CN103275711A - Fluorine titanium salt red-light material for white LED with two primary colors and preparation method of material - Google Patents
Fluorine titanium salt red-light material for white LED with two primary colors and preparation method of material Download PDFInfo
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- CN103275711A CN103275711A CN201310229779XA CN201310229779A CN103275711A CN 103275711 A CN103275711 A CN 103275711A CN 201310229779X A CN201310229779X A CN 201310229779XA CN 201310229779 A CN201310229779 A CN 201310229779A CN 103275711 A CN103275711 A CN 103275711A
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Abstract
The invention discloses a fluorine titanium salt red light material for a white LED with two primary colors and a preparation method of the material. The chemical composition of the material is Bati(1-x)F6: xMn <4+>, wherein x ranges from 0.25% to 2.5%. The preparation method comprises the steps as follows: tetrabutyl titanate or TiO2 is taken as a titanium source, BaF2 is taken as a barium source, KMnO4 is taken as an active ion manganese source, an HF aqueous solution with the concentration ranging from 4% to 10% is taken as a medium or a fluorinating agent, a reaction is performed for 3-12 hours at the temperature ranging from the room temperature to 180 DEG C, then suction filtration and drying are performed, and white powder is obtained. The product emits bright red light under an ultraviolet lamp, the maximum excitation band of the product is matched with blue light emitted by a GaN blue light chip completely, and the emission spectrum is located in a red zone. The material can be applied to the white LED with two primary colors to improve the CRI (color rendering index) of the LED. The product has uniform and slight particles, contains no rare earth, has a simple preparation method and is suitable for industrial production.
Description
Technical field
The present invention relates to luminescent material, particularly relate to a kind of two primary colours white light LEDs fluorine titanium salt red light material.Be specifically related to a kind of excitation wavelength and be positioned at blue region, emission wavelength is positioned at the fluotitanate luminescent material in ruddiness zone.
Background technology
The semi-conductor white light LEDs has the incomparable good characteristic of conventional light source: economize on electricity, light is adjustable, vibration resistance, not fragile, instantaneous starting, nothing are dodged frequency, long service life etc.Nowadays the champac two primary colours GaN base white light LEDs of being made up of blue light GaN chip and yellow fluorescent powder YAG:Ce is subjected to showing great attention to of people, this type of two primary colours white light LEDs is the minimum conversion of white light of Stocks displacement (power loss) in the white-light illuminating of invention up to now, because the blue light electroluminescence of GaN chip (450～470nm) excitated fluorescent powder YAG:Ce, produce the gold-tinted of 550nm, and the blue light electroluminescence of chip itself becomes white light with the gold-tinted complementation of fluorescent material.And have only in this light source, exciting light itself becomes the complementary color of white light.Moreover the electroluminescent efficiency height of blue light GaN chip itself makes the efficient of two primary colours white light LEDs far above conventional light source (at present large power white light LED generally reach 130 lumens/watt).
Because having only blue light and gold-tinted in the two primary colours white light LEDs spectrum forms, and lack the ruddiness composition, and and make that its colour rendering index is on the low side, especially can't obtain the warm white of low colour temperature (2700 ?3000K), high colour developing (Ra〉90), be that the color reducing power is poor, impinging upon can distortion on the object.The color developing of present two primary colours white light LEDs can't be compared with electricity-saving lamp, does not satisfy the domestic light application requirement.Investigators mix the co-activation ion Sm that glows in yellow fluorescent powder YAG:Ce
3+, Eu
3+, Pr
3+Because this type of ion luminous efficiency in YAG matrix is lower, to spectrum and the not obvious ［ Y.X.Pan that improves YAG:Ce, M.M.Wu, Q.Su, " Tailored photoluminescence of YAG:Ce phosphor through various methods ", J.Phys.Chem.Solid.65 (2004) 845 ］; Or with other ion (as Gd
3+) part replaces Y among the YAG:Ce
3+Ion, make emmission spectrum generation red shift, but when improving the emmission spectrum distribution, but have to sacrifice luminosity ［ C.C.Chiang, M.S.Tsai, M.H.Hon, " Preparation of cerium ?activated GAG phosphor powders influence of Co ?doping on crystallinity and luminescent properties ", J.Electrochem.Soc.154 (2007) J326 ?J329..Japan one research group report, in YAG:Ce, sneak into nitride red fluorescent material, can be in low colour temperature district (2700 ?3000K) obtain colour rendering index greater than 90 warm white ［ K.Uheda, N.Hirosaki, Y.Yamamoto, A.Naito, T.Nakajima, H.Yamamoto, " Luminescence properties of a red phosphor, CaAlSiN
3: Eu
2+, for white light ?emitting diodes ", Electrochem.Solid State Lett.9 (2006) H22 ?H25..Therefore, development of new blue-light excited down luminous efficiency at least can be suitable with YAG:Ce red light material, and it is sneaked into YAG:Ce, with the colour rendering index that improves two primary colours GaN base white light LEDs be comparison effectively and practical methods.
For improving the colour rendering index of two primary colours white light LEDs, the investigator has carried out the research of two primary colours white light LEDs with fluorine titanium salt red light material in external, this type of red light material need meet the following conditions: (1) maximum excitation spectrum is positioned at blue region, namely in blue region strong absorption (excitation spectrum has wide range line feature) is arranged; (2) emmission spectrum is positioned at the ruddiness zone, and the purity of color height, and namely emmission spectrum has narrow spectral line characteristic; (3) luminous efficiency height is suitable with commercial bloom YAG:Ce at least.The red light material such as the Eu that have reported at present
3+Be the silicate red fluorescent material of molybdenum (tungsten) of activator, because its absorption in blue region comes from Eu
3+F ?f, make its absorption in blue region very limited.Eu
2+The alkaline earth sulfide that activates have than broad absorption band in blue region, and emission band is positioned at the ruddiness zone, be to can be applicable to two primary colours white light LEDs theoretically, but after the light decay experiment of this type of LED through some months, the efficient of fluorescent material seriously descend, and emmission spectrum is broad band, and purity of color is not high.In addition, be Eu by commercial applications
2+The nitride red light material that activates, its matrix stability height, absorption bandwidth, purity of color height, luminous efficiency height, temperature quenching not obvious ［ X.Q.Piao, T.Horikawa, H.Hanzawa, K.Machida, " Characterization and luminescence properties of Sr
2Si
5N
8: Eu
2+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 Sr
2Si
5N
8: Eu
2+LED conversion phosphor ", J.Solid State Chem.181 (2008) 515 ?524..But the cost of nitride red light material very high (at least 30 ten thousand yuan/kilogram).Therefore, still need to research and develop better can be by blue-light excited novel two primary colours white light LEDs with fluorine titanium salt red light material.
In recent years, having many researchs to report utilizes etching method to prepare two primary colours white light LEDs red light materials ［ Y.K.Xu, S.Adachia, " Properties of Na
2SiF
6: Mn
4+And Na
2GeF
6: Mn
4+Red phosphors synthesized by wet chemical etching ", J.Appl.Phys.105 (2009) 013525.S.Adachia, T.Takahashi, " Direct synthesis and properties of K
2SiF
6: Mn
4+Phosphor by wet chemical etching of Si wafer ", Appl.Phys.104 (2008) 023512.Y.K.Xu, S.Adachi, " Properties of Mn
4+?Activated Hexafluorotitanate Phosphors ", J.Electrochem.Soc., 158 (2011) J58 ?J65., this red light material is with Mn
4+Be active ions, with the composite alkali metal fluorochemical [as Na
2SiF
6, Na
2GeF
6, A
2SiF
6(A=A=K, Cs, Na)] as matrix, material has wide band absorption in blue region, and launch the ruddiness of narrow spectral line characteristic, be particularly suitable for improving the colour rendering index of two primary colours white light LEDs.Often using expensive metal simple-substance (as titanium, germanium, silicon) in the method for bibliographical information is raw material, and etching liquid concentration height (40%HF solution), is unfavorable for large-scale commercial production.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of scale operation that is suitable for is provided, the ruddiness of emission is pure, and at the bottom of the synthesis temperature, the maximum excitation wavelength is positioned at blue region, the inorganic materials of energy efficient absorption GaN chip blue light and red-emitting.
Purpose of the present invention is achieved through the following technical solutions:
A kind of two primary colours white light LEDs fluorine titanium salt red light material: this material is with BaTiF
6Be matrix, with Mn
4+As activator, chemical constitution is BaTiF
6: Mn
4+Mn
4+Part replaces Ti
4+, Mn
4+The mole doping content be 0.25%～2.5%.
Further, the maximum excitation wavelength of this material is in blue region, is that the blue-ray LED of 440～470nm excites with wavelength, obtains the pure ruddiness of color; Chromaticity coordinates is positioned at: x=0.61, y=0.33.
The described two primary colours white light LEDs preparation method of fluorine titanium salt red light material: with reactant B aF
2, titanium source and KMnO
4, the HF aqueous solution and water mixes, normal temperature to 180 ℃ hydro-thermal reaction is 3～12 hours in reactor, gets white precipitate, suction filtration, oven dry obtains white powder; Wherein, The titanium source is tetrabutyl titanate or TiO
2Described BaF
2, titanium source and KMnO
4Concentration in reaction system is respectively 0.01～0.1mol/L, 0.01～0.1mol/L and 0.25%～2.5%mol/L; The mass ratio of the HF aqueous solution and water is 4～10:100; HF aqueous solution mass concentration is 40%.
The temperature of described hydro-thermal reaction is preferably 60 to 120 ℃.
The time of described hydro-thermal reaction is preferably 5～10 hours.
Described Mn
4+The mole doping content be preferably 0.5% ?2%.
With respect to prior art, the present invention has following advantage and effect:
(1) CaAl that mixes of the present invention and known tetravalence manganese
12O
19: Mn
4+Compare, higher in the assimilated efficiency in the zone of blue light, and material granule evenly disperses, and the ruddiness of emission is purer.
(2) the present invention than prior art than red light material KSiF
6: Mn
4+Low 10 times of the concentration of (it is yellow that powder is) required etching solution, and do not need to use expensive metal simple-substance raw material, be suitable for scale operation.The HF aqueous solution of the present invention and KMnO4 totally are called etching solution.Raw material of the present invention is that mass concentration is 40% the HF aqueous solution, but the concentration of reaction system is little more than this.And the document reaction density is 40%; The used KMnO4 concentration of prior art is also far away than the present invention height.
(3) the present invention does not contain rare earth because of material, and preparation process need not to keep away water and keeps away oxygen, need not high temperature sintering, and therefore, cost is far below than commercial nitride rouge and powder.
(4) synthesis temperature of the present invention compares CaAl
12O
19: Mn
4+Low 1200 degree.
Description of drawings
Fig. 1 is BaTiF among the embodiment 1
6: Mn
4+XRD standard card data and the XRD figure of product.
Fig. 2 is BaTiF among the embodiment 1
6: Mn
4+SEM figure.
Fig. 3 is BaTiF
6: Mn
4+The excitation spectrum of (embodiment 2) (the monitoring wavelength is 630nm) and emmission spectrum (excitation wavelength is 460nm).
Fig. 4 is the different K MnO in the embodiment of the invention 1～4
4BaTiF under the concentration
6: Mn
4+Emmission spectrum figure under 466nm excites.KMnO among a among the figure, b, c, the d
4Concentration be respectively 0.25%, 0.5%, 1%, 2.5%.
Fig. 5 is BaTiF among the embodiment 9
6: Mn
4+SEM figure.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 1.7ml tetrabutyl titanate solution, 5ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 85ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 120 ℃ of baking oven reactions after 12 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.Its XRD(Bruker D8Advance X-ray diffractometer detects) as shown in Figure 1, XRD shows that product is pure BaTiF
6Phase.Scanning electron microscope records at Nova NanoSEM200, under the effect of electron beam; As shown in Figure 2, amplify 20000 times, observe the product microscopic appearance and be tiny particulate state, distribution of sizes is narrower, and diameter is about 3～4 microns, and length is about 6 microns.The particle of product is more even, and its particle size size and scope distribute and also suit to be coated with the pipe application.Product does not contain rare earth, and the preparation method is simple, is suitable for industrial production.The chromaticity coordinates of material is positioned at: x=0.62, y=0.37.
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 1.7ml tetrabutyl titanate solution, 10ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 80ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 120 ℃ of baking oven reactions after 12 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.Utilize Fluoromax ?4 fluorescence spectrophotometer (HORIBA Jobin Yvon Inc.), the luminescent properties of testing product at ambient temperature, as shown in Figure 3, this material excitation spectrum by three lay respectively at 250nm, 350nm, the 460nm broadband is formed, its maximum excitation band (460nm) mates fully with the blue light that the GaN blue chip is sent out, emmission spectrum is made up of three spikes that lay respectively at 616nm, 634nm, 650nm, and the climax is positioned at 634nm.The chromaticity coordinates of material is positioned at: x=0.62, y=0.37.
Embodiment 3
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 1.7ml tetrabutyl titanate solution, 20ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 70ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 120 ℃ of baking oven reactions after 12 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.The chromaticity coordinates of material is positioned at: x=0.62, y=0.37.
Embodiment 4
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 1.7ml tetrabutyl titanate solution, 50ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 40ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 120 ℃ of baking oven reactions after 12 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Fig. 4 be the embodiment of the invention 1 ? different K MnO in 4
4BaTiF under the concentration
6: Mn
4+Emmission spectrum figure under 466nm excites.KMnO among a among the figure, b, c, the d
4Concentration be respectively 0.25%, 0.5%, 1%, 2.5%.Emmission spectrum is made up of three spikes, and the climax is positioned at 634nm.The chromaticity coordinates of material is positioned at: x=0.62, y=0.37.
Embodiment 5
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 1.7ml tetrabutyl titanate solution, 40ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 50ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 120 ℃ of baking oven reactions after 12 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Embodiment 6
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.5260g BaF respectively
2Solid, 1.0ml tetrabutyl titanate solution, 20ml concentration are the KMnO of 0.05mol/L
4Solution, 10ml volumetric concentration are 40% the HF aqueous solution, add the 70ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 30 minutes, the stainless steel cauldron of packing into was put room temperature reaction after 8 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Embodiment 7
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 1.7534g BaF respectively
2Solid, 3.4ml tetrabutyl titanate solution, 40ml concentration are the KMnO of 0.05mol/L
4Solution, 20ml volumetric concentration are 40% the HF aqueous solution, add the 40ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 20 minutes, the stainless steel cauldron of packing into was put 80 ℃ of baking oven reactions after 3 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Embodiment 8
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.1753g BaF respectively
2Solid, 0.34ml tetrabutyl titanate solution, 20ml concentration are the KMnO of 0.05mol/L
4Solution, 15ml volumetric concentration are 40% the HF aqueous solution, add the 65ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 15 minutes, the stainless steel cauldron of packing into was put 100 ℃ of baking oven reactions after 5 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Embodiment 9
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.1753g BaF respectively
2Solid, 0.0799g TiO
2Solid, 10ml concentration are the KMnO of 0.05mol/L
4Solution, 20ml volumetric concentration are 40% the HF aqueous solution, add the 70ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 30 minutes, the stainless steel cauldron of packing into was put 100 ℃ of baking oven reactions after 5 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.As shown in Figure 5, scanning electron microscope records at Nova NanoSEM200, under the effect of electron beam, amplifies 20000 times, and observing the product microscopic appearance, to be the large size micron bar-shaped, and diameter is about 10～15 microns, and length is about 50～60 microns.This sample is with TiO
2For the titanium source, though also can obtain the target luminescent material, its particle size is than among the embodiment 1～8 being that the product for preparing of raw material is a lot of greatly with the tetrabutyl titanate.
Embodiment 10
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 1.753g BaF respectively
2Solid, 0.799gTiO
2Solid, 10ml concentration are the KMnO of 0.05mol/L
4Solution, 20ml volumetric concentration are 40% the HF aqueous solution, add the 70ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 10 minutes, the stainless steel cauldron of packing into was put 60 ℃ of baking oven reactions after 5 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
Embodiment 11
Be in the tetrafluoroethylene inner liner of reaction kettle of 120ml at content volume, add 0.8767g BaF respectively
2Solid, 0.3994g TiO
2Solid, 20ml concentration are the KMnO of 0.05mol/L
4Solution, 15ml volumetric concentration are 40% the HF aqueous solution, add the 65ml deionized water again and make the reaction soln cumulative volume keep 100ml.Magnetic agitation 10 minutes, the stainless steel cauldron of packing into was put 140 ℃ of baking oven reactions after 3 hours, took out naturally cooling.Suction filtration, washing is dried naturally, obtains white powder.Product issues bright red at ultraviolet lamp.
The CaAl that the present invention and known tetravalence manganese mix
12O
19: Mn
4+Compare, higher in the assimilated efficiency in the zone of blue light, as the excitation spectrum (shown in Figure 3) of embodiment 2 samples, the maximum excitation band is in blue region, and the blue light of being sent out with the GaN blue chip mates fully, and CaAl
12O
19: Mn
4+The maximum excitation band in the near ultraviolet region, and material granule evenly disperses, the ruddiness of emission is purer.
The present invention than bibliographical information than red light material KTiF
6: Mn
4+Low 10 times of the concentration of (it is yellow that powder is) required etching solution, and do not need to use expensive metal simple-substance raw material, be suitable for scale operation.The concentration of used etching solution is all lower than the bibliographical information among all embodiment.Document need be used expensive titanium metal simple substance, and only needs among all embodiment of this patent to use titanium dioxide and tetrabutyl titanate as the titanium source.
The present invention does not contain rare earth because of material, and preparation process need not to keep away water and keeps away oxygen, need not high temperature sintering, and therefore, cost is far below than commercial nitride rouge and powder.Such material synthesis temperature of bibliographical information is up to 1500 degree, and the synthesis temperature among all embodiment of the present invention is than low 250 degree of prior art; Synthesis temperature of the present invention compares CaAl
12O
19: Mn
4+Low 1200 degree.
Claims (6)
1. a primary colours white light LEDs is with fluorine titanium salt red light material, and it is characterized in that: this material is with BaTiF
6Be matrix, with Mn
4+As activator, chemical constitution is BaTiF
6: Mn
4+Mn
4+Part replaces Ti
4+, Mn
4+The mole doping content be 0.25%～2.5%.
According to the described two primary colours white light LEDs of claim 1 with fluorine titanium salt red light material, it is characterized in that: the maximum excitation wavelength of material is in blue region, is that the blue-ray LED of 440～470nm excites with wavelength, obtains the pure ruddiness of color; Chromaticity coordinates is positioned at: x=0.61, y=0.33.
3. the described two primary colours white light LEDs of claim 1 is characterized in that: with reactant B aF with the preparation method of fluorine titanium salt red light material
2, titanium source and KMnO
4, the HF aqueous solution and water mixes, normal temperature to 180 ℃ hydro-thermal reaction is 3～12 hours in reactor, gets white precipitate, suction filtration, oven dry obtains white powder; Wherein, The titanium source is tetrabutyl titanate or TiO
2Described BaF
2, titanium source and KMnO
4Concentration in reaction system is respectively 0.01～0.1mol/L, 0.01～0.1mol/L and 0.25%～2.5%mol/L; The mass ratio of the HF aqueous solution and water is 4～10:100; HF aqueous solution mass concentration is 40%.
4. according to the preparation method of the described two primary colours white light LEDs of claim 3 with fluorine titanium salt red light material, it is characterized in that: the temperature of described hydro-thermal reaction is 60 to 120 ℃.
5. according to the preparation method of the described two primary colours white light LEDs of claim 3 with fluorine titanium salt red light material, it is characterized in that: the time of described hydro-thermal reaction is 5～10 hours.
6. according to the preparation method of the described two primary colours white light LEDs of claim 3 with fluorine titanium salt red light material, it is characterized in that: described Mn
4+The mole doping content be 0.5% ?2%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357050A (en) * | 2014-10-25 | 2015-02-18 | 云南民族大学 | High-color-purity red luminescent material for blue light excitation and preparation method of red luminescent material |
| CN109777418A (en) * | 2019-01-21 | 2019-05-21 | 温州大学 | A kind of Mn4+Adulterate compound fluotitanate red light material of double alkali metal and preparation method thereof |
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| US20060169998A1 (en) * | 2005-02-02 | 2006-08-03 | Gelcore, Llc | Red line emitting phosphor materials for use in LED applications |
| US20120299466A1 (en) * | 2011-03-23 | 2012-11-29 | General Electric Company | Color stable manganese-doped phosphors |
| CN103003388A (en) * | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture-resistant phosphor and associated method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060169998A1 (en) * | 2005-02-02 | 2006-08-03 | Gelcore, Llc | Red line emitting phosphor materials for use in LED applications |
| CN103003388A (en) * | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture-resistant phosphor and associated method |
| US20120299466A1 (en) * | 2011-03-23 | 2012-11-29 | General Electric Company | Color stable manganese-doped phosphors |
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| YAN KAI XU等: "Photoluminescence and Raman Scattering Spectra in (NH4)2XF6:Mn4+ (X = Si, Ge, Sn, and Ti) Red Phosphors", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357050A (en) * | 2014-10-25 | 2015-02-18 | 云南民族大学 | High-color-purity red luminescent material for blue light excitation and preparation method of red luminescent material |
| CN109777418A (en) * | 2019-01-21 | 2019-05-21 | 温州大学 | A kind of Mn4+Adulterate compound fluotitanate red light material of double alkali metal and preparation method thereof |
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