CN107974252A - A kind of nitride luminescent material and the light-emitting device for including it - Google Patents
A kind of nitride luminescent material and the light-emitting device for including it Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 19
- 230000005284 excitation Effects 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 5
- 238000000695 excitation spectrum Methods 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910003564 SiAlON Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910003669 SrAl2O4 Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7775—Germanates
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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
- H01L33/02—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 bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
- H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials
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- Luminescent Compositions (AREA)
Abstract
A kind of nitride luminescent material and the light-emitting device for including it.The luminescent material is M comprising chemical formulamAbXyDzInorganic compound, wherein M is combination more than one or both of La, Lu, Gd and Y, A is one or both of Si and Ge, X N, or is N and F, D is the one or more in Dy, Ce, Pr, Pr and/or Dy, and 2≤m≤4,5≤b≤7 must wherein be contained, 10.5≤y≤11.5,0 ＜ z≤0.5.The nitride luminescent material of the present invention can be a kind of preferable luminescent material by the effectively excitation of the light of 350 500nm wave-length coverages and in visible region efficient transmission.
Description
Technical field
The invention belongs to field of light emitting materials, shining in particular to a kind of nitride luminescent material and comprising it
Device.
Background technology
Light emitting diode (LED) has the advantages that low-voltage, specular removal, low energy consumption, the long-life, pollution-free, in semiconductor
Illumination and liquid crystal flat-panel display field are successfully applied.In recent years, new single-matrix white LED is caused extensively
Concern.The implementation of white light LEDs is broadly divided into two kinds at present：The first is the combination of three primary colours (red, blue, green) LED chip；
Another kind be with LED excitation fluorescence be mixed to form white light, i.e., by single-matrix by adulterating different activator ions,
Launch the light combination of different colours and form white light.Easily cause between a variety of activator ions there are mutual absorption
Luminous efficiency reduces, and singly mixes Dy3+Blue green light and yellow orange light can be launched after being excited respectively, combination forms white light and avoids
The problem of above-mentioned.In addition, doping Pr3+The light launched after ion under blue light excitation can also be applied to improve color during backlight is shown
Domain.
2008, Japanese material research institute and Mitsubishi Chemical disclosed a kind of new nitride luminescent material jointly
CexMIII 3-xMIV yX-III z(JP 2008088362A、JP 2010070773A).This nitride can be by 300~530nm or so
Light excite to obtain yellow light, its heat endurance is higher, and can by the ultraviolet excitation of 300~450nm, be it is a kind of have it is wide
The advanced luminescent material of general application prospect.
In addition, Dillip.G.R et al. is reported on borate by adulterating Dy3+Ion manufactures white light emitting material
Process (Dillip.G.R, Ramesh.B, Reddy.C.M, Mallikarjuna.K, Ravi.O, ＆Dhoble.S.J, et
al.X-ray analysis and optical studies ofDy3+,doped NaSrB5O9,microstructures
for white light generation.Journal of Alloys&Compounds,2014:719-727.), and Santa
Chawla et al. is reported on aluminate by adulterating Pr3+Ion come obtain the process of luminescent material (Chawla, S.,
Kumar,N.,&Chander,H.Broad yellow orange emission from SrAl2O4:Pr3+,phosphor
with blue excitation for application to white leds.Journal of Luminescence,
2009:114-118.), this has very big inspiration meaning for our research and development of luminescent material, however, above-mentioned technology manufactures
The luminous efficiency of luminescent material, heat endurance etc. still needs to be further improved.
The content of the invention
For this reason, it is an object of the present invention to provide a kind of nitride luminescent material.The nitride light-emitting material of the present invention
Material can be a kind of preferably luminous material by the effectively excitation of the light of 350-500nm wave-length coverages and in visible region efficient transmission
Material.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of nitride luminescent material, the inorganic compound it includes chemical formula for formula [I],
MmAbXyDz [I]
Wherein
M is combination more than one or both of La, Lu, Gd and Y,
A is one or both of Si and Ge,
X is N, or is N and F,
D is combination more than one or both of Dy, Ce, Pr, wherein Pr and/or Dy must be contained, and
2≤m≤4, m are, for example, 2.2,2.4,2.5,2.55,2.63,2.7,2.9,3.1,3.3,3.5,3.7,3.85,3.9
Deng,
5≤b≤7, b are, for example, 5.2,5.4,5.5,5.55,5.63,5.7,5.9,6.1,6.3,6.5,6.7,6.85,6.9
Deng,
10.5≤y≤11.5, y are, for example, 10.6,10.8,10.9,11.0,11.15,11.22,11.3,11.35,11.4,
11.45 etc.
0 ＜ z≤0.5, z is, for example, 0.02,0.04,0.06,0.08,0.1,0.15,0.2,0.22,0.26,0.32,
0.36th, 0.4,0.42,0.43,0.45,0.48 etc..Preferably, the luminescent material has and La3Si6N11Identical crystal
Structure.
Singly mix Dy3+Blue green light and yellow orange light can be launched after being excited respectively, combination forms white light and avoids due to more
The problem of easily being reduced between kind activator ion there are luminous efficiency caused by mutual absorption.In addition, doping Pr3+From
The light launched after son under blue light excitation is shown available for backlight to improve colour gamut.With La3Si6N11Crystal structure as matrix,
The luminescent material of high thermal stability can be further prepared, so as to be suitable for the device of high-energy-density excitation.
In nitride luminescent material of the present invention, its crystal structure is built by M-A polyhedrons, and by by M
The luminescent material of different structure can be obtained by being connect with A-N tetrahedrons with angle-angle or side-side chain.In order to make the nitridation of the present invention
Thing luminescent material has and La3Si6N11The same crystal structure, and unlikely other dephasigns of introducing, in the nitride of the present invention
In luminescent material, select M element for one or both of trivalent rare earth element La, Lu, Y, Gd the above combination when, Neng Goubao
The stringent growth of luminescent material lattice is demonstrate,proved, obtains high stability luminescent material.But the introduction volume of above-mentioned element should be suitable, when
During m ＜ 2, cause that pure phase cannot be generated so as to cause luminescent material performance to become due to the difference of element proportioning in roasting process
Difference；As m ＞ 4, excessive starting material left equally influences the generation of luminescent material pure phase, and the temperature characterisitic of luminescent material also can
It is deteriorated, therefore, it is necessary to limit：2≤m≤4.
X is N element, can make luminescent material and La synthesized by selected element3Si6N11Identical crystal structure.As y ＜
After 10.5 or y ＞ 11.5, since element proportioning difference causes crystals valence link uneven, cause the unstable of structure
Property, so as to be not readily available preferable luminescent material, therefore, it is necessary to limit：10.5≤y≤11.5.
In nitride luminescent material of the present invention, D ions find to swash as activator ion after many experiments
Agent concentration living has optimal effectiveness when limiting scope as 0 ＜ z≤0.5.When D contents are more than 0.5, on the one hand into after lattice
Due to ionic radius mismatch cause structural instability increase in addition generation dephasign, on the other hand, too many D ions can because from
The too small generation concentration quenching effect of sub- spacing, luminosity decline with the increase of D ions on the contrary.
Nitride luminescent material of the present invention, according to selected specific element species and the difference of consumption proportion,
There is also difference for the peak position of its excitation wavelength and the peak wavelength of launch wavelength.
Preferably, D is Dy.
Preferably, A Si.
Preferably, M La.
Preferably, the peak wavelength of the excitation spectrum of the luminescent material is located at 380~390nm, main transmitting peak-to-peak value
Wavelength is located at 570~580nm, and minor peaks wavelength is located at 470~480nm.
Preferably, D is Pr.
Preferably, A Si.
Preferably, M La.
Preferably, the peak wavelength of the excitation spectrum of the luminescent material is located at 450~470nm, main transmitting peak-to-peak value
Wavelength is located at 660~670nm, and minor peaks wavelength is located at 500~510nm.
Preferably, the luminescent material can be combination more than one or both of powder, ceramics or crystal.
The preparation method of the nitride luminescent material of the present invention can be prepared using methods known in the art, such as be made
Prepared with high temperature solid-state method.
In a kind of preferred embodiment of the present invention, according to needed for the general formula of nitride luminescent material of the present invention
The raw material and its ratio of each element are uniformly mixed, and carry out high-temperature calcination；After calcination by in-furnace temperature near less than 100 DEG C take
Go out, powder is carried out to include the post-processing steps such as grinding, pickling, sieving and drying.
Preferably, the raw material of each element is various metals and the simple substance or compound of nonmetalloid, wherein compound
Preferably nitride.
Preferably, calcining carries out under reducing atmosphere or inert atmosphere, preferably in reducing atmosphere or inert atmosphere protection
High pressure or atmospheric pressure kiln body in carry out, to ensure the low oxygen content of environment.
Preferably, the reducing atmosphere or inert atmosphere are groups one or more kinds of in nitrogen, hydrogen or CO gases
Close.
Nitride has stable covalent bond, it is necessary to which higher temperature can just facilitate the synthesis of product due to it.As excellent
Choosing, according to theoretical and experiment, the temperature of the high-temperature calcination is 1400-1800 DEG C, is preferably 1600 DEG C, and the time of calcining is
20min-24h, if soaking time is too short, reaction is not abundant enough, and when time is excessively normal causes abnormal grain growth, is preferably 6-
15h。
An object of the present invention, which also resides in, provides a kind of light-emitting device, it includes luminescent material of the present invention.
Preferably, the light-emitting device further includes radiation source.Preferably, the radiation source is laser light source or partly leads
Body light source.
Wherein laser light source includes but not limited to vacuum-ultraviolet emissions source, ultraviolet emission source, violet photoluminescence source or blue light hair
Penetrate source etc.；Semiconductor light source includes but not limited to ultraviolet LED, purple LED, blue-ray LED etc..
Preferably, also contain in the light-emitting device by other luminescent materials of the radiation source excitation.
Preferably, other described luminescent materials are combinations one or more kinds of in following fluorescent material：(Y,Gd,
Lu,Tb)3(Al,Ga)5O12:Ce3+、β-SiAlON:Eu2+、(Ca,Sr)AlSiN3:Eu2+、(Li,Na,K)2(Ti,Zr,Si,Ge)
F6:Mn4+、(Ca,Sr,Ba)MgAl10O17:Eu2+。
The present invention is by adjusting M：A：The ratio of D, can form the La using D ions as the centre of luminescence3Si6N11Crystal knot
Structure, this make it that activator center obtains the transition energy of higher under the action of Si-N tetrahedrons field, so as to obtain high efficiency hair
Penetrate, and with La3Si6N11Crystal structure so as to prepare the luminescent material of high thermal stability, thus can be adapted to use as matrix
In the device of high-energy-density excitation.
Brief description of the drawings
The accompanying drawings which form a part of this application are used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation are used to explain the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the XRD diffraction maximums and La that sample is made in embodiment 13Si6N11Standard card contrasts；
Sample La is made for embodiment 1 in Fig. 22.9Si6N11：0.1Dy3+Emission spectrum under the excitation of 387nm light；
Sample La is made for embodiment 15 in Fig. 32.91Si6N11：0.09Pr3+Emission spectrum under the excitation of 460nm light.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
It should be noted that in the following example, XRD spectrum carries out X-ray diffraction using Co targets (λ=1.78892nm).
Emission spectrum is obtained using the highly sensitive Integral fluorescent spectrometer collection of the FluoroMax-4 models of Horiba companies.
Comparative example 1
By chemical formula Y2.9Al5O11:Dy0.1Proportioning weighs raw material.By above-mentioned raw materials mixture in agate mortar, grinding is equal
After even, be fitted into corundum crucible, using carbon monoxide as reducing atmosphere, programming rate is 5 DEG C/min, with 1400 DEG C roasting 4 it is small when,
It is cooled to room temperature.Obtained sintered products obtain sample after grinding after waiting aftertreatment technology with ball milling is levigate.
Comparative example 2
By chemical formula Y2.91Al5O11:Pr0.09Proportioning weighs raw material.By above-mentioned raw materials mixture in agate mortar, grinding
After uniformly, it is fitted into corundum crucible, using carbon monoxide as reducing atmosphere, programming rate is 5 DEG C/min, small with 1400 DEG C of roastings 4
When, it is cooled to room temperature.Obtained sintered products obtain sample after grinding after waiting aftertreatment technology with ball milling is levigate.
Sample made from comparative example 1 and 2 is YAG fluorescent powder common on the market.
Embodiment 1
By will be according to La2.9Si6N11:Dy0.1LaN, CeN, Si that stoichiometric ratio weighs3N4, DyN powder is in mortar
Be uniformly mixed, when 1600 DEG C of insulations 3 are small under reducing atmosphere after, products obtained therefrom is obtained through broken, washed with impurities, sieving, drying
Product.
The XRD spectrum that sample is made in the present embodiment is shown in Fig. 1, it was demonstrated that generates La2.9Si6N11Phase；Under the excitation of 387nm light
Emission spectrum see Fig. 2, it was demonstrated that obtain meet we design spectrum.Through measurement, comparative example 1 is chosen as a comparison, this sample
Product relative luminous intensity is 145%.Remain to keep 87% luminous intensity when temperature is increased to 150 DEG C, embody the present invention
The good stability of product.The product of embodiment 2-22 remains to keep more than 83% luminous intensity when being increased to 150 DEG C.
Embodiment 2-14
There is synthetic method similar to Example 1 in embodiment 2-14.In embodiment 2-14, emission spectrum and Fig. 2
It is similar.Luminous intensity is as shown in table 1 corresponding thereto for the chemical formula of embodiment 2-14, and relative luminous intensity is made with comparative example 1 in table 1
For contrast.
Table 1
| Title | Chemical composition | Relative luminous intensity (%) |
| Embodiment 2 | La2Dy0.01Si6.35N10.5 | 110 |
| Embodiment 3 | Dy0.01Gd2.71Si5Ge0.835N10.5 | 105 |
| Embodiment 4 | Dy0.11La2.89Si6N11 | 137 |
| Embodiment 5 | Dy0.066Y2.1Si7N11.5 | 102 |
| Embodiment 6 | Dy0.15La2Si6.41N10.7 | 104 |
| Embodiment 7 | Dy0.07La2.93Si6N11 | 112 |
| Embodiment 8 | Dy0.386Gd2.834Si4.5Ge1.46N11F0.5 | 105 |
| Embodiment 9 | Dy0.07La2.93Si6N11 | 125 |
| Embodiment 10 | Dy0.06La4Si5N10.5F0.68 | 130 |
| Embodiment 11 | Dy0.5Sc2.33Si6.5N11.5 | 112 |
| Embodiment 12 | Dy0.04La3.3Si5.24N10F1.02 | 105 |
| Embodiment 13 | Lu4Dy0.33Si4.5Ge0.5N11 | 133 |
| Embodiment 14 | Dy0.05Ce0.02La2.93Si6N11 | 132 |
Embodiment 15
By will be according to La2.91Si6N11:Pr0.09LaN, CeN, Si that stoichiometric ratio weighs respectively3N4, PrN powder exists
Be uniformly mixed in mortar, when 1600 DEG C of insulations 3 are small under reducing atmosphere after, products obtained therefrom is through broken, washed with impurities, sieving, baking
It is dry, obtain product.
It is similar with Fig. 3 that emission spectrum of the sample under the excitation of 460nm light is made in the present embodiment.Through measurement, made with comparative example 2
For contrast, this sample luminous intensity is 150%.
Embodiment 16-22
There is the synthetic method similar to embodiment 15 in embodiment 16-22.In embodiment 16-22, emission spectrum is such as
Fig. 3.Luminous intensity is as shown in table 2 corresponding thereto for the chemical formula of embodiment 16-22, and relative luminous intensity is made with comparative example 2 in table 2
For contrast.
Table 2
| Title | Chemical composition | Relative luminous intensity (%) |
| Embodiment 16 | Pr0.5Lu4Ge5.25N11.5 | 145 |
| Embodiment 17 | Pr0.4La3.93Si5N11 | 146 |
| Embodiment 18 | Pr0.45Lu2.9Ge6N10F1.01 | 122 |
| Embodiment 19 | Lu0.02Pr0.07La3.23Si5.91N11.2 | 112 |
| Embodiment 20 | Y0.016Pr0.1Lu2.05Ge7N11.5 | 148 |
| Embodiment 21 | Dy0.03Ce0.02Lu1.45Pr0.35Gd2.115Si5.649N11.5 | 115 |
| Embodiment 22 | Dy0.2Lu0.8Pr0.01La1.2Si3.13Ge3N10F1.15 | 112 |
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of nitride luminescent material, it is characterised in that the luminescent material includes the inorganic chemical that chemical formula is formula [I]
Thing,
MmAbXyDz [I]
Wherein
M is combination more than one or both of La, Lu, Gd and Y,
A is one or both of Si and Ge,
X is N, or is N and F,
D is combination more than one or both of Dy, Ce, Pr, wherein Pr and/or Dy must be contained, and
2≤m≤4,
5≤b≤7,
10.5≤y≤11.5,
0 ＜ z≤0.5.
2. luminescent material according to claim 1, it is characterised in that the luminescent material has and La3Si6N11Identical
Crystal structure.
3. luminescent material according to claim 1 or 2, it is characterised in that D Dy；
Preferably, A Si；
Preferably, M La.
4. luminescent material according to claim 3, it is characterised in that the peak wavelength of the excitation spectrum of the luminescent material
Positioned at 380~390nm, main emission peak peak wavelength is located at 570~580nm, and minor peaks wavelength is located at 470~480nm.
5. luminescent material according to claim 1 or 2, it is characterised in that D Pr；
Preferably, A Si；
Preferably, M La.
6. luminescent material according to claim 5, it is characterised in that the peak wavelength of the excitation spectrum of the luminescent material
Positioned at 450~470nm, main emission peak peak wavelength is located at 660~670nm, and minor peaks wavelength is located at 500~510nm.
7. a kind of light-emitting device, it is characterised in that the light-emitting device shines material including claim 1-6 any one of them
Material.
8. light-emitting device according to claim 7, it is characterised in that the light-emitting device further includes radiation source；
Preferably, the radiation source is laser light source or semiconductor light source.
9. the light-emitting device according to claim 7 or 8, it is characterised in that also contain in the light-emitting device by the spoke
Penetrate other luminescent materials of source excitation.
10. according to claim 7-9 any one of them light-emitting devices, it is characterised in that other described luminescent materials are following
One or more kinds of combination in fluorescent material:(Y,Gd,Lu,Tb)3(Al,Ga)5O12:Ce3+、β-SiAlON:Eu2+、(Ca,
Sr)AlSiN3:Eu2+、(Li,Na,K)2(Ti,Zr,Si,Ge)F6:Mn4+、(Ca,Sr,Ba)MgAl10O17:Eu2+。
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| CN111073645A (en) * | 2019-12-28 | 2020-04-28 | 中国科学院长春光学精密机械与物理研究所 | Broadband fluorescent powder, preparation method thereof, application of broadband fluorescent powder and light-emitting device |
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| CN103946340A (en) * | 2011-11-15 | 2014-07-23 | 三菱化学株式会社 | Nitride phosphor and method of producing same |
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