CN106318381B - A kind of Mn4+Sodium bifluoride red light material of doping and preparation method thereof - Google Patents
A kind of Mn4+Sodium bifluoride red light material of doping and preparation method thereof Download PDFInfo
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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Abstract
The invention discloses a kind of Mn4+Sodium bifluoride red light material of doping and preparation method thereof.The chemical composition of the material is NaHF2:Mn4+, with 15~30mL HF (a concentration of wt 40%), 1 × 10‐4~9 × 10‐4mol K2MnF6Solid, 0.01~0.1mol NaF are raw material, add deionized water that total volume is made to be stirred to react at normal temperatures 0.5~2 hour for 40mL, filter, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp, and the blue spectrum that maximum excitation band is sent out with White LED Blue Light chip exactly matches, and emission spectrum is made of 7 red emission peaks of four 595~643nm of position.The material may be applied to two primary colours white light LEDs, to improve its colour rendering index.Product is free of rare earth, and preparation method is simple, suitable for industrial production.
Description
Technical field
The present invention relates to luminescent material, more particularly to a kind of red light material that can be used for white light LEDs and preparation method thereof；
It is located at blue region more particularly to a kind of excitation wavelength, launch wavelength is located at the Mn of red light region4+The sodium bifluoride of doping shines
Material and preparation method thereof.
Background technology
White light LEDs are the forth generation light sources after incandescent lamp, fluorescent lamp, are the new light sources generally acknowledged 21 century.Yin Qigao
Imitate energy saving, environmentally protective, long lifespan and it is small the advantages that, the multiple fields such as be widely used in illuminating, communicate and show, no
Only manufacturer provides perfect backlighting scheme, also provides economic good light source for general lighting.Nowadays leading market
White light LEDs product is by yellow fluorescent powder YAG:Ce is encapsulated with blue-ray LED, matches colors to obtain color white light LEDs by champac complementation,
Compared with traditional energy-saving lamp, such white LEDs are relatively low in low colour temperature area colour rendering index, can not meet large-scale lighting demand,
The reason is that there was only yellow light and blue light ingredient in its white light, and red ingredient is less.
In order to improve by yellow fluorescent powder YAG:The white light LEDs colour rendering index of Ce and blue chip composition, in YAG:In Ce
It is mixed into nitride red fluorescent powder, relatively effective and practical method.Two primary colours to be handed over of commercial applications can be reached at present
The Nitride systems that WLED is generally adulterated with red light material using divalent europium, such as Sr2‐x‐yBaxCaySi5N8:Eu2+, matrix is steady
Qualitative height, Absorber Bandwidth, excitation purity are high, luminous efficiency is high, temperature quenching unobvious, can effectively optimize the colour developing of two primary colours WLED
Index and colour temperature, the quantum efficiency under 465nm excitations reach 80%, and luminous intensity only reduces a few percent [X. at 150 DEG C
Q.Piao,T.Horikawa,H.Hanzawa,K.Machida,“Characterization and luminescence
properties of Sr2Si5N8:Eu2+ phosphor for white light‐emitting‐diode
illumination”,Appl.Phys.Lett.88(2006)161908.Y.Q.Li,De With G,H. T.Hintzen,
“The effect of replacement of Sr by Ca on the structural and luminescence
properties of the red‐emitting Sr2Si5N8:Eu2+LED conversion phosphor”,J.Solid
State Chem.181(2008)515‐524.].Alkaline earth nitride, silicon nitride due to being used for preparing the system red light material etc.
Raw material is very expensive, and batch mixing need to keep away water and keep away oxygen with the overall process prepared so that nitride red light material it is at high price.Mn4+
The red light material of doping is given birth to due to fortune, causes the great interest for carrying out people, is because it is in compound aluminate and composite fluoride
Excitation wavelength be located near ultraviolet to blue region, just matched with semiconductor-based purple light with the electroluminescence wavelength of blue-ray LED, energy
The purple light and blue light of LED chip are effectively absorbed, and its emission spectrum is located at red light region in sharp peak, the feux rouges of efficient transmission can have
Effect improves the colour rendering index of WLED, obtains the warm white of low colour temperature height colour developing.Mn4+Had it is this have Broad excitation band with it is narrow
What the luminosity of transmitting band was especially advantageously applied illumination.Therefore, LED industry expects Mn4+The red light material of doping can take
For the business nitride rouge and powder that synthesis condition is harsh, raw material is rare.
The Mn of Philips companies last century the '20s invention4+The fluogermanate red light emitting phosphor of doping is efficient,
Excitation purity height [G.Kemeny, C.H.Haake, " Activator center in magnesium fluorogermanate
Phosphors ", J.Chem.Phys.33 (1960) 783.], but it is expensive (because raw material contains GeO2), therefore, the rouge and powder mesh
Before be only applied to special fluorescent lamp to improve its colour rendering index, and its excitation spectrum is located at black light area, is not suitable for market
Leading blue chip base LED.Fluorescent powder CaAl12O19:Mn4+Feux rouges can be launched under the excitation of black light and blue light, from
Theoretically, the powder can potential application in LED, but its luminous efficiency it is still to be improved [T.Murata, T.Tanoue,
M.Iwasaki,K.Morinaga,T.Hase,“Fluorescence properties of Mn4+in
CaAl12O19compounds as red‐emitting phosphor for white LED”,J.Lumin.114(2005)
207；Y.X.Pan,G.K.Liu,“Enhancement of phosphor efficiency via composition
Modification ", Opt.Lett.33 (2008) 1], recently using anion exchange method, efficiently synthesize and have studied feux rouges
Material K2TiF6:Mn4+, light efficiency is up to 98%, by K2TiF6:Mn4+With yellowish green fluorescent powder YAG:Ce is packaged in blue light jointly
After LED chip, obtain low colour temperature (3088K), high-color rendering (CRI=90), high efficiency (82%) warm white WLED
[H.M.Zhu,C.C.Lin,W.Q.Luo,S.T.Shu,Z.G.Liu, Y.S.Liu,J.T.Kong,E.Ma,Y.G.Cao,
R.S.Liu,X.Y.Chen,"Highly efficient non‐rare‐earth red emitting phosphor for
warm white light‐emitting diodes",Nat.Commun.5(2014)4312.].Japanese researchers have synthesized one
Serial Mn4+The composite fluoride red light material of doping simultaneously studies its luminosity, but synthetic method is more complicated, and raw materials used high
Expensive (simple metal), etching liquid used is dense (40%HF aqueous solutions), KMnO4Concentration height (easily there is non-luminous by-product,
Such as MnO2)[S.Adachi,T.Takahashi,"A yellow phosphor K2SiF6activated by Mn2+ion",
J.Appl.Phys.108(2010) 063506；R.Kasa,S.Adachi,"Mn‐activated K2ZrF6and
Na2ZrF6phosphors:Sharp red and oscillatory blue‐green emissions",
J.Appl.Phys.112(2012)013506.；S.Adachi,T.Takahashi,"Photoluminescence and
Raman scattering spectroscopies of Ba SiF6:Mn4+red phosphor",J.Appl.Phys.106
(2009)013516.]。
Invention content
The shortcomings that it is an object of the invention to overcome the prior art, provide it is a kind of can effectively by the blue light of GaN chips excite,
And two inorganic primary colours white light LEDs red light materials for emitting feux rouges and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of Mn4+The sodium bifluoride red light material of doping：The material is with NaHF2For matrix, with Mn4+As the centre of luminescence,
Chemical composition is NaHF2:Mn4+, Mn4+Mole doping concentration be NaHF20.1%~1.0%；Mn4+Part substitution Na+With H+, and forming negative electron hole makes charge in crystal keep neutral.
It is preferred that the Mn4+Mole doping concentration be NaHF20.4%~0.6%.
The sodium bifluoride red light material is white powder, is shone uniform, maximum excitation wavelength is in blue region, launch wavelength
With in red light region.Specifically product sends out bright red in the UV lamp, and material emitted light spectrum is located at respectively by three
250nm, 350nm, 460nm broadband form, and maximum excitation band and the blue spectrum that White LED Blue Light chip is sent out are complete
Matching, emission spectrum are located at the point for being located at 593nm, 605nm, 608nm, 616nm, 626nm, 630nm and 642 nm respectively by 7
Peak forms, and top is located at 626nm.The photochromic coordinate of transmitting is located at:X=0.66；Y=0.33 is in close proximity to CIE marks
The chromaticity coordinates of quasi- feux rouges.
The Mn4+The preparation method of the sodium bifluoride red light material of doping：By K2MnF6Solid is dissolved in HF aqueous solutions, adds in
NaF solids add in deionized water, are stirred to react at normal temperatures 0.5~2 hour, filter, and room temperature naturally dry obtains white powder
Body target material；K2MnF6Molar ratio with NaF is 0.001~0.09:1.
Further to realize the object of the invention, it is preferable that the mass concentration of the HF solution is 40%.
Preferably, the dosage for the HF aqueous solutions that every 0.01~0.1mol NaF are added in is 15~30mL.
Preferably, the reaction time is 1~2 hour.
Preferably, the deionized water that every 0.01~0.1mol NaF are added in is 10-25mL.
In the present invention, the material is with having researched and developed Mn4+The composite fluoride A of doping2XF6:Mn4+(A=K, Na, Cs；X=
Si, Ge, Zr, Ti) red light material difference, have in the matrix of these red light materials and Mn4+It is all the positive from such as Si of+4 valencys4 +,Ge4+,Zr4+, Ti4+, Mn4+Part replaces positive sublattice position and sends out feux rouges, and prepare these materials and be frequently necessary in hydro-thermal
(heating pressurization) condition just carries out.Base NaHF2In have no+4 valencys cation, but NaHF2:Mn4+But it can shine, luminous efficiency reaches
88%.It can speculate Mn4+Part substitution Na+With H+, and forming negative electron hole makes charge in crystal keep neutral, reaction whole process exists
It carries out at room temperature.
Relative to the prior art, the invention has the advantages that and effect：
(1) present invention is compared with the aluminate of known tetravalence additive Mn, woth no need to high temperature sintering, because whole process is in air
In carry out at normal temperatures, material pattern due to no sintering uniformly disperses；Emission maximum mother-in-law of the present invention is grown in the region of blue light, therefore
Blue light can be more effectively absorbed, and because of Mn4+Narrowed emission makes feux rouges purer.
(2) Mn with having researched and developed4+The composite fluoride A of doping2XF6:Mn4+Red light material is compared, and the present invention only needs 3 kinds
Raw material：K2MnF6, HF and NaF, do not need to positive tetravalent metal raw material, therefore raw material is simple, and synthesis technology whole process at normal temperatures into
Row, can be mass-produced.
(3) because material is without rare earth, preparation process need not keep away water and keep away oxygen, and without high temperature sintering, therefore, cost is far below quotient
Industry nitride rouge and powder.
Description of the drawings
Fig. 1 NaHF2:Mn4+The XRD standard cards data of (embodiment 1) and the XRD diagram of embodiment product.
Fig. 2 NaHF2:Mn4+EDS (spectral distribution) figure of (embodiment 1).
Fig. 3 NaHF2:Mn4+Excitation spectrum (a of (embodiment 1):Monitoring wavelength is 626nm) and emission spectrum (b:Excitation
Wavelength is 460nm).
Specific embodiment
With reference to embodiment and attached drawing, the invention will be further described, but the scope of protection of present invention is not
It is confined to the range of embodiment expression.
Embodiment 1
In plastic containers, by 0.1235g (5 × 10‐4mol)K2MnF6Solid material is dissolved in 20mL HF (a concentration of wt
40%) it is raw material, then to add in 2.1g (0.05mol) NaF, and deionized water is added to make total volume, and for 40mL, stirring is anti-at normal temperatures
It answers 1.5 hours, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.Its XRD
(detection of Bruker D8Advance X-ray diffractometers) is as shown in Figure 1, XRD shows that product is pure NaHF2Phase, it is trace doped
Mn4+And have no significant effect object phase.As shown in Fig. 2, energy spectrum analysis measures on Nova NanoSEM 200, in electron beam
Under effect, energy spectrum analysis display elements：Na, F and Mn, and H can not be shown since quality is too small, it is seen that products obtained therefrom ingredient is
NaHF2:Mn4+.As shown in figure 3, using Fluoromax-4 Fluorescence Spectrometer (HORIBA Jobin Yvon Inc.), in room temperature
Under the conditions of detect the luminescent properties of product, the excitation spectrum of the white powder product by three be located at respectively 250 nm, 350nm,
460nm broadbands form, and the blue light that maximum excitation band (460nm) is sent out with GaN blue chips exactly matches, emission spectrum position
It is formed in the spike for being located at 593nm, 605nm, 608nm, 616nm, 626nm, 630nm and 642nm respectively by 7, highest
Peak is located at 626nm.The particle of product is more uniform, and particle size and range distribution are also suitable for applying pipe application.Product is free of
Rare earth, preparation method is simple, suitable for industrial production.
Embodiment 2
In plastic containers, by 0.0988g (4 × 10‐4mol)K2MnF6Solid material is dissolved in 30mL HF (a concentration of wt
40%) it is raw material, then to add in 0.42g (0.01mol) NaF, and deionized water is added to make total volume, and for 40mL, stirring is anti-at normal temperatures
It answers 0.5 hour, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.The white powder
XRD diagram, surface sweeping electron microscope and the fluorescence spectrum and Fig. 1-3 of material are essentially identical.
Embodiment 3
In plastic containers, by 0.1482g (6 × 10‐4mol)K2MnF6Solid material is dissolved in 15mL HF (a concentration of wt
40%) it is raw material, then to add in 3.36g (0.08mol) NaF, and deionized water is added to make total volume, and for 40mL, stirring is anti-at normal temperatures
It answers 1 hour, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.The white powder material
XRD diagram, surface sweeping electron microscope and the fluorescence spectrum and Fig. 1-3 of material are essentially identical.
Embodiment 4
In plastic containers, by 0.0247g (1 × 10‐4mol)K2MnF6Solid material is dissolved in 18mL HF (a concentration of wt
40%) it is raw material, then to add in 2.52g (0.06mol) NaF, and deionized water is added to make total volume, and for 40mL, stirring is anti-at normal temperatures
It answers 2 hours, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.The white powder material
XRD diagram, surface sweeping electron microscope and the fluorescence spectrum and Fig. 1-3 of material are essentially identical.
Embodiment 5
In plastic containers, by 0.2223g (9 × 10‐4mol)K2MnF6Solid material is dissolved in 25mL HF (a concentration of wt
40%) it is raw material, then to add in 4.2g (0.1mol) NaF, adds deionized water that total volume is made to be stirred to react at normal temperatures for 40mL
It 1.8 hours, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.The white powder material
XRD diagram, surface sweeping electron microscope and the fluorescence spectrum and Fig. 1-3 of material are essentially identical.
Embodiment 6
In plastic containers, by 0.1235g (5 × 10‐4mol)K2MnF6Solid material is dissolved in 25mL HF (a concentration of wt
40%) it is raw material, then to add in 2.94g (0.07mol) NaF, and deionized water is added to make total volume, and for 40mL, stirring is anti-at normal temperatures
It answers 1.6 hours, filters, room temperature naturally dry obtains white powder.Product sends out bright red in the UV lamp.The white powder
XRD diagram, surface sweeping electron microscope and the fluorescence spectrum and Fig. 1-3 of material are essentially identical.
From above-described embodiment as it can be seen that the present invention is compared with the aluminate of known tetravalence additive Mn, woth no need to high temperature sintering,
Because whole process carries out at normal temperatures in air, material pattern due to no sintering uniformly disperses；Maximum emission wavelength of the present invention exists
The region of blue light, therefore blue light can be more effectively absorbed, and because of Mn4+Narrowed emission makes feux rouges purer.
With the Mn researched and developed4+The composite fluoride A of doping2XF6:Mn4+Red light material is compared, and the present invention only needs 3 kinds of originals
Material： K2MnF6, HF and NaF, do not need to positive tetravalent metal raw material, therefore raw material is simple, and synthesis technology whole process at normal temperatures into
Row, can be mass-produced.
Because material is without rare earth, preparation process whole process carries out in air, and oxygen is kept away without keeping away water, without high temperature sintering, because
This, cost is far below business nitride rouge and powder.
Claims (7)
1. a kind of Mn4+The sodium bifluoride red light material of doping, it is characterised in that：The material is with NaHF2For matrix, with Mn4+As
The centre of luminescence, chemical composition NaHF2:Mn4+, Mn4+Mole doping concentration be NaHF20.1%~1.0%；Mn4+Part takes
For Na+With H+, and forming negative electron hole makes charge in crystal keep neutral；The sodium bifluoride red light material is white powder, is sent out
Light is uniform, and maximum excitation wavelength is located at red light region in blue region, launch wavelength；The photochromic coordinate of transmitting is located at:X=
0.66, y=0.33, it is in close proximity to the chromaticity coordinates of CIE standard feux rouges.
2. Mn according to claim 14+The sodium bifluoride red light material of doping, it is characterised in that：The Mn4+Mole doping
A concentration of NaHF20.4%~0.6%.
3. Mn described in claim 14+The preparation method of the sodium bifluoride red light material of doping, it is characterised in that：By K2MnF6Solid
HF aqueous solutions are dissolved in, add in NaF solids, deionized water is added in, is stirred to react at normal temperatures 0.5~2 hour, are filtered, room temperature is certainly
It so dries, obtains white powder target material；K2MnF6Molar ratio with NaF is 0.001~0.09:1.
4. Mn according to claim 34+The preparation method of the sodium bifluoride red light material of doping, it is characterised in that：It is described
The mass concentration of HF solution is 40%.
5. Mn according to claim 44+The preparation method of the sodium bifluoride red light material of doping, it is characterised in that：Often
The dosage for the HF aqueous solutions that 0.01~0.1mol NaF are added in is 15~30mL.
6. Mn according to claim 34+The preparation method of the sodium bifluoride red light material of doping, it is characterised in that：Institute
It is 1~2 hour to state the reaction time.
7. Mn according to claim 34+The preparation method of the sodium bifluoride red light material of doping, it is characterised in that：It is described
The deionized water that every 0.01~0.1mol NaF are added in is 10-25mL.
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| US7648649B2 (en) * | 2005-02-02 | 2010-01-19 | Lumination Llc | Red line emitting phosphors for use in led applications |
| CN105038774A (en) * | 2014-05-01 | 2015-11-11 | 通用电气公司 | Process for preparing red-emitting phosphors |
| CN105793389A (en) * | 2013-12-13 | 2016-07-20 | 通用电气公司 | Process for preparing color stable manganese-doped complex fluoride phosphors |
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| US9580643B2 (en) * | 2012-02-16 | 2017-02-28 | Koninklijke Philips N.V. | Coated narrow band red-emitting fluorosilicates for semiconductor LEDS |
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|---|---|---|---|---|
| US7648649B2 (en) * | 2005-02-02 | 2010-01-19 | Lumination Llc | Red line emitting phosphors for use in led applications |
| CN105793389A (en) * | 2013-12-13 | 2016-07-20 | 通用电气公司 | Process for preparing color stable manganese-doped complex fluoride phosphors |
| CN105038774A (en) * | 2014-05-01 | 2015-11-11 | 通用电气公司 | Process for preparing red-emitting phosphors |
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Application publication date: 20170111 Assignee: INSTITUTE OF NEW MATERIALS & INDUSTRIAL TECHNOLOGY, WENZHOU University Assignor: Wenzhou University Contract record no.: X2020330000095 Denomination of invention: A Mn4 +doped sodium hydrogen fluoride red light material and its preparation method Granted publication date: 20180619 License type: Common License Record date: 20201112 |