2008-04-28 | Red light-emitting material and light emitting device using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101570688B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947481B (en) * | 2017-03-29 | 2019-04-16 | 江苏师范大学 | A kind of red Illuminant nanometer fluorescent powder of europium ion activation, preparation method and application |
| CN108417701B (en) * | 2018-01-24 | 2020-04-03 | 厦门信达光电物联科技研究院有限公司 | Preparation method of white light LED healthy light source |
| CN114891507B (en) * | 2022-04-28 | 2023-09-29 | 东南大学 | Far-infrared fluorescent powder material for LED and preparation method thereof |
Citations (3)
| 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 | Red light-emitting phosphor powder excited by UV and blue light LED |
| 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 |
-
2008
- 2008-04-28 CN CN 200810011201 patent/CN101570688B/en active Active
Patent Citations (3)
| 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 | Red light-emitting phosphor powder excited by UV and blue light LED |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101570688A (en) | 2009-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101077973B (en) | Silicate luminescent material, preparation method thereof and luminescent device using the same | |
| CN101134895B (en) | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same | |
| CN102660269B (en) | Illumination system comprising a radiation source and a luminescent material | |
| KR101439567B1 (en) | Silicate base luminescent materials having multiple emission peaks, processes for preparing the same and light emitting devices using the same | |
| CN100571478C (en) | The illuminator that comprises yellow green-emitting luminescent material | |
| CN104357051B (en) | A kind of fluorescent material and preparation method thereof, and light-emitting device | |
| CN103045256A (en) | LED (Light Emitting Diode) red fluorescence material and luminescent device containing same | |
| US20100244066A1 (en) | Red light fluorescent material and manufacturing method thereof, and white light luminescent device | |
| CN101724401A (en) | Red luminous silicon-oxygen nitride fluorescent material, preparation method and light emitting device using same | |
| CN101126023B (en) | Silicate substrate luminescent material with multiple emission peak, preparation method thereof and luminescent device using the same | |
| CN103045267B (en) | Nitride fluorescent powder and preparation method thereof, luminescent device containing fluorescent powder | |
| CN100560688C (en) | Long after glow luminous material and manufacture method thereof | |
| JP4619509B2 (en) | Light emitting device | |
| JP2023522185A (en) | Green-emitting phosphor and its device | |
| CN101570688B (en) | Red light-emitting material and light emitting device using same | |
| CN100383988C (en) | White light LED and light converting luminophore | |
| JP4433793B2 (en) | Phosphor and light emitting device using the same | |
| CN108728088B (en) | Europium ion excited silicate white light fluorescent powder and preparation method thereof | |
| CN102399554B (en) | Nitride red luminescence material, and luminescent part and luminescent device containing the same | |
| CN101880526B (en) | Blue-green silicate luminescent material | |
| CN101270282B (en) | Rare earth red fluorescent powder for light emitting diode and preparation method thereof | |
| CN101649199B (en) | Ultraviolet light stimulated phosphor | |
| JP4834312B2 (en) | Method for manufacturing phosphor for display device and method for manufacturing display device | |
| CN105567225B (en) | A kind of silicate green fluorescent powder and preparation method thereof | |
| CN117736734A (en) | Blue fluorescent material excited by ultraviolet light and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |