CN101570688A - Red light-emitting material and light emitting device using same - Google Patents

Red light-emitting material and light emitting device using same Download PDF

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CN101570688A
CN101570688A CNA2008100112016A CN200810011201A CN101570688A CN 101570688 A CN101570688 A CN 101570688A CN A2008100112016 A CNA2008100112016 A CN A2008100112016A CN 200810011201 A CN200810011201 A CN 200810011201A CN 101570688 A CN101570688 A CN 101570688A
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luminescent material
light
luminous
combination
light source
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CN101570688B (en
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王细凤
夏威
肖志国
辛易
温嘉琪
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Dalian Luming Science and Technology Group Co Ltd
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Dalian Luming Science and Technology Group Co Ltd
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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 or more 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

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 and be used for making the luminescent material that white light is and the red colour system light-emitting device is used that comprises semiconductor light-emitting elements (LED), it can be used as the ultraviolet of the emmission spectrum of excitation light source at 240～510nm---and the luminous element in green glow zone excites, absorb at least a portion emission 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 advantages such as less energy-consumption, long lifetime, volume be little, in light weight, and can eliminate the problem of environmental pollutions that objectionable impurities caused such as mercury in the luminescent lamp, more and more be subjected to people's attention.
This technology is by updating, and development realizes that with luminescent material the mode of white light has two kinds so far, promptly 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 bad problem of the not high or aging attenuation characteristic of luminous efficiency.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, is line spectrum but excite with emmission spectrum, and is bigger for the selectivity of led chip;
(3) tungstate rouge and powder: luminous efficiency is higher, is line spectrum but excite with emmission spectrum, and is bigger for the selectivity of led chip;
(4) nitrogenous compound rouge and powder: this rouge and powder is the most stable at present and luminous efficiency rouge and powder preferably, but complex manufacturing technology, and it is higher only to do cost, 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 approaching document and patent have 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 the 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, the tangible reducing atmosphere of this material is synthetic down, 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 making the green emitting phosphor that flat display apparatus uses, 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 applicant patent of application early, 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, the main just chemical expression formula of its spy 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 among the Zn; M is Al, Ga, Y, the combination of 1～3 kind of element among the Gd; R is Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, the combination of 1～3 kind of element among Tm and the 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 with Sm be 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 tangible 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, be badly in need of seeking the red illuminating material of a kind of luminous intensity height, stable chemical performance at present, can effectively be applied to the making of LED, particularly have 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, have the wide ranges of exciting (240～510nm), red-emitting (590～660nm), light conversion efficiency height, the luminescent material of ageing-resistant performance excellence; Another object of the present invention provides 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 among Mg, Ca, Sr, Ba, the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Sn, Y, Lu, Ga, Sb, Tb, Mn, the Pb; Lm is the combination of one or more element ions among Li, Na, K, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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, M is Mg in the chemical constitution expression (1), Ca, Sr, Ba, the combination of one or more elements among the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, the Mn; Lm is the combination of one or more element ions among Li, Na, K, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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, M is Mg in the chemical constitution expression (1), Ca, Sr, Ba, the combination of one or more elements among the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, the Mn; Lm is the combination of one or more element ions among Li, Na, K, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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, M is Mg in the chemical constitution expression (1), Ca, Sr, Ba, the combination of one or more elements among the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, the Mn; Lm is the combination of one or more element ions among Li, Na, K, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 the 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, M is Mg in the chemical constitution expression, Ca, Sr, Ba, the combination of one or more elements among the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, the Mn; Lm is the combination of one or both element ions among Li, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 the 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, M is Mg in the chemical constitution expression, Ca, Sr, Ba, the combination of one or more elements among the Zn; A is the combination of one or both elements among Y, the Gd; D is that the combination Ln of one or both element ions among Cl, the F is that the combination Lm of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sm, Lu, Tb, the Mn is the combination of one or both element ions among Li, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 the 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, M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; A is the combination of one or both elements among Y, the Gd; D is that the combination Ln of one or both element ions among Cl, the F is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the Ag; Mole coefficient a=1,0.001＜b≤1; 0.001≤β＜0.2, γ=12,0＜z＜0.1,0.001≤δ＜0.2.This material can by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 the 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, M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; A is the combination of one or both elements among Y, the Gd; D is that the combination Ln of one or both element ions among Cl, the F is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 the 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, M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 in the green range with emission peak, be issued to rare one with the red emission spectrum of upward peak in 590～660nm scope.This material can by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 in the green range with emission peak, 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 influences the wavelength and the luminous intensity of the emission peak of luminescent material.Kind by regulating its activator and content also can influence it and excites wavelength and luminous intensity with emmission spectrum in addition.
In the present invention, introducing element D, Ln and Lm also are important discovery and the innovations among the present invention, formed clad aluminum silicate material is not seen relevant bibliographical information and patent application at present, and its purpose and effect are the luminous intensities that can improve luminescent material widely.
At application number is the patent of 200510078430.6 (publication number is CN1880404A), passes 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 the 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 of fluorescence enhanced.
At application number is the patent of 200710105748.8 (publication number is CN:101054520A), and the technical program is an activator by Eu and/or Mn, and Ln realizes that fluorescence strengthens, and has higher phototranstormation efficiency.In the technical program,, also realize that by introducing transition metal Y, Yb, Ga, Gd spectrographic is adjustable except that by the alkaline-earth metal.
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 emmission spectrum peak value of luminous element is in the UV-light of 240～510nm---in the green glow regional extent, and the wavelength Conversion of first luminescent spectrum of the described luminous element of at least a portion become to have at least more than one peak wavelength to be in the light-emitting device of the luminescent material of 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 at luminescent material as the luminous element of excitation light source---have the emission peak wavelength more than 1 in the green glow regional extent at least.
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 employed luminescent material has more than one at least.
Light-emitting device according to a preferred embodiment of the present invention, as the emmission spectrum peak value of the luminous element of excitation light source UV-light at 240～510nm---in the green range, it is any clad aluminum salt luminescent material of the present invention that employed luminescent material has more than one at least; At least a portion luminescent conversion 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 becomes different and has at least more than one peak wavelength to be in emmission spectrum in 590～660nm wavelength region, and to mix the back acquisition mixed white luminous with luminous and/or non-other one or more the fluorescent material of the present invention of luminous element 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 emmission spectrum peak value of the luminous element of excitation light source UV-light at 240～510nm---in the green range, it is any clad aluminum salt luminescent material of the present invention that employed luminescent material 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 mixes back acquisition emitting red light with luminous and/or non-other one or more the light-emitting phosphor of the present invention of luminous element.Obtaining emitting red light can be: when the luminous wave band difference of the chip of choosing and non-light-emitting phosphor intensity of the present invention are lower than material luminous intensity of the present invention or 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.
Emitting red light described in the present invention comprises pink, pigment look, pale pinkish purple, nearly emitting red light such as amber.
According to the light-emitting device of a preferred embodiment of the present invention, employed luminescent material also contains 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, employed luminescent material also contains 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, second luminescent material wherein and/or the 3rd luminescent material and/or the 4th luminescent material are: rare earth doped activated nitric oxide fluorescent powder, and/or rare earth doped activated Nitride phosphor, and/or rare earth doped activated halogen silicate phosphor powder, and/or rare earth doped activated silicate fluorescent powder, and/or rare earth doped activated aluminate fluorescent powder, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated sulphide fluorescent material, and/or rare earth doped activated oxide fluorescent powder, and/or rare earth doped activated oxysulfide phosphor, and/or the sour magnesium fluorescent material of doped with Mn activated fluorine arsenic (germanium), and/or rare earth doped activated borate fluorescent powder, and/or rare earth doped activated phosphate phosphor, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated titanate fluorescent powder, and/or rare earth doped activated thiogallate fluorescent material.
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 to make the LED of emitting red light, also can be used to make white luminous LED.
When making silicate luminescent material of the present invention, raw materials used is the compound of each element in the expression (1), generally select for use in the 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, a halogenide of using their representative elements respectively; The compound of D is halogenide, halate, sulfide, oxysulfide, a vitriol of using their representative elements respectively; The compound of Al is to use oxide compound, oxyhydroxide, halogenide, carbonate, vitriol, nitrate.Element mole proportioning is followed mole coefficient in raw materials used: 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 the calcination 3～20 hours of dry, grind, sieve afterwards under oxidation or protection of inert gas or weakly reducing atmosphere; wherein the scope of calcination temperature is 1300～1600 ℃; after the cooling; pulverize, sieving forms.
High-temperature solid phase reaction method is: do with planetary/fire ball grinding machine and mix or an amount of various starting material of wet mixing; then with the powder that mixes through the calcination 3～20 hours under oxidation or protection of inert gas or weakly reducing atmosphere of oven dry back; wherein the scope of calcination temperature is 1300～1600 ℃; after the cooling; pulverize, sieving forms.
High-temperature solid phase reaction method also can adopt the method for twice firing: do with planetary/fire ball grinding machine and mix or an amount of various starting material of wet mixing, then the powder that mixes is taked the method for secondary calcination, wherein the condition of calcination for the first time is: in oxidation or weakly reducing atmosphere, calcination time is 2-10 hour, and temperature is 1000-1300 ℃; The condition of calcination for the second time is: in oxidation or weakly reducing atmosphere, calcination time is 2-20 hour, and calcination temperature is 1000-1600 ℃, after the cooling, pulverizes, and sieving forms.
In the present invention, adopt high temperature solid-state method to prepare this redness aluminate luminescent material, in order to make each starting material thorough mixing even, can adopt wet ball grinding to mix, ball-milling medium can be organic solvents such as alcohol, acetone, Virahol, also can be deionized water; Also can adopt dry ball milling to mix, ball mill can use high speed ball mill, also can adopt planetary fire ball grinding machine.
In the present invention, adopt high temperature solid-state method to prepare this redness aluminate luminescent material,, can in raw material, add other compounds of a small amount of (0%～30%), as NH in order to improve the quality of material 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.
The excitation spectrum of luminescent material and emmission spectrum adopt the test of F-4500 fluorescence spectrophotometer among the present invention.
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 excites and emmission spectrum for 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;
Fig. 4 embodiment 4 excites and emmission spectrum figure.
Fig. 5 embodiment 5 excites and emmission spectrum figure.
Fig. 6 comprises semiconductor light emitting 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 the semiconductor light emitting chip, luminescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes.Figure b is the mode of luminescent material and the indirect contact of semiconductor light emitting chip, and luminescent material is evenly distributed on epoxy skins.Figure c is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.Figure d is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material mixes the back film forming form of preparation and is covered on the semiconductor light emitting chip again with transparent medium.
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 by weighing 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 2The boric acid of adding 0.2% is fusing assistant, after fully ball milling mixes, pack in 99 porcelain crucibles, 1000 ℃ are incubated 6 hours under oxidizing atmosphere, cooling is ground the back in the following 1580 ℃ of insulations of oxygen atmosphere 4 hours, after the sintered compact cooling, the chemical constitution that pulverize, sieve, classification promptly obtains among the present invention is Ca (Al 0.995Gd 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:
Preparation process making according to embodiment 1 consists 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:
Preparation process making according to embodiment 1 consists 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:
Preparation process making according to embodiment 1 consists 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:
Preparation process making according to embodiment 1 consists 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:
Preparation process making according to embodiment 1 consists 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:
Preparation process making according to embodiment 1 consists 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 by weighing 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 the certain density nitric acid, with the preparation solution A, the aluminum nitrate with respective amount is dissolved in the deionized water then, with the preparation solution B; Again solution A is stirred in solution B, and adds an amount of ammoniacal liquor, regulate about its pH value to 9, then at 70 ℃ of about 3-8 of this solution of following continuously stirring hours; So that make mixing solutions generate gel; With the resulting gel drying of aforesaid method, 900 ℃ of following calcinations 60 minutes, make the desiccant gel that is obtained be decomposed to form oxide products then, promptly obtain presoma.In presoma, add CaF then 2, grind and evenly to be placed in the crucible, calcination 6 hours under 1400 ℃ of temperature under the weakly reducing atmosphere; Block after the calcination is ground classification, the Ca of 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 among the present invention, particularly use is packaged into warm white and red LED as the semiconductor LED of emission main peak in 250～510nm scope of the luminous element of excitation light source use.In the present invention, what packaged type can be among Fig. 6 is several: wherein scheme a and be the mode that luminescent material and semiconductor light emitting chip directly contact, luminescent material with evenly be coated on the semiconductor light emitting chip, among the reflector after transparent resin mixes.Figure b is the mode of luminescent material and the indirect contact of semiconductor light emitting chip, and luminescent material is evenly distributed on epoxy skins.Figure c is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material is evenly distributed among the Resins, epoxy, on the semiconductor light emitting chip.Figure d is the mode of luminescent material semiconductor light emitting chip indirect contact, and luminescent material mixes the back film forming form of preparation and is covered on the semiconductor light emitting chip again with transparent medium.
Illustrated with specific embodiment below.
Embodiment 9: one of manufacturing of white light LEDs
SrS:Eu with proper ratio 2+The fluorescent orange 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 invention 2, is dispersed in the Resins, epoxy, evenly is coated on purple light (emission wavelength the is 390-395nm) chip.To put the lead-in wire cup of glue, after putting into vacuum drying oven and solidifying, inserting to irritate has in the mould of Resins, epoxy, solidifies finally demould again through vacuum drying oven.Its encapsulation is (semiconductor light emitting chip 1, negative electrode 2, positive electrode 3, pin 4, luminescent material 5, packaged material 6, lead-in wire 7, reflection cup 8) shown in a among Fig. 6.Various powder send after the ultraviolet chip excites red, green, the mashed compound white light that goes out, 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 among Fig. 6 to prepare white light LEDs, with the red clad aluminum salt luminescent material and the mixed of the Yellow luminous material of YAG according to 93: 7 of the embodiment of the invention 1, selection blue light (emission wavelength is 457.5-460nm) chip is as source of radiation.Packaging process is with embodiment 10, but luminescent material is evenly distributed on epoxy skins, the emission spectrum of this white light LEDs be by above-mentioned luminescent material be subjected to respectively that blue chip launches blue-light excited after redness, the Yellow luminous white light that is composited launched respectively.The chromaticity coordinate of its encapsulation back 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 among Fig. 6 to prepare red LED, the red illuminating material of an amount of embodiment of the invention 3 is dispersed in the Resins, epoxy, evenly be coated on purple light (emission wavelength the is 390-395nm) chip.Packaging process is with embodiment 30, and chromaticity coordinate of its encapsulation back 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 among Fig. 6 to prepare red LED, with an amount of green luminescent material (Ca, Sr, Ba) Al 2O 4: Eu 2+The red illuminating material that reaches the embodiment of the invention 5 is dispersed in the Resins, epoxy, evenly is coated on purple light (emission wavelength the is 390-395nm) chip.Packaging process is with embodiment 10, and the chromaticity coordinate of its encapsulation back 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 among Fig. 6 to prepare pink LED, the red illuminating material of an amount of embodiment of the invention 1 is dispersed in the Resins, epoxy, evenly be coated on green glow (emission wavelength the is 500-505nm) chip.Packaging process is with embodiment 10, and the chromaticity coordinate of its encapsulation back 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 among Fig. 6 to prepare amber LED, with an amount of green luminescent material (Ca, Sr, Ba, Zn) 2SiO 4: Eu 2+The red illuminating material that reaches the embodiment of the invention 1 is dispersed in the Resins, epoxy, evenly is coated on blue light (emission wavelength the is 455-457.5nm) chip.Packaging process is with embodiment 10, and the chromaticity coordinate of its encapsulation back LED is X=0.4502, Y=0.2213, for amber luminous.
The luminous efficiency of clad aluminum salt luminescent material stable chemical performance of the present invention, anti-aging property excellence, emitting red light and all be better than existing technical scheme for the characteristics such as adaptability of chip.

Claims (22)

1. the luminescent material of an emitting red light particularly comprises the luminescent material that the light-emitting device of LED is used, and it 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 among Mg, Ca, Sr, Ba, the Zn; A is the combination of one or both elements among Y, the Gd; D is the combination of one or both element ions among Cl, the F; Ln is the combination of one or more element ions among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, Bi, Sn, Lu, Sb, Tb, the Pb; Lm is the combination of one or more element ions among Li, Na, K, the 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 by as the emmission spectrum of excitation light source 240～510nm ultraviolet---the luminous element in green glow zone excites, absorb at least a portion emission 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 mole coefficient 0＜x＜0.25,0＜y＜0.25 in the chemical constitution expression.
5. according to the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that Lm is the combination of one or both element ions among Li, the Ag in the chemical constitution expression; 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 the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that Lm is the combination of one or both element ions among Li, the Ag in the chemical constitution expression; 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 the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; Ln is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the Ag; Mole coefficient a=1,0.001＜b≤1; 0.001≤β＜0.2, γ=12.
8. according to the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; Ln is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the Ag; Mole coefficient a=0,0.8≤b≤2; 0.001≤β＜0.2, γ=12.
9. according to the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that M is Mg in the chemical constitution expression, Ca, the combination of one or more elements among the Sr; Ln is the combination of one or more element ions among Nd, Dy, Ho, La, Ce, Er, Pr, the Bi; Lm is the combination of one or both element ions among Li, the Ag; Mole coefficient a=1, b=1; 0.001≤β＜0.2, γ=12.
10. according to the luminescent material of claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that, described clad aluminum salt luminescent material is by the UV-light at 240～510nm---the optical excitation of the excitation light source in the green range with emission peak, be issued to rare one with the emmission spectrum of upward peak in 590～660nm scope.
11. luminescent material according to claim 1,2,3 or 4 described a kind of emitting red lights, it is characterized in that, described clad aluminum salt luminescent material is by the UV-light at 240～510nm---the optical excitation of the excitation light source in the green range with emission peak, and the emission peak wavelength of luminescent material is greater than the wavelength of the long wave side emission peak of excitation light source.
12. a 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, it is characterized in that:
The emmission spectrum peak value of luminous element is in the UV-light of 240～510nm---in the green glow regional extent, and the wavelength Conversion of first luminescent spectrum of the described luminous element of at least a portion become to have at least more than one peak wavelength to be in the light-emitting device of the luminescent material of second emmission spectrum in 590～660nm wavelength region, it is any one described clad aluminum salt luminescent material in the claim 1～11 that described luminescent material has more than one at least.
13. light-emitting device as claimed in claim 12 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 the emission peak wavelength more than 1 in the green glow regional extent at least.
14. as claim 12 or 13 described light-emitting devices, the luminescent layer that it is characterized in that described luminous element is nitride-based semiconductor or has the nitride-based semiconductor that contains In.
15., it is characterized in that it is any one described clad aluminum salt luminescent material in the claim 1～11 that employed luminescent material has more than one at least as claim 12 or 13 described light-emitting devices.
16. light-emitting device as claimed in claim 12, it is characterized in that as the emmission spectrum peak value of the luminous element of excitation light source UV-light at 240～510nm---in the green range, it is any one described clad aluminum salt luminescent material in the claim 1～11 that employed luminescent material has more than one at least; At least a portion luminescent conversion that luminescent material absorbs other fluorescent material in the luminous and/or combination of at least a portion of excitation light source becomes different and has at least more than one peak wavelength to be in emmission spectrum in 590～660nm wavelength region, and to mix the back acquisition mixed white luminous with one or more fluorescent material luminous of the luminous of luminous element and/or other.
17. light-emitting device as claimed in claim 12, it is characterized in that as the emmission spectrum peak value of the luminous element of excitation light source UV-light at 240～510nm---in the green range, it is any one described clad aluminum salt luminescent material in the claim 1～11 that employed luminescent material has more than one at least; 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 with one or more the luminous back acquisition emitting red light that mixes of fluorescent material of the luminous of luminous element and/or other.
18. as claim 12,13,16 or 17 described light-emitting devices, described luminescent material, also contain second luminescent material that together uses with any one described more than one clad aluminum salt luminescent material in the claim 1～11, 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 the described claim 1～11 and luminous element compound go out white luminous.
19. as claim 12,13,16 or 17 described light-emitting devices, described luminescent material, also contain second luminescent material that together uses with any one described more than one clad aluminum salt luminescent material in the claim 1～11, 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 the described claim 1～11 and luminous element is compound.
20. as claim 12,13,16 or 17 described light-emitting devices, it is characterized in that described second luminescent material and/or the 3rd luminescent material and/or the 4th luminescent material are: rare earth doped activated nitric oxide fluorescent powder, and/or rare earth doped activated Nitride phosphor, and/or rare earth doped activated halogen silicate phosphor powder, and/or rare earth doped activated silicate fluorescent powder, and/or rare earth doped activated aluminate fluorescent powder, and/or the fluorescent material of rare earth doped activated garnet structure, and/or rare earth doped activated sulphide fluorescent material, and/or rare earth doped activated oxide fluorescent powder, and/or rare earth doped activated oxysulfide phosphor, and/or the sour magnesium fluorescent material of doped with Mn activated fluorine arsenic (germanium), and/or rare earth doped activated borate fluorescent powder, and/or rare earth doped activated phosphate phosphor, and/or rare earth doped activated halogen-phosphate fluorescent material, and/or rare earth doped activated titanate fluorescent powder, and/or rare earth doped activated thiogallate fluorescent material.
21., 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 as claim 12,13,16 or 17 described light-emitting devices.
22., 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 as claim 12,13,16 or 17 described light-emitting devices
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CN106947481A (en) * 2017-03-29 2017-07-14 江苏师范大学 A kind of red Illuminant nanometer fluorescent material of europium ion activation, preparation method and application
CN108417701A (en) * 2018-01-24 2018-08-17 厦门信达光电物联科技研究院有限公司 A kind of preparation method of white light LEDs health light source
CN114891507A (en) * 2022-04-28 2022-08-12 东南大学 Far-red fluorescent powder material for LED and preparation method thereof

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CN106947481A (en) * 2017-03-29 2017-07-14 江苏师范大学 A kind of red Illuminant nanometer fluorescent material of europium ion activation, preparation method and application
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
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