CN109301058B - Phosphor mixture and light-emitting device thereof - Google Patents
Phosphor mixture and light-emitting device thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 154
- 238000001228 spectrum Methods 0.000 claims abstract description 22
- 230000005284 excitation Effects 0.000 claims description 29
- 238000009877 rendering Methods 0.000 claims description 23
- 229910052712 strontium Inorganic materials 0.000 claims description 22
- 229910052788 barium Inorganic materials 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 102100032047 Alsin Human genes 0.000 claims description 4
- 101710187109 Alsin Proteins 0.000 claims description 4
- 230000002596 correlated effect Effects 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 27
- 238000000295 emission spectrum Methods 0.000 description 27
- 238000004806 packaging method and process Methods 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- -1 rare earth aluminate Chemical class 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
The invention provides a full-spectrum fluorescent mixture and a light-emitting device manufactured by using the fluorescent composition.
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to phosphor blends for LED light source conversion, and more particularly, to a phosphor blend for converting a violet LED to a white light source for lighting applications and a light emitting device thereof.
[ background of the invention ]
The current LED white light emitting device is formed by combining a blue LED excited yellow phosphor. The phosphor absorbs a part of the LED radiation and converts it into yellow to mix the color, and can emit white light, but the spectral radiation intensities of the blue-green and red portions in the white spectrum cannot be sufficiently obtained, and the color reduction degree of the object to be illuminated is poor, that is, the color rendering index is low.
The light-emitting device of patent No. 201710382217.7 was applied to Nissan chemical industry Co., Ltd, and an LED violet chip (410-440nm) was used as an excitation light source to excite a mixture of five types of phosphors to emit white light.
The five phosphors are covered with a peak wavelength of 430-500nm, respectively, of the chemical formula (Ca, Sr, Ba)5(PO4)3(CL,Br):Eu2+The phosphor of (1); peak wavelength 440-550nm, chemical formula (Ca, Sr, Ba)4Al14O25:Eu2+And chemical formula (Ca, Sr, Ba)8MgSi4O16(F,Cl,Br)2:Eu2+The phosphor of (1); peak wavelength of 500-600nm, chemical formula (Y, Lu, Gd)3(Al,Ga)5O12：Ce3+(ii) a A peak wavelength of 610-650nm and a chemical formula of (Sr, Ca) AlSiN3:Eu2+The phosphor of (1); the peak wavelength is 610-650nm, and the chemical formula is 3.5Mg00.5MgF2GeO2：Mn4+The fluorescent powder of (1). The scheme is characterized in that continuous spectrum can be achieved in the 400-780nm wave band, the color rendering index Ra can be larger than 95, the special color rendering indexes R1-R15 can be larger than 90, and the effect of covering more continuous spectrum can be achieved.
However, this solution has the following disadvantages:
is made of (Ca, Sr, Ba)4Al14O25:Eu2+/(Ca,Sr,Ba)8MgSi4O16(F,Cl,Br)2:Eu2+The green phosphor is used as a luminescent material for green light emission, but the two green light emission luminescent materials have poor chemical stability due to the crystal structure, so that a luminescent device has large long-term light decay, and meanwhile, the matching efficiency between the phosphors is low and the spectrum coverage is still limited.
Therefore, there is a need to provide a new fluorescent powder with natural light emission and an LED light-emitting device.
[ summary of the invention ]
In order to solve the above problems, the present invention provides a phosphor mixture capable of emitting white light by excitation of a violet chip, which comprises the following specific schemes:
a fluorescent mixture, comprising:
a first phosphor, wherein the first phosphor comprises alkaline earth halophosphate activated by Eu, and the emission peak wavelength range of the first phosphor is 430-500 nm;
a second phosphor having a rare earth aluminate activated with Ce in the composition, the second phosphor having an emission peak wavelength range of 500-600 nm;
a third phosphor, wherein the composition of the third phosphor comprises calcium (strontium) aluminum silicon nitrogen activated by Eu, and the emission peak wavelength range of the third phosphor is 600-680 nm;
and the fourth phosphor is effectively excited by the light emitted by the first phosphor or the second phosphor, and the light emitting wavelength range of the fourth phosphor is 680-1200 nm.
Further wherein the first phosphor has a composition of: (Ca, Sr, Ba)5(PO4)3(Cl,Br):Eu2+。
Further wherein the first phosphor has a composition of: (Sr, Ba)5(PO4)3Cl:Eu2+。
Further, the second phosphor has the following composition: (Y, Lu)3(Al,Ga)5O12：Ce3+. The third phosphor has a composition of Eu-activated Ca (Sr) AlSiN with a chemical formula of (Ca, Sr) AlSiN3:Eu2+。
Further, the fourth phosphor composition includes rare earth gallium germano (silicate) activated with Cr.
Further, the fourth phosphor has the following composition: la3Ga5(Ge,Si)O14：Cr3+。
Further, the mass ratio of the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor satisfies: (20% -70%): (10% -65%): (1.5% -20%): (10% -40%).
Further, the mass ratio of the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor satisfies: (35% -65%): (10% -25%): (2% -6%): (18% -30%).
Further, glue is also included.
The invention also provides a light-emitting device comprising the fluorescent mixture.
Further, the light-emitting device comprises an LED violet chip or an ultraviolet chip as an excitation light source.
Further, the excitation light source has a peak wavelength of light emission in the range of 300-430 nm.
Further, the excitation light source has a peak wavelength of light emission in the range of 400-430 nm.
Furthermore, the spectrum of the light-emitting device covers a visible light region of 400-780nm and a near-infrared light region after 780 nm.
Further, the light emitting device has a general color rendering index Ra of more than 90.
Further, the light emitting device has an average color rendering index R1-R15 of greater than 90.
Further, the light emitting device has a correlated color temperature of 2500K to 8000K.
The invention has the beneficial effects that: the novel white light fluorescent mixture is provided, and the white light device prepared by applying the fluorescent mixture has full spectrum similar to natural light through the excitation of a purple light chip, so that the human eyes are better protected.
[ description of the drawings ]
FIG. 1 is a schematic cross-sectional view of a light-emitting device according to an embodiment of the present invention;
FIG. 2 is a 6500K spectrum test chart of the light-emitting device in embodiment 1 of the present invention;
FIG. 3 is a 5000K spectrum test chart of a light-emitting device in example 5 of the present invention;
FIG. 4 is a 4000K spectrum test chart of a light-emitting device in example 8 of the present invention;
FIG. 5 is a 2700K spectrum test chart of the light emitting device in embodiment 11 of the present invention;
FIG. 6 is a 6500K spectrum test chart of the light emitting device in embodiment 1 of the present invention and a spectrum test chart of comparative example 1.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to the following detailed description and accompanying fig. 1 to 5, so that aspects of the present invention and advantages thereof can be better understood. In the following examples, the following detailed description is provided to facilitate a more thorough understanding of the present disclosure and is not intended to limit the invention. Where words such as upper, lower, left, right, etc. indicate orientation, then only the position of the illustrated structure in the corresponding figure is considered.
Fig. 1 is a schematic cross-sectional view of a light-emitting device according to 1 embodiment of the present disclosure. In the present embodiment, the structure of a conventional light emitting device is described as an example, and for example, the light emitting device 100 includes: the light emitting chip comprises a substrate 10, a side wall 20 surrounding the substrate, and a cavity 40 for accommodating the light emitting chip 30 is enclosed by the substrate 10 and the side wall 20. The light emitting chip 30 is disposed on the substrate 10, and covers the fluorescent mixture 50 on the light emitting chip 30.
Specifically, the light-emitting chip 30 in the present embodiment employs, for example, a violet or ultraviolet excitation chip having an emission peak wavelength in a range of 300nm or more and 430nm or less. And a phosphor blend 50, wherein the phosphor blend 50 contains at least a first phosphor 51, a second phosphor 52, a third phosphor 53, and a fourth phosphor 54, wherein the first phosphor 51 has a blue phosphor having an emission peak wavelength in a range of 430nm or more and 500nm or less, and the first phosphor has a halogen element in its composition and is an alkaline earth phosphate activated with Eu. The second phosphor has an emission peak wavelength of 500-600nm and is a yellow-green phosphor, and the second phosphor composition contains, for example, a rare earth aluminate activated with Ce. The third phosphor is red phosphor with an emission peak wavelength of 600-680nm, and the third phosphor is, for example, calcium (strontium) aluminum silicon nitrogen with Eu-activated in the composition. The fourth phosphor is a near-infrared phosphor having an emission wavelength range of 680-1200nm, for example, a rare earth gallium germano (silicate) activated with Cr in the composition.
The light-emitting device 100 has a light-emitting element 30 having a specific emission peak wavelength and a fluorescent mixture 50 containing at least 4 specific phosphors and combined in a content ratio in a specific range, thereby making it possible to bring the emission spectrum of the light-emitting device 100 close to the spectrum of a reference light source in a very wide range from the short-wavelength side to the long-wavelength side of the visible light region involved in the calculation of the color-development evaluation number. Thereby, excellent color rendering properties can be achieved. In addition, by including the light emitting element 30 having an emission peak in a specific wavelength band, safety as a light source and high luminous efficiency can be realized.
Furthermore, the specific excitation chip 30 and the corresponding fluorescent mixture 50 can effectively improve the color rendering index Ra of the light emitting device.
The color rendering index Ra of sunlight is defined as 100, and the color rendering index of an incandescent lamp is very close to that of sunlight, and thus is considered as an ideal reference light source. The color rendering index of the light source is measured by comparing the degree of Deviation (development) of 8 colors under a test light source and a standard color sample with the same color temperature, and taking average Deviation value Ra20-100 as the highest value, wherein the larger the average color difference is, the lower the Ra value is. Light sources below 20 are generally not suitable for general use.
The light emitted by the light-emitting device 100 is a mixed light of the light-emitting element 30 and the fluorescence emitted by the fluorescent mixture 50, and can be, for example, a light whose chromaticity coordinates defined by CIE1931 are included in a range where x is 0.00 to 0.65 and y is 0.00 to 0.65, and can also be a light whose chromaticity coordinates defined by CIE1931 are included in a range where x is 0.25 to 0.40 and y is 0.25 to 0.40. The correlated color temperature of the light emitted by the light-emitting device 100 is, for example, 2000K or more or 2500K or more. The correlated color temperature is 8000K or less or 7500K or less.
In the present embodiment, the emission peak wavelength of the light-emitting chip 30 is in the range of 400nm or more and 430nm or less, and preferably in terms of light emission efficiency: 405-420 nm. The emission wavelength of the chip is shorter than 400nm, the luminous efficiency is influenced due to the influence of chip preparation technology, the wavelength of the chip is larger than 430nm, and the effect of exciting the first fluorescent powder by light emitted by the chip is poor due to deviation from the optimal excitation position of the first fluorescent powder.
By using the light-emitting chip 30 having an emission peak wavelength in this range as an excitation light source, the emission peak wavelength is on the longer wavelength side than the near ultraviolet region, and the ultraviolet component is small, so that the safety and the light emission efficiency as a light source are excellent.
The half-value width of the emission spectrum of the light-emitting chip 30 can be set to 30nm or less, for example.
A semiconductor light emitting element such as an LED is preferably used for the light emitting chip 30. By using a semiconductor light emitting element as a light source, the light emitting device 100 which has high efficiency, high linearity of output with respect to input, mechanical shock resistance, and stability can be obtained.
As the semiconductor light emitting chip, for example, a nitride semiconductor (In) is usedXAlYGa1-X-YN, where X and Y satisfy 0. ltoreq. X, 0. ltoreq. Y, X + Y. ltoreq.1), and a violet chip is selected as the semiconductor light-emitting element emitting blue, green, violet, or the like.
In the present embodiment, the fluorescent mixture 50 includes, for example, a first phosphor 51, a second phosphor 52, a third phosphor 53, a fourth phosphor 54, and a resin, which are arranged and mixed.
Among them, the first phosphor 51 absorbs the light emitted from the light emitting chip 30 and emits blue light, the second phosphor 52 emits yellow-green light, the third phosphor 53 emits red light, and the fourth phosphor 54 emits deep red and near-infrared light. Thus, by adjusting the proportions of the first phosphor 51, the second phosphor 52, the third phosphor 53, and the fourth phosphor 54, the light emission efficiency and the color rendering property of the light-emitting device 100 can be adjusted to fall within desired ranges.
Specifically, in the present embodiment, the first phosphor 51 has an emission peak wavelength in a range of 430nm or more and 500nm or less, and includes an alkaline earth phosphate which has a halogen element in its composition and is activated with Eu. The first phosphor 51 has, for example, the following composition (1):
(Ca，Sr，Ba)5(PO4)3(Cl，Br)：Eu2+ (1)
preferably, it has a composition of the following formula (2):
(Sr，Ba)5(PO4)3Cl:Eu2+ (2)
this makes it possible to obtain the respective emission characteristics of the first phosphor 51 described below relatively easily.
The effective excitation wavelength of the first phosphor 51 is, for example, 360nm or more and 440nm or less, and preferably 370nm or more and 430nm or less. The light can be efficiently excited in the range of the emission peak wavelength of the light-emitting chip 30. The emission peak wavelength of the first phosphor 51 is, for example, in the range of 430nm to 500nm, preferably 440nm to 480 nm. With this arrangement, the overlap of the emission spectrum of the first phosphor 51, the emission spectrum of the light-emitting chip 30, and the emission spectrum of the second phosphor 52 with respect to the emission spectrum of the light-emitting device 100, particularly in the blue region, is reduced. Furthermore, for the emission spectrum of the light emitting device 100, the emission spectrum of the first phosphor 51 and the emission spectrum of the light emitting chip 30 are used to make the emission intensity of the blue region from the light emitting chip 30 close to the reference light source, thereby effectively improving the color rendering property of the light emitting device 100.
The half-value width of the first phosphor 51 in the emission spectrum is, for example, 29nm or more and 49nm or less, and preferably 30nm or more and 44nm or less. By setting the half-value width range as described above, the color purity can be improved, the emission spectrum in the blue region can be made closer to the reference light source, and the color rendering property of the light-emitting device 100 can be further improved.
Specifically, in the present embodiment, the second phosphor 52 has an emission peak wavelength in a range of 500nm to 600nm, contains a rare earth aluminate activated with Ce in the composition, or a combination of both. The second phosphor 52 has, for example, the following formula (3):
(Y,Lu)3(Al,Ga)5O12：Ce3+ (3)
preferably, it has a composition of the following formula (4) or (5):
Y3(Al,Ga)5O12：Ce3+ (4)
Lu3Al5O12：Ce3+ (5)
the optimum excitation wavelength of the second phosphor 52 is, for example, 400nm to 480nm, preferably 420nm to 470 nm. The violet light emitted from the light emitting chip 30 can be used to excite the second phosphor, but since the violet light emitted from the light emitting chip 30 is not in the optimum excitation position of the second phosphor 52, the excitation effect is limited, but at this time, the blue light emitted from the first phosphor 51 can efficiently excite the second phosphor 52, and excellent emission effects of blue (green) light and green (yellow) light can be obtained by the efficient combination of the first phosphor 51 and the second phosphor 52.
The emission peak wavelength of the second phosphor 52 is, for example, in the range of 500nm to 580nm, preferably 520nm to 560 nm. With this arrangement, the overlap of the emission spectrum of the second phosphor 52, the emission spectrum of the light-emitting chip 30, and the emission spectrum of the first phosphor 51 with respect to the emission spectrum of the light-emitting device 100, particularly in the yellow-green region, is reduced. Furthermore, for the emission spectrum of the light emitting device 100, the emission spectrum of the second phosphor 52 and the emission spectrum of the light emitting chip 30 are utilized to make the emission intensity of the yellow-green region from the light emitting chip 30 close to the reference light source, thereby effectively improving the color rendering property of the light emitting device 100.
The half-value width of the second phosphor 52 in the emission spectrum is, for example, 80nm or more and 115nm or less, and preferably 90nm or more and 110nm or less. By setting the half-value width range as described above, the color rendering property can be improved, and the color rendering property of the light-emitting device 100 can be further improved by making the emission spectrum in the yellow region closer to the reference light source.
Specifically, in the present embodiment, the third phosphor 53 is a red phosphor having an emission peak wavelength in a range of 600nm or more and 680nm or less, for example, calcium (strontium) aluminum silicon nitrogen activated with Eu in the composition, and has the following composition (6):
(Ca1-x，Srx)AlSiN3:Eu2+，0≤x≤0.9， (6)
the effective excitation wavelength of the third phosphor 53 is, for example, 400nm or more and 500nm or less, and preferably 400nm or more and 470nm or less. In the emission spectrum of the light-emitting device 100, particularly in the red region, the overlap between the emission spectrum of the third phosphor 53 and the emission spectrum of the light-emitting chip 30 and the emission spectrum of the fourth phosphor 54 is reduced. Furthermore, for the emission spectrum of the light emitting device 100, the emission spectrum of the third phosphor 53 and the emission spectrum of the light emitting chip 30 are used to make the emission intensity of the red region close to the reference light source, thereby effectively improving the color rendering property of the light emitting device 100.
Specifically, the invention also comprises a fourth phosphor 54, wherein the fourth phosphor is deep red and near infrared phosphor powder with the light-emitting wavelength within the range of 680-1200 nm. Such as rare earth gallium germanosilicate activated with Cr.
Having the following composition (7):
La3Ga5(Ge1-x,Six)O14：Cr3+，0≤x≤1 (7)
the light-emitting wavelength of the fourth phosphor 54 is utilized to effectively supplement the components of deep red and near infrared spectrum after 700nm in the white light device, and realize the full-spectrum LED similar to natural light.
The effective excitation wavelength of the fourth phosphor 54 is, for example, 400nm or more and 550nm or less, preferably 420nm or more and 550nm or less. The violet light emitted from the light emitting chip 30 can be used to excite the fourth phosphor, but since the violet light emitted from the light emitting chip 30 is not in the optimum excitation position of the fourth phosphor 54, the excitation effect is limited, but at this time, the blue light emitted from the first phosphor 51 or the yellow-green light emitted from the second phosphor can effectively excite the fourth phosphor 54, and by combining the first, second and fourth phosphors, excellent blue, yellow-green and deep-red emission effects can be obtained.
The mass ratio of the first phosphor to the second phosphor to the third phosphor to the fourth phosphor satisfies: (20% -70%): (10% -65%): (1.5% -20%): (10% -40%).
Further, the mass ratio of the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor satisfies: (35% -65%): (10% -25%): (2% -6%): (18% -30%). By controlling the proportion of each fluorescent powder in the optimized range, the white light effect similar to natural light can be realized after the light emitted by each fluorescent powder is combined.
In the present invention, the first phosphor 51, the second phosphor 52, the third phosphor 53, and the fourth phosphor 54 are mixed according to a certain mass ratio, and mixed with glue to prepare the fluorescent mixture 50, wherein the glue can be thermoplastic resin and thermosetting resin, and the thermosetting resin includes epoxy resin, silicone resin, epoxy modified silicone resin, and the like.
The fluorescent mixture 50 may also include other ingredients such as fillers such as silica, barium titanate, titanium oxide, aluminum oxide, light stabilizers, colorants, and the like. The content of the other components is, for example, 0.01 to 20 parts by mass based on the resin.
Examples and comparative examples
The following are examples of the present invention, but the present invention is not limited to these examples.
The LED chip selects a purple light LED chip with the emission peak wavelength of 405nm-420 nm.
The packaging glue is selected from silicone resin or silica gel.
The phosphor composition comprises:
selection of blue phosphor (Ca, Sr, Ba))5(PO4)3(Cl,Br,F):Eu2+；
Yellow-green phosphor selection (Y, Lu)3(Al,Ga)5O12:Ce3+；
La is selected as near-infrared fluorescent powder3Ga5(Ge,Si)O14：Cr3+
CaAlSiN for red fluorescent powder selection3:Eu2+
The ratio of the fluorescent powder to the packaging glue is 1: 0.8-1.5, the package support comprises: patch, COB, straight (flat, concave, etc.), high power, etc., but are not limited to these types.
Color temperature 6500K:
example 1
The LED chip selects a purple light LED chip with an emission peak wavelength of 410nm, the packaging glue selects silicon resin, and the fluorescent powder combination comprises: the blue fluorescent powder selects (Sr, Ba) with the emission peak wavelength of 450nm5(PO4)3Cl:Eu2+(ii) a Yellow green fluorescent powder selects Y with emission peak wavelength of 530nm3(Al,Ga)5O12:Ce3+(ii) a Near-infrared fluorescent powder selects La with emission peak wavelength 765nm3Ga5(Ge,Si)O14:Cr3+(ii) a CaAlSiN with red fluorescent powder selective emission peak wavelength of 650nm3:Eu2+. The mass ratio of the blue fluorescent powder to the yellow-green fluorescent powder to the near-infrared fluorescent powder to the red fluorescent powder is 58.2:13.5:25.2: 3.1. The mass ratio of the fluorescent powder to the packaging glue is 1: 0.8. the packaging support is in a surface mounting type.
Example 2
The LED chip selects a purple light LED chip with an emission peak wavelength of 415nm, the packaging glue selects silicon resin, and the fluorescent powder combination comprises: the blue fluorescent powder selects (Sr, Ba) with the emission peak wavelength of 450nm5(PO4)3Cl:Eu2+(ii) a Lu with emission peak wavelength of 535nm selected by yellow-green fluorescent powder3Al5O12:Ce3+(ii) a La with emission peak wavelength of 763nm selected by near-infrared fluorescent powder3Ga5(Ge,Si)O14:Cr3 +(ii) a Red fluorescent powder selective emission peak wavelength 655nm CaAlSiN3:Eu2+. The mass ratio of the blue fluorescent powder to the yellow-green fluorescent powder to the near-infrared fluorescent powder to the red fluorescent powder is 55:16.8:25.8: 2.6. The mass ratio of the fluorescent powder to the packaging glue is 1: 0.9. the packaging support is in a surface mounting type.
Example 3
The LED chip selects a purple light LED chip with an emission peak wavelength of 420nm, the packaging glue selects silicon resin, and the fluorescent powder combination comprises: the blue fluorescent powder selects (Sr, Ba) with the emission peak wavelength of 450nm5(PO4)3Cl:Eu2+(ii) a Yellow green fluorescent powder selects Y with emission peak wavelength of 532nm3(Al,Ga)5O12:Ce3+(ii) a Near-infrared fluorescent powder selects La with emission peak wavelength 765nm3Ga5(Ge,Si)O14:Cr3+(ii) a CaAlSiN with red fluorescent powder selective emission peak wavelength of 660nm3:Eu2+. The mass ratio of the blue fluorescent powder to the yellow-green fluorescent powder to the near-infrared fluorescent powder to the red fluorescent powder is 60:12.7:24.4: 2.9. The mass ratio of the fluorescent powder to the packaging glue is 1: 1. the packaging support is in a surface mounting type.
Comparative example 1
The LED chip selects a purple light LED chip with an emission peak wavelength of 420nm, the packaging glue selects silicon resin, and the fluorescent powder combination comprises: the blue fluorescent powder selects (Sr, Ba) with the emission peak wavelength of 450nm5(PO4)3Cl:Eu2+(ii) a Yellow green fluorescent powder selects Y with emission peak wavelength of 535nm3(Al,Ga)5O12:Ce3+(ii) a CaAlSiN with red fluorescent powder selective emission peak wavelength of 650nm3:Eu3+. The mass ratio is 74:22.6: 3.4. The mass ratio of the fluorescent powder to the packaging glue is 1: 0.95. the packaging support is in a surface mounting type.
The results of the tests on examples 1 to 3 according to the invention and comparative example 1 are shown in table 1.
Table 1: test results of examples 1 to 3 and comparative example 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Ra | 98.8 | 98 | 98.2 | 96.1 |
| R1 | 99.6 | 98.6 | 99 | 97.9 |
| R2 | 98.9 | 97 | 97.4 | 96.2 |
| R3 | 97.9 | 97.7 | 98.8 | 93.7 |
| R4 | 97.3 | 972 | 96.1 | 95.2 |
| R5 | 98.9 | 98 | 98.3 | 97.4 |
| R6 | 99.4 | 96.8 | 97.2 | 95.9 |
| R7 | 99.2 | 97.1 | 97.1 | 96.1 |
| R8 | 99.2 | 97.3 | 98.2 | 96.3 |
| R9 | 99.1 | 96.9 | 99 | 95 |
| R10 | 98.2 | 94.6 | 97.4 | 90.6 |
| R11 | 95.5 | 96 | 98.8 | 95.5 |
| R12 | 96.5 | 98.7 | 98.3 | 93.9 |
| R13 | 99.2 | 97.9 | 98.5 | 97.2 |
| R14 | 98.7 | 97.8 | 98.8 | 96.2 |
| R15 | 99.4 | 98.3 | 98.9 | 97.4 |
| 750-900nm spectral coverage | Is provided with | Is provided with | Is provided with | Is not provided with |
As can be seen, the color rendering index Ra of the LED using the fluorescent powder provided by the invention is higher than that of the comparative example 1, and the spectral coverage of the near infrared region of 750-900nm is obviously enhanced. (see FIG. 2: spectra of example 1, FIG. 6: comparison of spectra of example 1 and comparative example 1.).
Color temperature 5000k:
examples 4 to 6 and comparative example 2 were designed corresponding to examples 1 to 3 and comparative example 1, and the specific formulations are shown in Table 2. The results of the tests on examples 4 to 6 according to the invention and comparative example 2 are shown in table 3.
Table 2: quality ratio table of examples 4 to 6 and comparative example 2
Table 3: test results of examples 4 to 6 and comparative example 2
| Example 4 | Example 5 | Example 6 | Comparative example 2 | |
| Ra | 98.3 | 98.1 | 98.1 | 95.8 |
| R1 | 98.9 | 98.5 | 99.1 | 98.7 |
| R2 | 99 | 99.2 | 98.6 | 97.5 |
| R3 | 96.4 | 96.3 | 96 | 92.8 |
| R4 | 97.1 | 96.7 | 96.9 | 94.6 |
| R5 | 98.9 | 98.6 | 98.8 | 98 |
| R6 | 99.4 | 99.5 | 98.9 | 97.1 |
| R7 | 98.6 | 98.4 | 98.3 | 95.7 |
| R8 | 98.3 | 97.6 | 98.1 | 96.1 |
| R9 | 98 | 96.2 | 98.3 | 99.1 |
| R10 | 97.3 | 97.7 | 96.5 | 92.9 |
| R11 | 95.8 | 95.3 | 95.7 | 90.5 |
| R12 | 96.7 | 97.2 | 96.5 | 93.3 |
| R13 | 99.2 | 98.9 | 99.2 | 99.5 |
| R14 | 97.6 | 97.5 | 97.4 | 95.3 |
| R15 | 99.5 | 98.9 | 99.7 | 98.4 |
| 750-900nm spectral coverage | Is provided with | Is provided with | Is provided with | Is not provided with |
As can be seen, the color rendering index Ra of the LED using the fluorescent powder provided by the invention is higher than that of the comparative example 2, and the spectral coverage of the near infrared region of 750-900nm is obviously enhanced. (see FIG. 3 spectrum of example 5).
Color temperature 4000K:
examples 7 to 9 and comparative example 3 were designed corresponding to examples 4 to 6 and comparative example 2, and the specific formulations are shown in Table 4. The results of the tests on examples 7 to 9 according to the invention and comparative example 3 are shown in table 5.
Table 4: quality proportioning table of examples 7-9 and comparative example 3
Table 5: test results of examples 7 to 9 and comparative example 3
Therefore, the color rendering index Ra of the LED using the fluorescent powder provided by the invention is higher than that of the comparative example 3, and the spectral coverage of the near infrared region of 750-900nm is obviously enhanced. (see FIG. 4 spectrum of example 8).
Color temperature 2700K:
examples 10 to 12 and comparative example 4 were designed corresponding to examples 7 to 9 and comparative example 3, and the specific formulations are shown in Table 6. The results of the tests on examples 10 to 12 of the present invention and comparative example 3 are shown in Table 7.
TABLE 6 quality ratio tables for examples 10 to 12 and comparative example 4
Table 7: test results of examples 10 to 12 and comparative example 3
As can be seen, the color rendering index Ra of the LED using the fluorescent powder provided by the invention is higher than that of the comparative example 4, and the spectral coverage of the near infrared region of 750-900nm is obviously enhanced. (see FIG. 5 spectrum of example 11).
According to the invention, the deep red and near infrared fluorescent powder is added into the fluorescent powder, so that the fluorescent powder mixture can obtain a spectrum containing natural light with the wavelength of more than 700nm, and the waveband with the wavelength of more than 700nm has a good protection effect on human eyes, so that the fluorescent powder has a good market prospect.
In the above-mentioned embodiments of the present invention, since the relative amount of the phosphor is influenced by the manufacturing process, the particle size, the content of the activator, and the like, the ratio of the phosphors used in the embodiments of the present invention can be used as a reference, not an absolute ratio.
While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (11)
1. A phosphor blend, comprising:
a first phosphor having (Ca, Sr, Ba) in the composition5(PO4)3(Cl,Br):Eu2+The light-emitting peak wavelength range of the first phosphor is 430-500 nm;
a second phosphor having a composition of (Y, Lu)3(Al,Ga)5O12:Ce3+The wavelength range of the light-emitting peak of the second phosphor is 500-600 nm;
a third phosphor having (Sr, Ca) AlSiN in the composition3:Eu2+The wavelength range of the emission peak of the third phosphor is 600-680 nm;
a fourth phosphor having La in the composition3Ga5(Ge,Si)O14:Cr3+The fourth phosphor is effectively excited by the light emitted by the first phosphor or the second phosphor, and the light-emitting wavelength range of the fourth phosphor is 760-1200 nm;
the first phosphor is the same as the first phosphor in terms of (Ca, Sr, Ba)5(PO4)3(Cl,Br):Eu2+The effective excitation wavelength is 360-440 nm, and the half-width peak is 29-49 nm;
(Y, Lu) in the second phosphor3(Al,Ga)5O12:Ce3+The effective excitation wavelength is 400-480 nm, and the half-width peak is 90-110 nm;
the (Sr, Ca) AlSiN in the third phosphor3:Eu2+The effective excitation wavelength of (A) is 400-500 nm;
the La of the fourth phosphor3Ga5(Ge,Si)O14:Cr3+The effective excitation wavelength of the light source is 400 nm-550 nm;
the phosphor mixture is applied to LED illumination, and has a general color rendering index Ra of more than 90 and special color rendering indexes R1-R15 of more than 90.
2. The phosphor mixture of claim 1, wherein:
the first phosphor has (Sr, Ba)5(PO4)3Cl:Eu2+。
3. The phosphor mixture of claim 1, wherein:
the first phosphor is the same as the first phosphor in terms of (Ca, Sr, Ba)5(PO4)3(Cl,Br):Eu2+The effective excitation wavelength is 370 nm-430 nm, and the half-width peak is 30-44 nm;
(Y, Lu) in the second phosphor3(Al,Ga)5O12:Ce3+The effective excitation wavelength is 420-470 nm, and the half-width peak is 90-110 nm;
the (Sr, Ca) AlSiN in the third phosphor3:Eu2+The effective excitation wavelength of (A) is 400-470 nm;
the La of the fourth phosphor3Ga5(Ge,Si)O14:Cr3+The effective excitation wavelength of (A) is 420 nm-550 nm.
4. The phosphor mixture of any of claims 1-3, wherein the mass ratio of the first phosphor, the second phosphor, the third phosphor, and the fourth phosphor satisfies: (20% -70%): (10% -65%): (1.5% -20%): (10% -40%).
5. A phosphor mixture according to any of claims 1 to 3, further comprising a glue.
6. A light-emitting device comprising the phosphor mixture according to any one of claims 1 to 5.
7. The light-emitting device according to claim 6, wherein the light-emitting device comprises an LED violet chip or an ultraviolet chip as an excitation light source.
8. The apparatus as claimed in claim 7, wherein the excitation light source has a peak wavelength of light emission within the range of 300-430 nm.
9. The apparatus as claimed in claim 8, wherein the excitation light source has a peak wavelength of light emission within the range of 400-430 nm.
10. The light-emitting device according to claim 6, wherein the spectrum of the light-emitting device covers a visible light region of 400-780nm and a near-infrared light region after 780 nm.
11. The lighting device of claim 6, wherein the lighting device has a correlated color temperature of 2500K to 8000K.
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| CN201811444819.1A CN109301058B (en) | 2018-11-29 | 2018-11-29 | Phosphor mixture and light-emitting device thereof |
| PCT/CN2018/118646 WO2020107425A1 (en) | 2018-11-29 | 2018-11-30 | Fluorescent mixture and light-emitting device thereof |
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| JP7323787B2 (en) * | 2019-07-31 | 2023-08-09 | 日亜化学工業株式会社 | Lighting device and lighting device with infrared camera |
| CN112310263B (en) * | 2019-08-02 | 2022-04-05 | 江苏博睿光电有限公司 | Full-spectrum LED light source |
| CN110635013A (en) * | 2019-09-20 | 2019-12-31 | 深圳市长方集团股份有限公司 | Full-spectrum cold-white LED light source excited by purple light |
| CN111129263A (en) * | 2019-12-30 | 2020-05-08 | 北京宇极芯光光电技术有限公司 | White light LED light source with infrared band added in spectrum |
| WO2022181372A1 (en) * | 2021-02-24 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Light emitting device and electronic apparatus using same |
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| CN101331206A (en) * | 2005-12-27 | 2008-12-24 | 化成欧普东尼克斯株式会社 | Blue light emitting alkaline earth chlorophosphate phosphor for cold cathode fluorescent lamp, cold cathode fluorescent lamp, and color liquid crystal display device |
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| CN108559491B (en) * | 2018-05-16 | 2019-05-28 | 广东旭宇光电有限公司 | Full spectrum fluorescent powder, Quan Guangpu diode and full spectrum plant lamp |
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| CN1621491A (en) * | 2003-11-28 | 2005-06-01 | 上海师范大学 | Rare-earth blue luminescent materials, preparation method and use thereof |
| CN101331206A (en) * | 2005-12-27 | 2008-12-24 | 化成欧普东尼克斯株式会社 | Blue light emitting alkaline earth chlorophosphate phosphor for cold cathode fluorescent lamp, cold cathode fluorescent lamp, and color liquid crystal display device |
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