CN109301058A - Phosphor mixture and light-emitting device thereof - Google Patents
Phosphor mixture and light-emitting device thereof Download PDFInfo
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- CN109301058A CN109301058A CN201811444819.1A CN201811444819A CN109301058A CN 109301058 A CN109301058 A CN 109301058A CN 201811444819 A CN201811444819 A CN 201811444819A CN 109301058 A CN109301058 A CN 109301058A
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- fluorophor
- emitting device
- light emitting
- light
- fluorescent
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 16
- 238000001228 spectrum Methods 0.000 claims abstract description 54
- 230000005284 excitation Effects 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 229910052712 strontium Inorganic materials 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- -1 aluminium silicon nitrogen Chemical compound 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims description 3
- 230000002596 correlated effect Effects 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 description 62
- 230000000052 comparative effect Effects 0.000 description 27
- 238000004020 luminiscence type Methods 0.000 description 23
- 238000009877 rendering Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229920002050 silicone resin Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 241000736199 Paeonia Species 0.000 description 4
- 235000006484 Paeonia officinalis Nutrition 0.000 description 4
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical compound [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 238000005457 optimization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 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
- 230000003595 spectral effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- 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]
It is particularly a kind of that purple LED is converted to illumination the present invention relates to the phosphor blends of LED light source conversion
The phosphor blends and its light emitting device of the white light source of application.
[background technique]
LED white light emitting device at present is to be composed blue led excitation yellow fluorophor.The fluorophor absorbs one
The radiant light of part LED, which is converted into yellow, which carries out colour mixture, can issue the light of white color system, but in the spectrum of white colours, Wu Fachong
Get the spectral radiance of blue-green and RED sector, poor so as to cause the color reduction degree of illuminated object, i.e. colour developing refers to
Number is lower.
Nichia Chemical Industries, Ltd has applied for the light emitting device patent of Patent No. 201710382217.7, application
Scheme is that LED purple light chip (410-440nm) is used as excitation light source, and the mixture of five class fluorophor of excitation issues white light system
Light.
Its five kinds of fluorophor coverings are respectively a length of 430-500nm of spike, chemical formula (Ca, Sr, Ba)5(PO4)3(CL,
Br):Eu2+Fluorescent powder；The a length of 440-550nm of spike, chemical formula (Ca, Sr, Ba)4Al14O25:Eu2+With chemical formula (Ca, Sr,
Ba)8MgSi4O16(F,Cl,Br)2:Eu2+Fluorescent powder；The a length of 500-600nm of spike, chemical formula (Y, Lu, Gd)3(Al,Ga)5O12: Ce3+；The a length of 610-650nm of spike, chemical formula are (Sr, Ca) AlSiN3:Eu2+Fluorescent powder；The a length of 610- of spike
650nm, chemical formula 3.5Mg00.5MgF2GeO2: Mn4+Fluorescent powder.This Scheme Characteristics can be reached in 400-780nm wave band
To continuous spectrum, and colour rendering index Ra can be greater than 95, and special colour rendering index R1 to R15 can be greater than 90, can reach the more company of covering
The effect of continuous spectrum.
But the program has the disadvantage that
Using (Ca, Sr, Ba)4Al14O25:Eu2+/(Ca,Sr,Ba)8MgSi4O16(F,Cl,Br)2:Eu2+Green emitting phosphor
As the luminescent material of green emission, but two kinds of green emission fluorescent materials chemistry due to crystal structure aspect is steady
Qualitative poor, will lead to light emitting device, there are larger long-term light decays, while the cooperation efficiency between fluorescent powder is relatively low and light
Spectrum covering is still limited.
Therefore, it is necessary to provide a kind of new naturally photoemissive fluorescent powder of class and LED light emitting device.
[summary of the invention]
To solve the above-mentioned problems, the present invention provides a kind of fluorescence that can excite and issue white light using purple light chip
Body mixture, concrete scheme are as follows:
A kind of fluorescent mixture, which is characterized in that the fluorescent mixture includes:
First fluorophor, has the alkali earths halogen-phosphate activated with Eu in first fluorophor composition, and described first
The peak luminous wavelength range of fluorophor is 430-500nm；
Second fluorophor has the terres rares aluminate activated with Ce in second fluorophor composition, and described second is glimmering
The peak luminous wavelength range of body of light is 500-600nm；
Third fluorophor has calcium (strontium) the aluminium silicon nitrogen activated with Eu in third fluorophor composition, and the third is glimmering
The peak luminous wavelength range of body of light is 600-680nm；
4th fluorophor, the 4th fluorophor are effectively excited by the light of the first fluorophor or the second phosphor emission, institute
Stating the 4th light-emitting phosphor wave-length coverage is 680-1200nm.
Further, wherein first fluorophor has following composition: (Ca, Sr, Ba)5(PO4)3(Cl,Br):Eu2+。
Further, wherein first fluorophor has following composition: (Sr, Ba)5(PO4)3Cl:Eu2+。
Further, second fluorophor has following composition: (Y, Lu)3(Al,Ga)5O12: Ce3+.Third fluorophor
There is calcium (strontium) the aluminium silicon nitrogen activated with Eu, chemical formula is (Ca, Sr) AlSiN in composition3:Eu2+。
Further, have in the 4th fluorophor composition and germanium (silicon) hydrochlorate is sowed with the terres rares that Cr is activated.
Further, the 4th fluorophor has following composition: La3Ga5(Ge,Si)O14: Cr3+。
Further, first fluorophor, second fluorophor, the third fluorophor, the 4th fluorophor
Mass ratio meet: (20%-70%): (10%-65%): (1.5%-20%): (10%-40%).
Further, first fluorophor, second fluorophor, the third fluorophor, the 4th fluorophor
Mass ratio meet: (35%-65%): (10%-25%): (2%-6%): (18%-30%).
Further, it also include glue.
The present invention also proposes a kind of light emitting device, including fluorescent mixture proposed by the invention.
Further, the light emitting device includes using LED purple light chip or UV chip as excitation light source.
Further, the excitation light source has the peak luminous wavelength within the scope of 300-430nm.
Further, the excitation light source has the peak luminous wavelength within the scope of 400-430nm.
Further, the spectrum covering visible light region 400-780nm and later close red 780nm of the light emitting device
Outer smooth region.
Further, the light emitting device has the general colour rendering index Ra greater than 90.
Further, the light emitting device has the average color rendering index R1-R15 greater than 90.
Further, the light emitting device has the correlated colour temperature of 2500K to 8000K.
The beneficial effects of the present invention are: providing a kind of novel white fluorescence mixture, is excited, made by purple light chip
The full spectrum that there is class natural light using white light parts prepared by fluorescent mixture of the invention is obtained, is better achieved to human eye
Protection.
[Detailed description of the invention]
Fig. 1 is the diagrammatic cross-section of light emitting device in the embodiment of the present invention；
Fig. 2 is the 6500K spectrum test figure of light emitting device in the embodiment of the present invention 1；
Fig. 3 is the 5000K spectrum test figure of light emitting device in the embodiment of the present invention 5；
Fig. 4 is the 4000K spectrum test figure of light emitting device in the embodiment of the present invention 8；
Fig. 5 is the 2700K spectrum test figure of light emitting device in the embodiment of the present invention 11；
Fig. 6 is the spectrum test figure of the 6500K spectrum test figure of light emitting device and comparative example 1 in the embodiment of the present invention 1.
[specific embodiment]
Below by specific embodiment combination attached drawing 1 to attached drawing 5, invention is further described in detail, so as to
The advantages of more fully understanding the solution of the present invention and its various aspects.Below in an example, embodiment party in detail below is provided
The purpose of formula is easy for becoming apparent from thorough explanation to present disclosure, rather than limiting the invention.Wherein upper,
Under, the words of the indicating positions such as left and right be only for shown structure in respective figure for position.
Fig. 1 is the fragmentary cross sectional view of light emitting device involved in 1 embodiment disclosed by the invention.In the present embodiment with
It is illustrated for the structure of common luminescent device, such as light emitting device 100 has: substrate 10, the side wall 20 around substrate, base
Plate 10 and side wall 20 surround the cavity 40 for accommodating luminescence chip 30.Luminescence chip 30 is arranged on the substrate 10, is covered on this and shines
Fluorescence mixture 50 on chip 30.
Specifically, the luminescence chip 30 in the present embodiment is for example, by using in 300nm or more and 430nm range below has
The purple light or burst of ultraviolel chip of peak luminous wavelength.Fluorescence mixture 50, it is glimmering which includes at least first
Body of light 51, the second fluorophor 52, third fluorophor 53, the 4th fluorophor 54, wherein the first fluorophor 51 in 430nm or more and
500nm range below have peak luminous wavelength blue colour fluorescent powder, the first fluorophor composition in have halogen and with
The alkali earths phosphate of Eu activation.The peak luminous wavelength range of second fluorophor is 500-600nm, is yellowish green fluorescent powder,
For example with the terres rares aluminate activated with Ce in second fluorophor composition.Third fluorophor is to emit with 600-680nm
The red fluorescence powder of peak wavelength, third fluorophor are, for example, to have calcium (strontium) the aluminium silicon nitrogen activated with Eu in forming.4th is glimmering
Have in body of light, such as composition and germanium (silicon) hydrochlorate is sowed with the terres rares that Cr is activated, to be 680- with emission wavelength range
The near-infrared fluorescent powder of 1200nm.
By having the light-emitting component 30 with specific peak luminous wavelength and including at least 4 kinds of specific fluorophor
And the fluorescent mixture 50 being composed is matched with the content of specific range, so as to develop the color involved by the calculating of review number
Visible light region shortwave side to the extremely wide range of long wave side in make the luminescent spectrum of light emitting device 100 close to reference light
The spectrum in source.Brilliant colour rendering can be reached as a result,.In addition, there is shining for luminescence peak by the inclusion of in specific wave band
Element 30 is able to achieve safety and high luminous efficiency as light source.
In turn, the present embodiment can be promoted effectively luminous by specifically exciting chip 30 and corresponding fluorescent mixture 50
The colour rendering index Ra of device.
The colour rendering index Ra of sunlight is defined as 100, and the colour rendering index of incandescent lamp is accordingly regarded as managing very close to daylight
The reference light source thought.It is examined, is compared under testing light source and under the benchmark of same colour temperature with 8 kinds of chromas medium standard color samples
Deviation (Deviation) degree of this 8 color takes average deviation Ra20-100, to measure the colour rendering index of the light source with 100
For highest, average color difference is bigger, and Ra value is lower.Light source lower than 20 is normally unsuitable for general service.
The light that light emitting device 100 is issued is the colour mixture of the light of light-emitting component 30 and fluorescence that fluorescent mixture 50 is issued
Light, such as range of the chromaticity coordinate included in x=0.00 to 0.65 and y=0.00 to 0.65 of CIE1931 defined can be set as
Light, moreover it is possible to the chromaticity coordinate for being set as CIE1931 defined is included in the range of x=0.25 to 0.40 and y=0.25 to 0.40
Light.In addition, the correlated colour temperature for the light that light emitting device 100 is issued is, for example, 2000K or more or 2500K or more.In addition, related
Colour temperature is 8000K or less or 7500K or less.
In the present embodiment, the peak luminous wavelength of luminescence chip 30 is in 400nm or more and 430nm range below,
It for the angle of luminous efficiency, is preferably in: 405-420nm.Chip emission wavelength is shorter than 400nm, since chip prepares skill
The influence of art, luminous efficiency are affected, and chip wavelength is greater than 430nm, due to deviating from the best excitation position of the first fluorescent powder
It sets, the light of chip emission excites the first fluorescent powder less effective.
By will have the luminescence chip 30 of peak luminous wavelength to be used as excitation light source, peak luminous wavelength ratio in the range
Near ultraviolet region more leans on long wavelength side, and the ingredient of ultraviolet light is less, therefore safety as light source and luminous efficiency are outstanding.
The half breadth of the luminescent spectrum of luminescence chip 30 can for example be set as 30nm or less.
It is preferable to use the semiconductor light-emitting elements such as LED in luminescence chip 30.By the way that semiconductor light-emitting elements are used as light
Source can obtain high-efficient and output phase for the linear height of input, also mechanical resistant impact and stable light emitting device 100.
As semiconductor luminous chip, for example, by using nitride semiconductor (InXAlYGa1-X-YN, here, X and Y is full
Foot 0≤X, 0≤Y, X+Y≤1) issue blue, green, purple etc. light semiconductor light-emitting elements, select in the present invention
Purple light chip.
In the present embodiment, fluorescent mixture 50 is for example including the first fluorophor 51, the second fluorophor 52, third fluorophor
53, the 4th fluorophor 54 and resin configuration mix.
Wherein, the first fluorophor 51 absorbs the light and the light for issuing blue that luminescence chip 30 issues, the second fluorophor 52 hair
The light of yellow green out, third fluorophor 53 issue red light, and the 4th fluorophor 54 issues the light of peony and near-infrared.By
This can will send out by adjusting the ratio of the first fluorophor 51, the second fluorophor 52, third fluorophor 53, the 4th fluorophor 54
Luminous efficiency, the colour rendering of electro-optical device 100 are adjusted in desired extent.
Specifically, in the present embodiment, the first fluorophor 51 has in 430nm or more and 500nm range below has
Peak luminous wavelength, comprising in the composition with halogen and with the alkali earths phosphate of Eu activation.First fluorophor 51
As having such as following formula (1) to form:
(Ca, Sr, Ba)5(PO4)3(Cl, Br): Eu2+ (1)
Preferably, there is the composition such as following formula (2):
(Sr, Ba)5(PO4)3Cl:Eu2+ (2)
Each characteristics of luminescence of the first fluorophor 51 described below can be relatively easily obtained as a result,.
Effective excitation wavelength of first fluorophor 51 is, for example, 360nm or more and 440nm hereinafter, preferably 370nm or more
And 430nm or less.It efficiency can be excited well in the range of the peak luminous wavelength of above-mentioned luminescence chip 30.First fluorescence
The peak luminous wavelength of body 51 is preferably in 440nm or more and 480nm for instance in 430nm or more and 500nm range below
Range below.By so set, luminescent spectrum for light emitting device 100, especially for blue region, the first fluorescence
The luminescent spectrum of body 51 and the repetition of the luminescent spectrum of luminescence chip 30 and the luminescent spectrum of the second fluorophor 52 tail off.Into
And for the luminescent spectrum of light emitting device 100, utilize the luminescent spectrum of the first fluorophor 51 and shining for luminescence chip 30
Spectrum, so that the luminous intensity for being originated from the blue region of luminescence chip 30 effectively promotes light emitting device 100 close to reference light source
Colour rendering.
Half breadth in the luminescent spectrum of first fluorophor 51 is, for example, 29nm or more and 49nm hereinafter, preferably 30nm
Above and 44nm or less.By being set as the range of such half breadth, excitation purity can be promoted, the luminous light in blue region is made
Spectrum can more promote the colour rendering of light emitting device 100 close to reference light source.
Specifically, in the present embodiment, the second fluorophor 52 has in 500nm or more and 600nm range below has
Peak luminous wavelength, comprising having the combination comprising the terres rares aluminate activated with Ce or the two in the composition.Second is glimmering
Body of light 52 is for example formed with such as following formula (3):
(Y,Lu)3(Al,Ga)5O12: Ce3+ (3)
Preferably, there is the composition such as following formula (4) or (5):
Y3(Al,Ga)5O12: Ce3+ (4)
Lu3Al5O12: Ce3+ (5)
The maximum excitation wavelength of second fluorophor 52 is, for example, 400nm or more and 480nm hereinafter, preferably 420nm or more
And 470nm or less.The purple light that luminescence chip 30 emits can be used for exciting the second fluorophor, but due to the purple of the transmitting of luminescence chip 30
Light is not on the best excitation position of the second fluorophor 52, so stimulation effect is restricted, but the first fluorophor 51 at this time
The blue light of transmitting can effectively excite the second fluorophor 52, can by the efficient combination of the first fluorophor 51 and the second fluorophor 52
Obtain the launching effect of excellent indigo plant (green) light and green (Huang) light.
The peak luminous wavelength of second fluorophor 52 is preferably in for instance in 500nm or more and 580nm range below
520nm or more and 560nm range below.By so set, luminescent spectrum for light emitting device 100, especially for
Yellow green region, the luminescent spectrum of the second fluorophor 52 and the luminescent spectrum of luminescence chip 30 and the first fluorophor 51 shine
The repetition of spectrum tails off.In turn, for the luminescent spectrum of light emitting device 100, the luminescent spectrum of the second fluorophor 52 is utilized
With the luminescent spectrum of luminescence chip 30 so that being originated from the luminous intensity in the yellow green region of luminescence chip 30 close to reference light
Source effectively promotes the colour rendering of light emitting device 100.
Half breadth in the luminescent spectrum of second fluorophor 52 is, for example, 80nm or more and 115nm hereinafter, preferably
90nm or more and 110nm or less.By being set as the range of such half breadth, colour rendering can be promoted, is made in yellow area
Luminescent spectrum can more promote the colour rendering of light emitting device 100 close to reference light source.
Specifically, in the present embodiment, third fluorophor 53 has in 600nm or more and 680nm range below has
The red light fluorescent powder of peak luminous wavelength for example, has calcium (strontium) the aluminium silicon nitrogen activated with Eu in composition, have such as following formula (6)
Composition:
(Ca1-x, Srx)AlSiN3:Eu2+, 0≤x≤0.9, (6)
Effective excitation wavelength of third fluorophor 53 is, for example, 400nm or more and 500nm hereinafter, preferably 400nm or more
And 470nm or less.For the luminescent spectrum of light emitting device 100, especially for red area, the luminous light of third fluorophor 53
The repetition with the luminescent spectrum of the luminescent spectrum and the 4th fluorophor 54 of luminescence chip 30 is composed to tail off.In turn, for the dress that shines
It sets for 100 luminescent spectrum, using the luminescent spectrum of third fluorophor 53 and the luminescent spectrum of luminescence chip 30, so that red
The luminous intensity in region effectively promotes the colour rendering of light emitting device 100 close to reference light source.
It specifically, further include the 4th fluorophor 54 in the present invention, the 4th fluorophor is emission wavelength in 680-1200nm model
Peony and near-infrared fluorescent powder in enclosing.For example, have and germanium silicate is sowed with the terres rares that Cr is activated.
It is formed with such as following formula (7):
La3Ga5(Ge1-x,Six)O14: Cr3+, 0≤x≤1 (7)
Using the emission wavelength of the 4th fluorophor 54, effectively supplemented with peony later containing 700nm in white light parts
With near infrared spectrum ingredient, the full-spectrum LED of class natural light is realized.
Effective excitation wavelength of 4th fluorophor 54 be, for example, 400nm or more and 550nm hereinafter, it is preferred that 420nm or more and
550nm or less.The purple light that luminescence chip 30 emits can be used for exciting the 4th fluorophor, but due to the purple light of the transmitting of luminescence chip 30
It is not on the best excitation position of the 4th fluorophor 54, so stimulation effect will receive limitation, but the first fluorophor 51 at this time
The green-yellow light of the blue light of transmitting or the second phosphor emission can effectively excite the 4th fluorophor 54, by by first, second and
Four fluorescent powders are combined, and can get the launching effect of excellent blue light, green-yellow light, dark red light.
The mass ratio satisfaction of first fluorophor, second fluorophor, the third fluorophor, the 4th fluorophor:
(20%-70%): (10%-65%): (1.5%-20%): (10%-40%).
Further, first fluorophor, second fluorophor, the third fluorophor, the 4th fluorophor
Mass ratio meet: (35%-65%): (10%-25%): (2%-6%): (18%-30%).By by the ratio of each fluorescent powder
In this optimization range, each fluorescent powder issues the quality white light of achievable similar natural light after light combination for example control.
In the present invention, the first fluorophor 51, the second fluorophor 52, third fluorophor 53, the 4th fluorophor 54, according to one
Fixed mass ratio mixing, is equipped with glue and is modulated into fluorescent mixture 50, wherein glue can be thermoplastic resin and thermosetting
Change resin, wherein heat reactive resin is for example including epoxy resin, silicone resin, epoxy-modified silicone resin etc..
Fluorescent mixture 50 can also include that other ingredients, such as silica, barium titanate, titanium oxide, aluminium oxide etc. are filled out
Material, light stabilizer, colorant etc..The content of other ingredients such as accounts for the 0.01-20 mass parts of resin.
Examples and Comparative Examples
Hereinafter, being the embodiment of the present invention, but the present invention is not limited to these Examples.
The purple LED chip of LED chip selection emission peak wavelength 405nm-420nm.
Packaging plastic wet concentration selects silicone resin or silica gel.
Phosphor combination includes:
Blue colour fluorescent powder selects (Ca, Sr, Ba)5(PO4)3(Cl,Br,F):Eu2+；
Yellowish green fluorescent powder selects (Y, Lu)3(Al,Ga)5O12:Ce3+；
Near-infrared fluorescent powder selects La3Ga5(Ge,Si)O14: Cr3+
Red fluorescence powder selects CaAlSiN3:Eu2+
The ratio of fluorescent powder and encapsulation glue is 1:0.8-1.5, and package support includes: patch, COB, and straight cutting (tack, it is interior
It is recessed etc.), it is high-power etc., but it is not limited to these types.
Colour temperature 6500K:
Embodiment 1
LED chip selects the purple LED chip of emission peak wavelength 410nm, and packaging plastic wet concentration selects silicone resin, phosphor combination
It include: (Sr, the Ba) of blue colour fluorescent powder selection emission peak wavelength 450nm5(PO4)3Cl:Eu2+；Yellowish green fluorescent powder selection transmitting
The Y of the long 530nm of spike3(Al,Ga)5O12:Ce3+；The La of near-infrared fluorescent powder selection emission peak wavelength 765nm3Ga5(Ge,Si)
O14:Cr3+；The CaAlSiN of red fluorescence powder selection emission peak wavelength 650nm3:Eu2+.Blue colour fluorescent powder, yellowish green fluorescent powder,
Mass ratio is 58.2:13.5:25.2:3.1 between near-infrared fluorescent powder and red fluorescence powder.The matter of fluorescent powder and encapsulation glue
Amount ratio is 1:0.8.Package support selects patch type.
Embodiment 2
LED chip selects the purple LED chip of emission peak wavelength 415nm, and packaging plastic wet concentration selects silicone resin, phosphor combination
It include: (Sr, the Ba) of blue colour fluorescent powder selection emission peak wavelength 450nm5(PO4)3Cl:Eu2+；Yellowish green fluorescent powder selection transmitting
The Lu of the long 535nm of spike3Al5O12:Ce3+；The La of near-infrared fluorescent powder selection emission peak wavelength 763nm3Ga5(Ge,Si)O14:Cr3 +；The CaAlSiN of red fluorescence powder selection emission peak wavelength 655nm3:Eu2+.Blue colour fluorescent powder, yellowish green fluorescent powder, near-infrared
Mass ratio is 55:16.8:25.8:2.6 between fluorescent powder and red fluorescence powder.Fluorescent powder and the mass ratio for encapsulating glue are
1:0.9.Package support selects patch type.
Embodiment 3
LED chip selects the purple LED chip of emission peak wavelength 420nm, and packaging plastic wet concentration selects silicone resin, phosphor combination
It include: (Sr, the Ba) of blue colour fluorescent powder selection emission peak wavelength 450nm5(PO4)3Cl:Eu2+；Yellowish green fluorescent powder selection transmitting
The Y of the long 532nm of spike3(Al,Ga)5O12:Ce3+；The La of near-infrared fluorescent powder selection emission peak wavelength 765nm3Ga5(Ge,Si)
O14:Cr3+；The CaAlSiN of red fluorescence powder selection emission peak wavelength 660nm3:Eu2+.Blue colour fluorescent powder, yellowish green fluorescent powder,
Mass ratio is 60:12.7:24.4:2.9 between near-infrared fluorescent powder and red fluorescence powder.The quality of fluorescent powder and encapsulation glue
Ratio is 1:1.Package support selects patch type.
Comparative example 1
LED chip selects the purple LED chip of emission peak wavelength 420nm, and packaging plastic wet concentration selects silicone resin, phosphor combination
It include: (Sr, the Ba) of blue colour fluorescent powder selection emission peak wavelength 450nm5(PO4)3Cl:Eu2+；Yellowish green fluorescent powder selection transmitting
The Y of the long 535nm of spike3(Al,Ga)5O12:Ce3+；The CaAlSiN of red fluorescence powder selection emission peak wavelength 650nm3:Eu3+.Matter
Amount ratio is 74:22.6:3.4.The mass ratio of fluorescent powder and encapsulation glue is 1:0.95.Package support selects patch type.
It is as shown in table 1 for the test result of 1-3 of the embodiment of the present invention and comparative example 1.
Table 1: 1 test result of embodiment 1-3 and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 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 |
| The covering of 750-900nm spectrum | Have | Have | Have | No |
As it can be seen that the LED colour rendering index Ra using fluorescent powder proposed by the invention is high compared with comparative example 1, while 750-900nm
The spectrum covering of near infrared region is significant to be reinforced.(referring to referring to fig. 2: the spectrum of embodiment 1, Fig. 6: embodiment 1 and comparative example 1
Spectrum comparison.).
Colour temperature 5000k:
Design embodiment 4-6 corresponding with embodiment 1-3, comparative example 1, comparative example 2, specific formula is referring to table 2.For this
The test result of inventive embodiments 4-6 and comparative example 2 is as shown in table 3.
Table 2: 2 quality proportioning table of embodiment 4-6 and comparative example
Table 3: the test result of embodiment 4-6 and comparative example 2
| Embodiment 4 | Embodiment 5 | Embodiment 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 |
| The covering of 750-900nm spectrum | Have | Have | Have | No |
As it can be seen that the LED colour rendering index Ra using fluorescent powder proposed by the invention is high compared with comparative example 2, while 750-900nm
The spectrum covering of near infrared region is significant to be reinforced.(referring to the spectrum of Fig. 3 embodiment 5).
Colour temperature 4000K:
Design embodiment 7-9 corresponding with embodiment 4-6, comparative example 2, comparative example 3, specific formula is referring to table 4.For this
The test result of inventive embodiments 7-9 and comparative example 3 is as shown in table 5.
Table 4: 3 quality proportioning table of embodiment 7-9 and comparative example
Table 5: the test result of embodiment 7-9 and comparative example 3
As it can be seen that the LED colour rendering index Ra using fluorescent powder proposed by the invention is high compared with comparative example 3, while 750-900nm
The spectrum covering of near infrared region is significant to be reinforced.(spectrum of embodiment 8 referring to fig. 4).
Colour temperature 2700K:
Design embodiment 10-12 corresponding with embodiment 7-9, comparative example 3, comparative example 4, specific formula is referring to table 6.For
The test result of 10-12 of the embodiment of the present invention and comparative example 3 is as shown in table 7.
4 quality proportioning table of 6 embodiment 10-12 of table and comparative example
Table 7: the test result of embodiment 10-12 and comparative example 3
As it can be seen that the LED colour rendering index Ra using fluorescent powder proposed by the invention is high compared with comparative example 4, while 750-900nm
The spectrum covering of near infrared region is significant to be reinforced.(referring to the spectrum of Fig. 5 embodiment 11).
The present invention enables phosphor blends by way of adding peony and near-infrared fluorescent powder in fluorescent powder
It is enough to obtain the class natural light spectrum comprising 700nm or more, since 700nm above band has good protective effect to human eye,
Therefore, fluorescent powder of the invention will have good market prospects.
The embodiment of invention described above, since the relative usage of fluorescent powder is contained by processing procedure, partial size, activator
The influence of the factors such as amount, so the ratio of each fluorescent powder used in the embodiment of the present invention can be used as reference, non-absolute ratio
Value.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
It encloses.
Claims (16)
1. a kind of fluorescent mixture, which is characterized in that the fluorescent mixture includes:
First fluorophor has the alkali earths halogen-phosphate activated with Eu, first fluorescence in first fluorophor composition
The peak luminous wavelength range of body is 430-500nm；
Second fluorophor has the terres rares aluminate activated with Ce, second fluorophor in second fluorophor composition
Peak luminous wavelength range be 500-600nm；
Third fluorophor has (calcium, strontium) the aluminium silicon nitrogen activated with Eu, the third fluorophor in third fluorophor composition
Peak luminous wavelength range be 600-680nm；
4th fluorophor, the 4th fluorophor are effectively excited by the light of the first fluorophor or the second phosphor emission, and described
Four light-emitting phosphor wave-length coverages are 680-1200nm.
2. fluorescent mixture according to claim 1, which is characterized in that wherein first fluorophor has such as the following group
At: (Ca, Sr, Ba)5(PO4)3(Cl,Br):Eu2+。
3. fluorescent mixture according to claim 3, which is characterized in that wherein first fluorophor has such as the following group
At: (Sr, Ba)5(PO4)3Cl:Eu2+。
4. fluorescent mixture according to claim 1, which is characterized in that second fluorophor has following composition: (Y,
Lu)3(Al,Ga)5O12: Ce3+。
5. fluorescent mixture according to claim 1, which is characterized in that have in the 4th fluorophor composition and swashed with Cr
Terres rares living sows germanium (silicon) hydrochlorate.
6. fluorescent mixture according to claim 5, which is characterized in that the 4th fluorophor has following composition:
La3Ga5(Ge,Si)O14: Cr3+。
7. fluorescent mixture according to claim 1, which is characterized in that first fluorophor, second fluorophor,
The mass ratio satisfaction of the third fluorophor, the 4th fluorophor: (20%-70%): (10%-65%): (1.5%-
20%): (10%-40%).
8. fluorescent mixture according to claim 1-6, which is characterized in that also include glue.
9. a kind of light emitting device, which is characterized in that including the described in any item fluorescent mixtures of claim 1-8.
10. light emitting device according to claim 9, which is characterized in that the light emitting device includes using LED purple light chip
Or UV chip is as excitation light source.
11. light emitting device according to claim 10, which is characterized in that the excitation light source has in 300-430nm model
Enclose interior peak luminous wavelength.
12. light emitting device according to claim 11, which is characterized in that the excitation light source has in 400-430nm model
Enclose interior peak luminous wavelength.
13. light emitting device according to claim 9, which is characterized in that the spectrum of the light emitting device covers 400-780nm
Visible light region and the later near infrared light region 780nm.
14. light emitting device according to claim 9, which is characterized in that the light emitting device has general aobvious greater than 90
Colour index Ra.
15. light emitting device according to claim 9, which is characterized in that the light emitting device has special aobvious greater than 90
Colour index R1-R15.
16. light emitting device according to claim 9, which is characterized in that the light emitting device has 2500K to 8000K's
Correlated colour temperature.
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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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| 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 |
| CN112310263A (en) * | 2019-08-02 | 2021-02-02 | 江苏博睿光电有限公司 | Full-spectrum LED light source |
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| WO2020107425A1 (en) | 2020-06-04 |
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