WO2016127843A1 - 固体光源用荧光材料、其制造方法及包含该荧光材料的组合物 - Google Patents

固体光源用荧光材料、其制造方法及包含该荧光材料的组合物 Download PDF

Info

Publication number
WO2016127843A1
WO2016127843A1 PCT/CN2016/073063 CN2016073063W WO2016127843A1 WO 2016127843 A1 WO2016127843 A1 WO 2016127843A1 CN 2016073063 W CN2016073063 W CN 2016073063W WO 2016127843 A1 WO2016127843 A1 WO 2016127843A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorescent material
group
fluorescent
nitride
formula
Prior art date
Application number
PCT/CN2016/073063
Other languages
English (en)
French (fr)
Inventor
常耀辉
维什尼亚科夫A•B
李士明
潘长魁
陈琳
潘惠俏
Original Assignee
大连利德照明研发中心有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 大连利德照明研发中心有限公司 filed Critical 大连利德照明研发中心有限公司
Publication of WO2016127843A1 publication Critical patent/WO2016127843A1/zh

Links

Images

Classifications

    • 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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • 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

Definitions

  • the invention relates to a fluorescent material for a solid light source, in particular to a fluorescent material for a light emitting diode (LED) and a preparation method thereof, the fluorescent material can be combined with a plurality of matrix yellow and green phosphors to produce a fluorescent material combination for a white LED. Things.
  • a fluorescent material for a solid light source in particular to a fluorescent material for a light emitting diode (LED) and a preparation method thereof, the fluorescent material can be combined with a plurality of matrix yellow and green phosphors to produce a fluorescent material combination for a white LED. Things.
  • the utility model has the advantages of high luminous efficiency, energy saving, stable performance, long service life (up to 50,000 hours), green environmental protection, instant start, fast response and strong practicability.
  • the realization of white LED can be divided into the following three types: (1) three-primary LED multi-chip combination, (2) near-ultraviolet ( ⁇ 395nm) chip excitation, and (3) blue ( ⁇ 465nm) LED chip excitation;
  • the white light system of the (3) blue LED-yellow phosphor combination has high efficiency, simple preparation, and good temperature stability.
  • the principle is: when a forward DC voltage of 3 to 5 V is applied to both ends of the GaN/InGaN diode, The semiconductor chip emits blue light of 455-475 nm, and the Ce 3+ activated yttrium aluminum garnet YAG:Ce 3+ phosphor coated on the surface of the chip is excited by part of the blue light to emit yellow light, yellow light and transmitted.
  • the blue light is combined, white light is produced.
  • due to its lack of red light components it is difficult to produce high color rendering index, low color temperature and high level white LED.
  • the nitride red fluorescent material is mainly composed of an alkaline earth metal and a rare earth metal. Since the chemical properties of the alkaline earth metal element and the rare earth metal element are active, it is easy to form impurities with water and oxygen, thereby affecting the components of the synthesized product, and affecting the final product. Optical performance. Therefore, the raw materials and the atmosphere in the synthesis process Putting higher requirements makes the processing more difficult and the cost increases.
  • the present invention herein discloses a novel nitride red fluorescent material that is chemically stable and has high luminous efficiency.
  • the method for preparing a fluorescent material according to the present invention uses a metal nitride having a more stable property and a low price as a raw material for production, thereby making the process more safe and reliable, and at the same time reducing the production cost.
  • the object of the present invention is to provide an improved nitride fluorescent material with high color rendering property, high stability, low light decay, energy saving and the like in view of the shortcomings of the red light efficiency of the fluorescent material in the prior art.
  • the present invention performs charge compensation on the charged center formed by the Al and Si matrix structures by using the principle of monovalent charge compensation.
  • the introduction of a monovalent charge compensator allows the phosphor to reach charge balance
  • the luminous efficiency of the light material is significantly enhanced.
  • the amount of the monovalent charge compensator can be adjusted as needed to obtain a fluorescent material of a desired color.
  • the introduction of the flux reduces the synthesis temperature of the fluorescent material of the present invention to about 950 to 1580 ° C, which is important for reducing the production cost.
  • the weighing and oscillating mixing of the nitride are performed in a nitrogen atmosphere, which can effectively prevent oxidation of the nitride in the air.
  • a fluorescent material comprising a compound of the formula (I):
  • M is selected from the group consisting of divalent metals Ca, Sr, Ba, Mg, Zn, and combinations thereof;
  • M' is selected from the group consisting of monovalent metals Li, Na, and combinations thereof;
  • N is the N element
  • X is the F element
  • the ⁇ RE-1 is selected from the group consisting of Eu, Mn, and combinations thereof;
  • the ⁇ RE-2 is selected from the group consisting of Ce, Pr, La, Tb, Er, and combinations thereof;
  • n 2/3(1+ ⁇ )+z+1/3b+4/3d+c-1/3y;
  • the fluorescent material comprises a compound of formula (I-1):
  • M is selected from the group consisting of Ca, Sr, Ba, Zn, and combinations thereof; and ⁇ RE-2 is selected from the group consisting of Pr, La, Tb, Er, and combinations thereof.
  • RE represents a rare earth activator
  • the ⁇ RE-1 is an activator selected from the group consisting of a rare earth element Eu, a transition metal element Mn, and a combination thereof
  • the ⁇ RE-2 being a co-activator selected from the group consisting of rare earth elements a group consisting of Ce, Pr, La, Tb, Er, and combinations thereof;
  • the fluorescent material is selected from the group consisting of:
  • the fluorescent material is selected from the group consisting of:
  • the fluorescent material of the present invention comprises a compound having the formula:
  • the fluorescent material of the present invention comprises a compound having the formula:
  • a method of preparing a fluorescent material comprising:
  • the metal nitride is selected from the group consisting of aluminum nitride, silicon nitride, lithium nitride, and rare earth nitride.
  • the mixture is calcined at a temperature of 950 to 1580 ° C for 5 to 6 hours under a reducing atmosphere of a mixed gas of nitrogen and hydrogen.
  • a fluorescent material composition comprising the fluorescent material of the present invention; and a green fluorescent powder; wherein a weight ratio of the fluorescent material to the green fluorescent powder is about 4%: 96% - 20%: 80%.
  • a fluorescent material composition comprising the fluorescent material of the present invention; and a yellow fluorescent powder; wherein a weight ratio of the fluorescent material to the green fluorescent powder is about 4%: 96% - 20%: 80%.
  • the weight ratio of the fluorescent material to the green phosphor is about 10%: 90% to 12%: 88%.
  • the green phosphor is any of yttrium aluminum garnet, silicate.
  • the green phosphor is a yttrium aluminum garnet structural compound having a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7 .
  • the green phosphor is a yttrium aluminum garnet having a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7 .
  • the green phosphor is a silicate of the formula Y 0.7 Sr 0.613 Ba 0.96 Si 0.875 O 3.5 :Eu 2+ .
  • the fluorescent material of the present invention employed in the fluorescent material composition is (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 .
  • the fluorescent material for solid-state light source of the present invention has a light-emitting characteristic that the activator Eu 2+ forms a broad characteristic emission band in the orange-red region of 550 nm to 750 nm, and the 4f-5d energy attributed to Eu 2+
  • the level transitions are between 525 nm and 610 nm, the spectral coverage is between 623 nm and 666 nm, and the half width is in the range of 86 to 93 nm.
  • the red fluorescent material for a solid light source according to the present invention is characterized in that it can be excited by ultraviolet light of 250 nm to 490 nm to blue light.
  • the invention provides a method for preparing a red fluorescent material for a solid light source, the method comprising the following steps:
  • a starting material comprising a nitride of M or a simple substance thereof, a nitride of M', and a nitride of AlN, Si 3 N 4 and a rare earth element or a simple substance thereof;
  • the fluorescent material provided by the present invention is a compound having the formula (I):
  • the measurement index (1+ ⁇ ) changes from 1.005 to 1.0525, and the corresponding ratio From 0.249 to 0.3509, the element ratio is compared to the CaAlSiN 3 compound.
  • the scope is expanded.
  • the optical properties of the sample change significantly.
  • the (1+ ⁇ ) value decreases, the red color of the emitted light darkens and the peak shifts red.
  • the coordinates become longer and the half-width variation is weak.
  • the fluorescent material for a solid-state light source according to the present invention can be excited by violet-blue light of 250 nm to 490 nm.
  • the fluorescent material for a solid-state light source according to the present invention may be combined with yttrium aluminum garnet, silicate green phosphor or with Y 3 Al 5 O 12 :Ce 3+ yellow phosphor to form a white LED.
  • the green phosphor used in the above white LED may be a green phosphor having a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7 .
  • the green phosphor used in the above white LED may be a green phosphor having a molecular formula of Y 0.7 Sr 0.613 Ba 0.96 Si 0.875 O 3.5 :Eu 2+ .
  • Figure 1 shows (a) (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 and (b) (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 XRD of fluorescent material Spectrum.
  • 2 is an emission spectrum of a fluorescent material prepared by the first embodiment and having a molecular formula of (Sr 0.99 , Eu 0.01 ) 1.005 Li 1.0 Al 3 N 4 F 0.01 under excitation of a 460 nm blue LED.
  • 3 is an emission spectrum of a fluorescent material prepared by the method 2 (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 excited by a 460 nm blue LED.
  • Figure 5 shows the molecular formulas (Sr 0.961 , Ca 0.019 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7132 F 0.0263 , (Sr 0.96 , Ba 0.02 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.713 F 0.0267 and (Sr 0.88 Zn 0.1 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7164 F
  • Figure 6 is doped with a fluorescent material, respectively, Pr 3+, La 3+ and Tb 3+ emission spectra at 460nm blue LED excitation.
  • the molecular formulas of the fluorescent materials are:
  • Figure 7 shows the emission spectra of fluorescent materials with different Mn 2+ contents excited by 460 nm blue LEDs.
  • the molecular formulas of the fluorescent materials are:
  • Figure 8 shows the emission spectra of fluorescent materials with different Li + contents excited by 460 nm blue LEDs.
  • the molecular formulas of the fluorescent materials are:
  • Figure 9 shows the emission spectra of fluorescent materials (Sr 1- ⁇ , Eu ⁇ ) 1 + ⁇ Al 0.1 Si 2.2 N n F y with different (1 + ⁇ ) values excited by a 460 nm blue LED.
  • the molecular formulas of the fluorescent materials are:
  • Figure 10 shows the emission spectra of a fluorescent material (Sr 1- ⁇ , Eu ⁇ ) 1 + ⁇ Li b Al 0.1 Si 2.2 N n F y with different (1 + ⁇ ) values under excitation of a 460 nm blue LED.
  • the molecular formulas of the fluorescent materials are:
  • Figure 11 shows the emission spectra of a fluorescent material (Sr 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Al 0.1 Si d N n F y with different Si 4+ contents under excitation of a 460 nm blue LED.
  • the molecular formulas of the fluorescent materials are:
  • Figure 12 shows the emission spectra of a fluorescent material (M 1- ⁇ , Eu ⁇ ) 1 + ⁇ Al c Si d N n X y with different Al 3+ contents under excitation of a 460 nm blue LED.
  • the molecular formulas of the fluorescent materials are:
  • Figure 13 shows the emission spectra of a fluorescent material (Sr 1- ⁇ , Eu ⁇ ) 1 + ⁇ Al 0.1 Si 2.2 N n F y with different Eu 2+ contents under excitation of a 460 nm blue LED.
  • the molecular formulas of the fluorescent materials are:
  • FIG. 14 is a graph showing a fluorescent material having a molecular formula of (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 prepared according to Example 2 of the present invention, respectively, having a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7 and Y 0.7 Sr 0.613 Ba 0.96 Si 0.875 O 3.5 : Eu 2+ green phosphor ratio, and with the molecular formula Y 3 Al 5 O 12 :Ce 3+ yellow phosphor
  • the fluorescent material of the formula (Sr, Ba) 1.88 SiO 4 :Eu 2+ has a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7
  • the white phosphor LED formed by the green phosphor ratio is tested in a
  • the fluorescent material prepared by the invention has the following composition:
  • the fluorescent material sample shown in the embodiment is obtained by high-temperature baking of a mixture of metal nitride, aluminum nitride, silicon nitride, and rare earth nitride.
  • the starting material particle size (D50) used was less than 3 microns (measured by a laser particle size analyzer).
  • a fluorescent material is prepared by a high temperature solid phase reaction method.
  • the dry powder of the starting material (metal nitride or its element, and cesium fluoride or lithium fluoride) is weighed in a closed glove box filled with nitrogen, and shaken and mixed uniformly to obtain a mixture.
  • cesium fluoride or lithium fluoride in the mixture can act as a flux to form a liquid phase in the reaction of the solid surface, thereby accelerating the mass transfer rate and accelerating the formation rate of the target product.
  • the mixture was ground and mixed, and then placed in a boron nitride (BN) crucible.
  • BN boron nitride
  • the boron nitride crucible containing the uniformly mixed mixture is placed in a kiln, and calcined at 950 to 1700 ° C for about 3 to 10 hours in an atmosphere of nitrogen-hydrogen reduction (75% by volume). Then, the calcined material was cooled to below 100 ° C and taken out from the furnace.
  • the calcined material is dry sieved and then alcohol washed with isopropyl alcohol, and then 5 ⁇ orthosilicate is added to coat the surface of the powder with a silicon film layer, and finally a loose and smooth powder is obtained.
  • Inventive fluorescent material is dry sieved and then alcohol washed with isopropyl alcohol, and then 5 ⁇ orthosilicate is added to coat the surface of the powder with a silicon film layer, and finally a loose and smooth powder is obtained.
  • the fluorescent material obtained by the above method has a peak of emission spectrum at a red light band of 623 nm to 656 nm under excitation of 460 nm blue light.
  • a fluorescent material having a molecular formula of (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 was prepared, and the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN and SrF 2 , and the starting materials were used.
  • the stoichiometric index is in accordance with (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 , and the calcination temperature is 1580 ° C in the atmosphere of nitrogen reduction (volume ratio of 75%), and the calcination is continued for 6 hours.
  • the emission spectrum of the obtained fluorescent material (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 under the excitation of a 460 nm blue LED is shown in FIG. 3 .
  • a fluorescent material having a molecular formula of (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 was prepared, and the starting materials were Sr 3 N 2 , Li 3 N, AlN, Si 3 N 4 , EuN and SrF 2 , The amount of starting materials used is such that the stoichiometric index is consistent with (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 , and the calcination temperature is 1480 ° C under a nitrogen-hydrogen reduction (75% by volume) atmosphere. Continue to roast for 6 hours.
  • the obtained molecular formula is (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012
  • the emission spectrum of the fluorescent material excited by a 460 nm blue LED is shown in FIG. 4 .
  • the molecular formula was prepared (Sr 0.961 , Ca 0.019 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7132 F 0.0263 , (Sr 0.96 , Ba 0.02 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.713 F 0.0267 and (Sr 0.88 , Zn 0.1 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7164 F 0.0167 fluorescent material, starting materials are Sr 3 N 2 , AlN, Si 3 N 4 , EuN, SrF 2 , CaF 2 , BaF 2 and Zn, starting materials used It was made to conform to the stoichiometric index of the molecular formula, and the calcination temperature was 1570 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and baking was continued for 6 hours.
  • the obtained molecular formula is (Sr 0.961 , Ca 0.019 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7132 F 0.0263 , (Sr 0.96 , Ba 0.02 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.713 F 0.0267 and (Sr 0.88 , Zn 0.1 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7164 F
  • the emission spectrum of 0.0167 fluorescent material excited by a 460 nm blue LED is shown in Fig. 5.
  • the starting materials are Sr 3 N 2 , AlN, Si 3 N 4 , EuN, SrF 2 , PrN, metal La and metal Tb, and the calcination temperature is 1580 ° C in an atmosphere of nitrogen reduction (75% by volume), and the calcination is continued. 6 hours.
  • the obtained molecular formula is (Sr 0.96 , Eu 0.04 ) 1.024 Pr 0.005 Al 0.1 Si 2.2 N 3.7167 F 0.012 , (Sr 0.96 , Eu 0.04 ) 1.024 La 0.02 Al 0.1 Si 2.2 N 3.7317 F 0.012 and (Sr 0.96 , Eu 0.04 ) 1.024 Tb 0.005 Al 0.1 Si 2.2 N 3.7167 F
  • the emission spectrum of the 0.012 fluorescent material excited by a 460 nm blue LED is shown in FIG.
  • Fluorescent materials with different Mn 2+ contents were prepared, and the starting materials were used in such a way that their stoichiometric indices correspond to the following molecular formulas:
  • the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN, SrF 2 and Mn, and the calcination temperature was 1,580 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and calcination was continued for 6 hours.
  • Fluorescent materials with different Li + contents are prepared, and the starting materials are used in such a way that their stoichiometric indices respectively conform to the following formula:
  • the starting materials are Sr 3 N 2 , Li 3 N, AlN, Si 3 N 4 , EuN, Mg and SrF 2 , calcined at 1480 ° C in an atmosphere of nitrogen reduction (75% by volume), and calcined for 6 hours. .
  • the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN and SrF 2 , and the calcination temperature was 1,580 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and the calcination was continued for 6 hours.
  • the starting materials were Sr 3 N 2 , Li 3 N, AlN, Si 3 N 4 , EuN and SrF 2 , and the calcination temperature was 1480 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and the calcination was continued for 6 hours.
  • the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN and SrF 2 , and the calcination temperature was 1,580 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and the calcination was continued for 6 hours.
  • the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN, CaF 2 and SrF 2 , and the calcination temperature was 1,580 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and the calcination was continued for 6 hours.
  • Fluorescent materials with different Eu 2+ content were prepared, and the starting materials were used in such a way that their stoichiometric indices were consistent with the following molecular formulas:
  • the starting materials were Sr 3 N 2 , AlN, Si 3 N 4 , EuN and SrF 2 , and the calcination temperature was 1,580 ° C in an atmosphere of nitrogen-hydrogen reduction (75% by volume), and calcination was continued for 6 hours.
  • the red fluorescent material (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 prepared by using the second embodiment of the present invention has a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F, respectively).
  • the white phosphor LED composition formed by the combination of the green phosphors of 11.7 , the spectrum obtained by the test is shown in FIG. 14 .
  • Figure 1 (a), (b) shows (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 and (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 fluorescent material XRD spectrum.
  • the main diffraction peak positions of (a) and (b) are almost identical, indicating that the doping of Li + does not have a large influence on the crystal structure of the fluorescent material.
  • the emission spectrum of the present embodiment covers a red narrow band of 600 nm to 750 nm, the half width is only 53.4 nm, the emission peak is significantly red-shifted, and is located at 654 nm, and the red light is more concentrated to make the color rendering index and luminescence of the fluorescent material. The brightness has been greatly improved.
  • the emission spectrum is an emission spectrum of a fluorescent material having a molecular formula of (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 excited by a 460 nm blue LED.
  • the emission spectrum covers a continuous broadband of 550 nm to 750 nm, and the emission peak is located near 626 nm, and the half width is 90.2 nm.
  • the emission spectrum is an emission spectrum of a fluorescent material having a molecular formula of (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 excited by a 460 nm blue LED.
  • the emission spectrum covers a continuous wave band of 550 nm to 750 nm, and the emission peak is located near 624 nm, and the half width is 89.4 nm.
  • Figure 5 is a molecular formula of (Sr 0.961 , Ca 0.019 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7132 F 0.0263 , (Sr 0.96 , Ba 0.02 , Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.713 F 0.0267 and (Sr 0.88 , Zn 0.1 ,Eu 0.02 ) 1.0334 Al 0.1 Si 2.2 N 3.7164 F
  • the emission spectrum of 0.0167 fluorescent material excited by 460 nm blue LED It can be seen from the figure that the emission spectrum covers a continuous broadband of 550 nm to 750 nm.
  • the emission peaks are red-shifted, and the peaks are located at 624 nm, 631 nm and 639 nm, respectively, and the half width is half. Gradually increase, the red light area increases.
  • Figure 6 is a view showing the emission spectrum of a fluorescent material doped with Pr 3+ , La 3+ and Tb 3+ ions under excitation of a 460 nm blue LED.
  • the molecular formulas are: (Sr 0.96 , Eu 0.04 ) 1.024 Pr 0.005 Al 0.1 Si 2.2 N 3.7167 F 0.012 , (Sr 0.96 , Eu 0.04 ) 1.024 La 0.02 Al 0.1 Si 2.2 N 3.7317 F 0.012 and (Sr 0.96 , Eu 0.04 ) 1.024 Tb 0.005 Al 0.1 Si 2.2 N 3.7167 F 0.012 . It can be seen from the figure that the spectrum covers a continuous broadband of 550 nm to 750 nm, and the emission peak of the La 3+ doped fluorescent material is relatively red-shifted, the half-width is increased, and the color coordinate is long.
  • Figure 7 is a graph showing the effect of changes in the Mn 2+ content of the fluorescent material on its emission spectrum.
  • the molecular formulas are: (Sr 0.975 , Mn 0.005 , Eu 0.02 ) 1.024 Al 0.1 Si 2.5 N 4.112 F 0.012 , (Sr 0.965 , Mn 0.015 , Eu 0.02 ) 1.024 Al 0.1 Si 2.5 N 4.112 F 0.012 and (Sr 0.95 , Mn 0.03 , Eu 0.02 ) 1.024 Al 0.1 Si 2.5 N 4.112 F 0.012 .
  • the spectrum covers a continuous broadband of 550 nm to 750 nm.
  • the position of the emission peak hardly changes, and the peaks are located at 627 nm, 626 nm, and 627 nm, respectively.
  • Fig. 8 is a graph showing the effect of changes in Li + content on the emission spectrum of a fluorescent material having a molecular formula of (Sr 1- ⁇ , Eu ⁇ ) 1 + ⁇ Li b Al 0.1 Si 2.2 N n F y .
  • the molecular formulas are: (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 , (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.05 Al 0.1 Si 2.2 N 3.7287 F 0.012 , (Sr 0.975 , Eu 0.025 ) 1.024 Li 0.1 Al 0.1 Si 2.2 N 3.7453 F 0.012 , (Sr 0.86 , Mg 0.1 , Eu 0.04 ) 1.024 Li 0.2 Al 0.1 Si 2.2 N 3.7754 F 0.012 , (Sr 0.86 , Mg 0.1 , Eu 0.04 ) 1.024 Li 0.3 Al 0.1 Si 2.2 N 3.8117 F 0.012 .
  • the spectrum covers a continuous broadband of 550 nm to 750 nm.
  • the emission peaks are red-shifted, and the peaks are located at 628 nm, 624 nm, 623 nm, 625 nm, and 656 nm, respectively, and the color coordinates become long.
  • the introduction of the charge compensator Li + causes the phosphor to reach charge balance and enhances the luminous efficiency of the fluorescent material.
  • Figure 9 is a graph showing the effect of the (1+ ⁇ ) value change on the emission spectrum of a fluorescent material in a fluorescent material of the formula (Sr 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Al 0.1 Si 2.2 N n F y , the molecular formulas are: Sr 0.975, Eu 0.025) 1.0191 Al 0.1 Si 2.2 N 3.7095 F 0.0096, (Sr 0.975, Eu 0.025) 1.0287 Al 0.1 Si 2.2 N 3.7143 F 0.01433, (Sr 0.975, Eu 0.025) 1.0382 Al 0.1 Si 2.2 N 3.719 F 0.0191 and (Sr 0.975, Eu 0.025) 1.0478 Al 0.1 Si 2.2 N 3.7238 F 0.0239, seen from FIG, continuous broadband spectrum covering 550nm ⁇ 750nm with increasing (1 + ⁇ ), the emission peak position does not change, a peak at 623nm ⁇ Near 630nm.
  • Figure 10 is a graph showing the effect of the (1+ ⁇ ) value change on the emission spectrum of a fluorescent material in a fluorescent material of the formula (Sr 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Li 0.05 Al 0.1 Si 2.2 N n F y .
  • Figure 11 is a graph showing the effect of changes in Si 4+ content on the emission spectrum of phosphors in a fluorescent material of the formula (Sr 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Al 0.1 Si d N n F y .
  • the molecular formulas are: (Sr 0.98 , Eu 0.02) 1.0287 Al 0.1 Si 1.9 N 3.314 F 0.01433, (Sr 0.98, Eu 0.02) 1.0287 Al 0.1 Si 2.0 N 3.448 F 0.01433, (Sr 0.98, Eu 0.02) 1.0287 Al 0.1 Si 2.2 N 3.7143 F 0.01433, (Sr 0.98 ,Eu 0.02 ) 1.0287 Al 0.1 Si 2.5 N 4.1144 F 0.01433 , as shown in the figure, the spectrum covers a continuous broadband of 550 nm to 750 nm. As the content of Si 4+ increases, the emission peak gradually shifts red, and the peaks are located at 625 nm and 625 nm, respectively. At
  • Figure 12 is a graph showing the effect of changes in Al 3+ content on the emission spectrum of phosphors in a fluorescent material of the formula (M 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Al c Si 2.2 N n F y , the molecular formulas are: (Sr 0.975 ,Eu 0.025 ) 1.0287 Al 0.08 Si 2.2 N 3.694 F 0.01433 ,(Sr 0.975 ,Eu 0.025 ) 1.0287 Al 0.1 Si 2.2 N 3.7143 F 0.01433 ,(Sr 0.493 ,Ca 0.493 ,Eu 0.014 ) 1.0287 Al 1.0 Si 1.0 N 2.9319 F 0.2608 As can be seen from the figure, the spectrum covers a continuous broadband of 550 nm to 750 nm. As the content of Al 3+ increases, the emission peaks are significantly red-shifted, and the peaks are at 625 nm, 626 nm, and 652 nm, respectively, and
  • Figure 13 is a graph showing the effect of changes in Eu 2+ content on the emission spectrum of phosphors in a fluorescent material of the formula (Sr 1- ⁇ ,Eu ⁇ ) 1+ ⁇ Al 0.1 Si 2.2 N n F y .
  • the molecular formulas are: (Sr 0.975 ,Eu 0.025 ) 1.0287 Al 0.1 Si 2.2 N 3.7143 F 0.01433 ,(Sr 0.96 ,Eu 0.04 ) 1.0287 Al 0.1 Si 2.2 N 3.7143 F 0.01433 ,(Sr 0.92 ,Eu 0.08 ) 1.0525 Al 0.1 Si 2.2 N 3.7259 F 0.0263 ,(Sr 0.88 ,Eu 0.12 ) 1.0525 Al 0.1 Si 2.2 N 3.7259 F 0.0263 , as shown in the figure, the spectrum covers a continuous broadband of 550 nm to 750 nm.
  • the emission peaks are significantly red-shifted, and the peaks are located at 628 nm and 635 nm, respectively.
  • the half-value width increases, the color coordinates become significantly longer, and the red light region increases.
  • Figure 14 is a fluorescent material of the formula (Sr 0.975 , Eu 0.025 ) 1.024 Al 0.1 Si 2.2 N 3.712 F 0.012 of the present invention and a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 a green phosphor of 11.7 and Y 0.7 Sr 0.613 Ba 0.96 Si 0.875 O 3.5 :Eu 2+ , and a yellow phosphor with a molecular formula of Y 3 Al 5 O 12 :Ce 3+ , and a molecular formula of (Sr, Ba) a white fluorescent LED composition of 1.88 SiO 4 :Eu 2+ fluorescent material and a green phosphor having a molecular formula of [Lu 0.4415 Y 0.45 Ce 0.05 Ba 0.0585 ] 2.8 Al 5 (O 0.995 , F 0.01 ) 11.7 spectrum.
  • the synthesized sample was tested in a blue light diode-based solid white light source.
  • the results show that the white LED formed by the present invention and the yttrium aluminum garnet green phosphor has a color rendering index (Ra) of 86.9 and a corresponding color temperature (Tc) of 3495K.
  • the spectral band is wider and the effect is better.
  • the data obtained from the summary shows that the optical properties of the sample change significantly as the stoichiometric index (1+ ⁇ ) changes from 1.005 to 1.0525.
  • (1+ ⁇ ) value gradually decreases, the red color is added Deep, the peak is red-shifted, the corresponding color coordinates become longer, and the half-width variation is weaker.
  • the present invention provides a fluorescent material having the formula [M 1- ⁇ , ( ⁇ RE-1) ⁇ ] 1 + ⁇ ( ⁇ RE-2) z M' b Al c Si d N n X y Among them, by changing the different ratios of M, rare earth elements, aluminum and silicon, the luminescent color of the fluorescent material can be adjusted.
  • the fluorescent material according to the present invention can be combined with yellow and green phosphors of yttrium aluminum garnet, silicate and phosphate matrix to obtain white LEDs with high color rendering and stability, which has practical applications. Important and very important.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

本发明涉及一种固体光源用荧光材料，其化学通式为：[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM'bAlcSidNnXy，其中，M为金属元素Mg、Ca、Sr、Ba、Zn中的一种；M'为IA族Li、Na中的一种元素；N为氮元素，RE为稀土元素。本发明的荧光材料具有高显色性、高稳定性、高光效和低衰减等优点。本发明还涉及制备所述荧光材料的方法。此外，本发明还涉及包括所述荧光材料的荧光材料组合物。

Description

固体光源用荧光材料、其制造方法及包含该荧光材料的组合物 技术领域
本发明涉及一种固体光源用荧光材料，具体涉及一种发光二极管(LED)用荧光材料及其制备方法，所述荧光材料可以与多种基质黄、绿色荧光粉组合产生白光LED用荧光材料组合物。
背景技术
20世纪90年代蓝光LED在技术上的突破及产业化极大地推动和实现白光发光二极管(White light-emitting diode，WLED)的发展。其具有发光效率高，节能；性能稳定，使用寿命长(可达5万小时)；绿色环保；瞬时启动，响应快，实用性强等优点。
白光LED的实现途径可分为以下三种：(1)三基色LED多芯片组合、(2)近紫外光(～395nm)芯片激发型、(3)蓝光(～465nm)LED芯片激发型；其中第(3)种蓝光LED-黄色荧光粉组合的白光体系效率高、制备简单、温度稳定性较好，原理是：当GaN/InGaN二极管的两端加上3～5V的正向直流电压时，半导体芯片就会发射出455～475nm的蓝光，涂敷在芯片表面的Ce3+激活的钇铝石榴石YAG:Ce3+荧光粉受到部分蓝光的激发而发出黄光，黄光与透过的蓝光复合，便产生了白光。但是由于其缺少红光成分，使得难以制作高显色指数、低色温高水平白光LED。
目前，商用红色荧光粉主要有：稀土硫氧化物(R2O2S:Ln(R＝La,Gd,Y,Lu；Ln＝Eu,Tb,Sm,Pr)、氧化物(Y2O3:Eu3+和Gd2O3:Eu3+)钨钼酸盐(Ca(WO4)2(MoO4):Eu3+)、钒磷硼酸盐(YVO4:Eu3+)、硼酸盐(GdMgB5O10:Ce3+,Mn2+)以及硅酸盐(Ca8Mg(SiO4)4Cl2)等基质的荧光粉。由于上述基质荧光粉存在化学性和热稳定性很差，在空气中易潮解，受热易分解，生产过程中对环境存在污染等问题而使其在LED领域的广泛应用受到限制。
近年来，在固态照明推动下，具有热稳定性好、化学稳定性高、发光性能优良、光衰小，环保无毒的Eu2+激活的氮化物荧光材料成为在LED暖白光和液晶显示器背光源领域最有希望取代硫化物等红色荧光粉的高品质红色荧光材料。
目前，氮化物红色荧光材料主要由碱土金属与稀土金属组成，由于碱土金属元素和稀土金属元素的化学性质活泼，与水和氧容易形成杂质进而影响合成产物的组分，而影响到终产物的光学性能。因此对合成过程中的原材料以及气氛环境 提出较高要求，使得加工难度增大，成本提高。
最早的氮化物荧光粉专利是欧洲专利申请EP1104799A1，其中公开了一种化学式为MxSiyNz:Eu2+的红色荧光粉，即258结构氮化物，其首次提出可应用于白光LED照明领域获得白光。随后，欧洲专利申请EP1413618 A1中公开了可应用于LED照明领域的MSi2O2N2：Eu2+(M＝Ca，Sr，Ba)橙红色荧光粉；但由于此结构化合物在化学稳定性、发光效率方面表现较差，使得其的广泛应用受到限制。
随后，在授予日本同和矿业(DOWA)的美国专利US7252788B2中，公开了一种化学式为CaAlSiN3:Eu2+的荧光材料，其具有以往红色荧光粉所没有的一些优点：发光效率高、化学性质稳定、光衰小等，在蓝光芯片激发下，可发射峰值范围600-750nm深红色光谱，成为改善LED白光和液晶显示器背光源显指的最佳甚至唯一的高品质红色荧光材料。
在授予Intematix的美国专利US8274215B2中，在DOWA专利基础上，添加Sr2+取代部分Ca2+，各元素比例为1:1:1:3，提出了化学式为(Ca,Sr)AlSiN3:Eu2+的荧光材料。其中，Sr取代Ca使得荧光材料发光颜色加深，并且认为卤素在合成过程中提供一种吸杂效果，使得结构中的氧杂质含量保持在一个较低的水平，但合成温度偏高。
近年，飞利浦公司合成了LED用窄带红色Sr[LiAl3N4]:Eu2+荧光材料，其中因Li-Al键长相近，因此可以采用Li补偿Al3+的方法，进而较大幅度地提高了荧光粉的显色指数和发光亮度。但是，其采用的原材料中Al，Li元素来源为氢化铝锂复合氢化物，遇水易爆炸，工业生产上存在很大危险性。
基于上述分析可见，仍存在对于化学性质稳定、发光效率高，且工艺流程更加安全可靠，生产成本低廉的荧光材料的需求。因此，本发明在此公开一种新型氮化物红色荧光材料，所述荧光材料化学性质稳定，发光效率高。同时，本发明涉及的荧光材料制备方法采用性质更加稳定、价格偏低的金属氮化物作为生产原料，使得工艺流程更加安全可靠，同时降低生产成本。
发明内容
本发明目的在于针对现有技术中荧光材料红光效率不高的缺点，提出一种改进的氮化物荧光材料，其具有高显色性、稳定性强、低光衰、节能等优点。
本发明在已有技术基础上，采用一价电荷补偿原理，对Al、Si基质结构形成的带电中心进行电荷补偿。一价电荷补偿剂的引入使荧光粉达到电荷平衡，对荧 光材料的发光效率有明显增强作用。并且，可以根据需要调节一价电荷补偿剂含量获得所需颜色的荧光材料。
助熔剂的引入使得本发明的荧光材料的合成温度降低到950～1580℃左右，这对于降低生产成本有着重要意义。
根据本发明提供的荧光材料的制备方法，氮化物的称量、振荡混匀均在氮气气氛中进行，这样可以有效防止氮化物在空气中的氧化。
根据本发明的一个方面，提供一种荧光材料，所述荧光材料包括通式(I)的化合物：
[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)；
其中，
M选自由二价金属Ca,Sr,Ba,Mg,Zn及其组合组成的组；
M’选自由一价金属Li,Na及其组合组成的组；
N为N元素；
X为F元素；
所述∑RE-1选自由Eu、Mn及其组合组成的组；所述∑RE-2选自由Ce,Pr,La,Tb,Er及其组合组成的组；
n＝2/3(1+α)+z+1/3b+4/3d+c-1/3y；
0＜α≤0.2；
0≤b≤1.0；
0.01＜c≤3.0；
0≤d≤2.8；
0.005≤γ≤0.15；
0≤z≤0.05；
0≤y≤0.05。
在一些实施方案中，所述荧光材料包括通式(I-1)的化合物：
[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zAlcSidNnXy   (I-1)；
其中，∑RE-2选自由Pr,La,Tb,Er及其组合组成的组；并且b＝0。
在一些实施方案中，M选自由Ca、Sr、Ba、Zn及其组合组成的组；并且∑RE-2选自由Pr,La,Tb,Er及其组合组成的组。
RE代表稀土激活剂，其中，所述∑RE-1是激活剂，选自由稀土元素Eu、过渡金属元素Mn及其组合组成的组，所述∑RE-2是共激活剂，选自稀土元素Ce,Pr,La,Tb,Er及其组合组成的组；
在一些实施方案中，0.001≤α≤0.06。
在一些实施方案中，所述荧光材料选自由如下化合物组成的组：
(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012；
(Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263；
(Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267；
(Sr0.88Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167；
(Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012；
(Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012；
(Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012；
(Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
(Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
(Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
(Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096；
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433；
(Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191；
(Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239；
(Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433；
(Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433；
(Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433；
(Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433；
(Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433；
(Sr0.493,Ca0.493,Eu0.014)1.0287Al1,0Si1.0N2.9319F0.0287；
(Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433；
(Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263；
(Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263。
在一些实施方案中，所述荧光材料选自由如下化合物组成的组：
(Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01；
(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012；
(Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012；
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012；
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012；
(Sr0.975,Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096；
(Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012；
(Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433；
(Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167。
在一些实施方案中，本发明的荧光材料包括具有如下分子式的化合物：
(Sr1-γ,Euγ)1.024Al0.1Si2.2N3.712Fy。
在一些实施方案中，本发明的荧光材料包括具有如下分子式的化合物：
(Sr1-γ,Euγ)1.024Li0.05Al0.1Si2.2N3.7287Fy。
根据本发明的一个方面，提供一种制备荧光材料的方法，包括：
将金属氮化物或其单质与氟化锶或氟化锂，以及，可选地，锰单质混合，其中将各原料按照权利要求1-6中任一项所述的荧光材料的元素摩尔配比称量，并混合均匀形成混合物料；以及将所述混合物料在氮、氢混合气体的还原气氛下，于950～1700℃的温度，焙烧3～10小时。
在一些实施方案中，所述金属氮化物选自由氮化铝，氮化硅，氮化锂，稀土氮化物组成的组。
在一些实施方案中，所述混合物料在氮、氢混合气体的还原气氛下，于950～1580℃的温度，焙烧5～6小时。
根据本发明的一个方面，提供一种荧光材料组合物，包括本发明的荧光材料；以及绿色荧光粉；其中，所述荧光材料与所述绿色荧光粉的重量比约为4％：96％～20％：80％。
根据本发明的一个方面，提供一种荧光材料组合物，包括本发明的荧光材料；以及黄色荧光粉；其中，所述荧光材料与所述绿色荧光粉的重量比约为4％：96％～20％：80％。
在一些实施方案中，所述荧光材料与所述绿色荧光粉的重量比约为10％：90％～12％：88％。
在一些实施方案中，绿色荧光粉是钇铝石榴石、硅酸盐中的任一种。
在一些实施方案中，所述绿色荧光粉是分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的钇铝石榴石结构化合物。
在一些实施方案中，绿色荧光粉是分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的钇铝石榴石。
在一些实施方案中，所述绿色荧光粉是分子式为Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的硅酸盐。
在一些实施方案中，荧光材料组合物中所采用的本发明的荧光材料是(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012。
在一些实施方案中，本发明所述的固体光源用荧光材料，其发光特征为激活剂Eu2+在550nm～750nm橙红区域形成较宽的特征发射带，归属于Eu2+的4f-5d能级跃迁，峰值位于525nm～610nm，光谱覆盖范围位于623nm～666nm，半峰宽范围在86～93nm。
本发明所述的固体光源用红色荧光材料，其特征为可以被250nm～490nm的紫外光到蓝光所激发。
根据本发明所提出的通式，显而易见，1+α不等于1，范围在1到1.5之间。因此，在已知的氮化物荧光粉专利解决方案之外，属于非化学计量化合物。
本发明提供一种固体光源用红色荧光材料的制备方法，所述方法包括如下步骤：
(1)提供起始原料，所述起始原料包括M的氮化物或其单质、M’的氮化物以及AlN、Si3N4和稀土元素的氮化物或其单质；
(2)在充满氮气的氮气手操箱中，按照通式(I)规定的摩尔配比：
[M1-γ(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)；
称量(1)中提供的起始原料，并将其混合均匀形成混合物料；
(3)将(2)中混合均匀的混合物料放入窑炉中，在氮、氢气混合气氛中于950～1700℃，焙烧约3～10个小时，冷却后，得到通式(I)的化合物：
[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)
(4)将(3)中得到的通式(I)的化合物用研钵磨碎，经过水洗、醇洗等一系列后处理步骤，并完成包膜；
(5)将(4)中处理后的产品在140℃下烘干约12小时，得到具有高显色性、高稳定性、低光衰优点的荧光材料。
如上所述，本发明提供的荧光材料是具有通式(I)的化合物：
[M1-γ，(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)
其中，计量指数(1+α)从1.005变化到1.0525，相应的比值
Figure PCTCN2016073063-appb-000001
从0.249变化到0.3509，元素比例相比于CaAlSiN3化合物中
Figure PCTCN2016073063-appb-000002
范围扩大。
随着化学计量指数(1+α)从1.005变化到1.0525，样品的光学特性发生显著变化，随着(1+α)值的逐渐减小，发射红光颜色加深，峰值发生红移，相应色坐标变长，半峰宽变化微弱。
本发明所述的固体光源用荧光材料，可以被250nm～490nm的紫光-蓝光所激发。本发明所述的固体光源用荧光材料可以与钇铝石榴石、硅酸盐绿色荧光粉组合，或者与Y3Al5O12:Ce3+黄色荧光粉组合，形成白光LED。
上述白光LED所采用的绿色荧光粉，可以是分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的绿色荧光粉。
上述白光LED所采用的绿色荧光粉，可以是分子式为Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的绿色荧光粉。
附图说明
图1所示为(a)(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012和(b)(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012荧光材料的XRD谱图。
图2所示为由实施例1制备的分子式为(Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01的荧光材料在460nm蓝光LED激发下的发射光谱。
图3所示为由实施例2制备的分子式为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料在460nm蓝光LED激发下的发射光谱。
图4所示为由实施例3制备的分子式为(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012的荧光材料在460nm蓝光LED激发下的发射光谱。
图5所示为分子式分别为(Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263、(Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267和(Sr0.88Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167的荧光材料在460nm蓝光LED激发下的发射光谱。
图6所示为分别掺杂Pr3+、La3+和Tb3+的荧光材料在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012，
(Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012，和
(Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012。
图7所示为具有不同Mn2+含量的荧光材料在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，
(Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，和
(Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012。
图8所示为具有不同Li+含量的荧光材料在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012，
(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012，
(Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012，
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012，和
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012。
图9所示为具有不同(1+α)值的荧光材料(Sr1-γ,Euγ)1+αAl0.1Si2.2NnFy在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191，和
(Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239。
图10所示为具有不同(1+α)值的荧光材料(Sr1-γ,Euγ)1+αLibAl0.1Si2.2NnFy在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096，
(Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012，
(Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433，和
(Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167。
图11所示为具有不同Si4+含量的荧光材料(Sr1-γ,Euγ)1+αAl0.1SidNnFy在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433。
图12所示为具有不同Al3+含量的荧光材料(M1-γ,Euγ)1+αAlcSidNnXy在460nm 蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.493,Ca0.493,Eu0.014)1.0287Al1.0Si1.0N2.9319F0.2608。
图13所示为具有不同Eu2+含量的荧光材料(Sr1-γ,Euγ)1+αAl0.1Si2.2NnFy在460nm蓝光LED激发下的发射光谱。其中所述荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263，和
(Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263。
图14所示为根据本发明实施例2制备的分子式为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料分别与分子式分别为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7和Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的绿色荧光粉配比，以及与分子式为Y3Al5O12:Ce3+黄色荧光粉配比，以及现有技术中的分子式为(Sr,Ba)1.88SiO4:Eu2+的荧光材料与分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的绿色荧光粉配比形成的白光LED在蓝光二极管为基础的固体白光光源中测试得到的光谱。
具体实施方式
本发明所制备的荧光材料，其组成符合如下分子式：
[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)
按照化学计量指数(1+α)取值的不同，以及使用稀土元素和掺杂铝、硅的不同配比合成32个样品。
作为具体实施例，我们给出32个样品的数据，这些样品的光学性质呈现一定规律性变化。
实施方式中所示的荧光材料样品，由金属氮化物、氮化铝、氮化硅和稀土氮化物等混合物高温焙烧制得。所用起始原料粒径(D50)均小于3微米(由激光粒度分析仪测得)。
制备实施例:
目前合成氮化物荧光材料的方法主要有以下几种：高温固相反应法、气体还 原氮化法和碳热还原氮化法等。
本发明中采用高温固相反应法制备荧光材料。
所需原料：
Sr3N2--------------(3N)
Li3N---------------(4N)
AlN---------------(3N)
Si3N4--------------(4N)
EuN---------------(4N)
SrF2---------------(3N)
LiF----------------(3N)
CaF2--------------(3N)
BaF2--------------(3N)
Mn----------------(4N)
将起始原料(金属氮化物或其单质，以及氟化锶或氟化锂)干粉在充满氮气的密闭手操箱中称量，并振动混合均匀得到混合物料。
在煅烧制备过程中，混合物料中的氟化锶或氟化锂可以作为助熔剂，起到在固体表面反应中形成液相，从而加快传质速度，使得目标产品生成速度加快的作用。
将上述混合物料经研磨混匀后，装入氮化硼(BN)坩埚中。将装有研磨均匀的混合物料的氮化硼坩埚置于窑炉中，在氮氢还原(体积比为75％)气氛中，950～1700℃下焙烧约3～10个小时。然后，将焙烧后的物料冷却至100℃以下，从炉中取出。
将焙烧后的物料干筛后用异丙醇进行醇洗，之后加入5‰正硅酸乙酯，使粉体表面包覆一层硅膜层，最后得到疏松滑顺的粉体，即为本发明的荧光材料。
使用上述方法获得的荧光材料在460nm蓝光激发下，发射光谱峰值位于623nm～656nm红光波带。
实施例1：
制备分子式为(Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01的荧光材料，起始原料为Sr3N2，AlN，EuN，Li3N和LiF，起始原料使用量使其化学计量指数符合(Sr0.99, Eu0.01)1.005Li1.0Al3N4F0.01，在氮氢还原(体积比为75％)气氛下，焙烧温度为950℃，持续焙烧5小时。
所得分子式(Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01的荧光材料在460nm蓝光LED激发下的发射光谱，如图2所示。
实施例2：
制备分子式为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料，起始原料为Sr3N2，AlN，Si3N4，EuN和SrF2，起始原料使用量使其化学计量指数符合(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012，在氮氢还原(体积比为75％)气氛下，焙烧温度为1580℃，持续焙烧6小时。
所得分子式(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料在460nm蓝光LED激发下的发射光谱，如图3所示。
实施例3：
制备分子式为(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012的荧光材料，起始原料为Sr3N2，Li3N，AlN，Si3N4，EuN和SrF2，起始原料使用量使其化学计量指数符合(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012，在氮氢还原(体积比为75％)气氛下，焙烧温度为1480℃，持续焙烧6小时。
所得分子式为(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012的荧光材料在460nm蓝光LED激发下的发射光谱，如图4所示。
实施例4：
制备分子式为(Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263、(Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267和(Sr0.88,Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167的荧光材料，起始原料为Sr3N2，AlN，Si3N4，EuN，SrF2，CaF2，BaF2和Zn，起始原料使用量使其符合分子式的化学计量指数，在氮氢还原(体积比为75％)气氛下，焙烧温度为1570℃，持续焙烧6小时。
所得分子式为(Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263、(Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267和(Sr0.88,Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167的荧光材料在460nm蓝光LED激发下 的发射光谱，如图5所示。
实施例5：
制备分别掺杂了激活剂Pr、Tb和La的三种荧光材料，分子式分别为：
(Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012，
(Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012，和
(Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012，
起始原料为Sr3N2，AlN，Si3N4，EuN，SrF2，PrN、金属La和金属Tb，在氮氢还原(体积比为75％)气氛下焙烧温度为1580℃，持续焙烧6小时。
所得分子式为(Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012、(Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012和(Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012的荧光材料在460nm蓝光LED激发下的发射光谱，如图6所示。
实施例6：
制备具有不同Mn2+含量的荧光材料，起始原料使用量使其化学计量指数分别符合以下分子式：
(Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，
(Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，和
(Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
起始原料为Sr3N2，AlN，Si3N4，EuN，SrF2和Mn，在氮氢还原(体积比为75％)气氛下焙烧温度为1580℃，持续焙烧6小时。
所得具有不同Mn2+含量的荧光材料的分子式分别为：
(Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，
(Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，和
(Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图7所示。
实施例7：
制备具有不同Li+含量的荧光材料，起始原料使用量使其化学计量指数分别符合以下分子式：
(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012，
(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012，
(Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012，
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012，和
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012；
起始原料为Sr3N2，Li3N，AlN，Si3N4，EuN，Mg和SrF2，在氮氢还原(体积比为75％)气氛下焙烧温度为1480℃，持续焙烧6小时。
所得具有不同Li+含量的荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012，
(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012，
(Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012，
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012，和
(Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图8所示。
实施例8：
制备具有不同(1+α)值的(Sr1-γ,Euγ)1+αAl0.1Si2.2NnFy基质荧光粉，起始原料使用量使其化学计量指数分别符合如下分子式：
(Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191，和
(Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239；
起始原料为Sr3N2，AlN，Si3N4，EuN和SrF2，在氮氢还原(体积比为75％)气氛下，焙烧温度为1580℃，持续焙烧6小时。
所得具有不同(1+α)值的荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191，和
(Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图9所示。
实施例9：
制备不同(1+α)值的(Sr1-γ,Euγ)1+αLi0.05Al0.1Si2.2NnFy基质荧光材料，起始原料使用量使其化学计量指数分别符合如下分子式：
(Sr0.975,Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096，
(Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012，
(Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433，和
(Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167；
起始原料为Sr3N2，Li3N，AlN，Si3N4，EuN和SrF2，在氮氢还原(体积比为75％)气氛下，焙烧温度为1480℃，持续焙烧6小时。
所得具有不同(1+α)值的荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096，
(Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012，
(Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433，和
(Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图10所示。
实施例10：
制备具有不同Si4+含量的(Sr0.98,Eu0.02)1+αAl0.1SidNnFy基质荧光材料，起始原料使用量使其化学计量指数分别符合如下分子式：
(Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433；
起始原料为Sr3N2，AlN，Si3N4，EuN和SrF2，在氮氢还原(体积比为75％)气氛下，焙烧温度为1580℃，持续焙烧6小时。
所得具有不同Si4+含量的荧光材料的分子式分别为：
(Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433，
(Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图11所示。
实施例11：
制备不同Al3+含量的(Sr1-γ,Euγ)1+αAlcSidNnFy基质荧光材料，起始原料使用量使其化学计量指数分别符合如下分子式：
(Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.493,Ca0.493,Eu0.014)1.0287Al1.0Si1.0N2.9319F0.2608；
起始原料为Sr3N2，AlN，Si3N4，EuN，CaF2和SrF2，在氮氢还原(体积比为75％) 气氛下，焙烧温度为1580℃，持续焙烧6小时。
所得具有不同Al3+含量的荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433，
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，和
(Sr0.493,Ca0.493,Eu0.014)1.0287Al1.0Si1.0N2.9319F0.2608；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图12所示。
实施例12：
制备不同Eu2+含量的荧光材料，起始原料使用量使其化学计量指数分别符合以下分子式：
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263，和
(Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263；
起始原料为Sr3N2，AlN，Si3N4，EuN和SrF2，在氮氢还原(体积比为75％)气氛下焙烧温度为1580℃，持续焙烧6小时。
所得具有不同Eu2+含量的荧光材料的分子式分别为：
(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433，
(Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263，和
(Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263；
上述荧光材料在460nm蓝光LED激发下的发射光谱如图13所示。
实施例13：
采用本发明实施例2制备的红色荧光材料(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012分别与分子式分别为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7和Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的绿色荧光粉配比组合形成的白光LED荧光材料组合物，或者与分子式为Y3Al5O12:Ce3+的黄色荧光粉配比组合形成的白光LED荧光材料组合物，以及现有技术中的分子式为(Sr,Ba)1.88SiO4:Eu2+的荧光材料与分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的绿色荧光粉配比组合形成的白光LED荧光材料组合物，测试得到的光谱如图14所示。
实施例样品光学特性参数由设备(EVERFINE)HAAS-2000测量。测量了样品反射的复合蓝光(455nm)二极管辐射的黄-橙色荧光光谱，反射角为45°，波 长范围在500nm～800nm。实施例1～12的荧光材料的光学特性数据见表1，其中样品编号对应于实施例编号。
1.相对亮度(I)
2.主波长位置(λdom，nm)，峰值波长(λpeak，nm)。
3.色坐标x，y
4.半峰宽(nm)
表1 荧光材料的光学特性
Figure PCTCN2016073063-appb-000003
Figure PCTCN2016073063-appb-000004
图1(a)、(b)所示为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012和(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012荧光材料的XRD谱图。由图可知，(a)、(b)的主要衍射峰位置几乎一致，说明掺杂Li+对荧光材料的晶体结构没有较大影响。
图2为分子式为(Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01的荧光材料在460nm蓝光LED激发下的发射光谱。由图中可知，本实施例的发射光谱覆盖600nm～750nm的红色窄带，半峰宽仅为53.4nm，发射峰发生明显红移，位于654nm，红光更加集中使得荧光材料的显色指数和发光亮度得到了较大幅度的提高。
图3为分子式为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料在460nm蓝光LED激发下的发射光谱。由图中可知，发射光谱覆盖550nm～750nm的连续宽带，发射峰值位于626nm附近，半峰宽为90.2nm。
图4为分子式为(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012的荧光材料在460nm蓝光LED激发下的发射光谱。由图可知，发射光谱覆盖550nm～750nm的连续波带，发射峰值位于624nm附近，半峰宽为89.4nm。
图5为分子式为(Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263、(Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267和(Sr0.88,Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167的荧光材料在460nm蓝光LED激发下的发射光谱。由图可知，发射光谱均覆盖550nm～750nm的连续宽带，随着Ca2+,Ba2+,Zn2+的取代，发射峰红移，峰值分别位于624nm、631nm和639nm处，并且半峰宽逐渐增加，红光区域增大。
图6为考察掺杂Pr3+、La3+和Tb3+离子的荧光材料在460nm蓝光LED激发下的发射光谱。分子式分别为：(Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012、(Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012和(Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012。由图可知，光谱均覆盖550nm～750nm的连续宽带，掺杂La3+的荧光材料的发射峰相对红移，半峰宽增加，色坐标变长。
图7为考察荧光材料中的Mn2+含量变化对其发射光谱的影响。分子式分别为：(Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012，(Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012和(Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012。由图可知，光谱覆盖550nm～750nm的连续宽带，随着Mn2+含量的增加，发射峰位置几乎没有变化，峰值分别位于627nm、626nm和627nm。
图8为考察分子式为(Sr1-γ,Euγ)1+αLibAl0.1Si2.2NnFy的荧光材料中的Li+含量变化对其发射光谱的影响。分子式分别为：(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012，(Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012，(Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012，(Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012，(Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012。由图可知，光谱覆盖550nm～750nm的连续宽带，随着Li+含量的逐渐增加，发射峰红移，峰值分别位于628nm、624nm、623nm、625nm和656nm处，色坐标变长。电荷补偿剂Li+的引入使荧光粉达到电荷平衡，并且对荧光材料的发光效率起到增强作用。
图9为考察分子式为(Sr1-γ,Euγ)1+αAl0.1Si2.2NnFy的荧光材料中(1+α)值变化对荧光粉发射光谱的影响，分子式分别为：(Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096，(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，(Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191和(Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239，由图可知，光谱覆盖550nm～750nm的连续宽带，随着(1+α)的增加，发射峰位置没有变化，峰值位于623nm～630nm附近。
图10为考察分子式为(Sr1-γ,Euγ)1+αLi0.05Al0.1Si2.2NnFy的荧光材料中(1+α)值变化对荧光粉发射光谱的影响，分子式分别为：(Sr0.975, Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096，(Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012，(Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433，(Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167，由图中可知，光谱覆盖550nm～750nm的连续宽带，随着(1+α)的增加，光谱形状和发射峰位置几乎没有变化，峰值位于623nm附近。
图11为考察分子式为(Sr1-γ,Euγ)1+αAl0.1SidNnFy的荧光材料中Si4+含量变化对荧光粉发射光谱的影响，分子式分别为：(Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433，(Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433，(Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433，(Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433，由图可知，光谱覆盖550nm～750nm的连续宽带，随着Si4+含量的增加，发射峰逐渐红移，峰值分别位于625nm、625nm、627nm和632nm处，半峰宽逐渐增加。
图12为考察分子式为(M1-γ,Euγ)1+αAlcSi2.2NnFy的荧光材料中Al3+含量变化对荧光粉发射光谱的影响，分子式分别为：(Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433，(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，(Sr0.493,Ca0.493,Eu0.014)1.0287Al1.0Si1.0N2.9319F0.2608，由图可知，光谱覆盖550nm～750nm的连续宽带，随着Al3+含量的增加，发射峰明显红移，峰值分别为625nm、626nm和652nm处，半峰宽增加，色坐标变长。
图13为考察分子式为(Sr1-γ,Euγ)1+αAl0.1Si2.2NnFy的荧光材料中Eu2+含量变化对荧光粉发射光谱的影响，分子式分别为：(Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433，(Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433，(Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263，(Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263，由图可知，光谱覆盖550nm～750nm的连续宽带，随着Eu2+含量的增加，发射峰显著红移，峰值分别位于628nm、635nm、645nm和656nm处，半峰宽增加，色坐标明显变长，红光区域增大。
图14为本发明的分子式为(Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012的荧光材料分别与分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7和Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的绿色荧光粉，以及与分子式为Y3Al5O12:Ce3+的黄色荧光粉配比，以及分子式为(Sr,Ba)1.88SiO4:Eu2+的荧光材料与分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的绿色荧光粉配比形成的白光LED荧光材料组合物的光谱。合成的样品在蓝光二极管为基础的固体白光光源中测试，结果表明本发明与钇铝石榴石绿色荧光粉形成的白光LED的显色指数(Ra)达到86.9，相应色温(Tc)为3495K，形成的光谱带覆盖更宽，效果更佳。
总结取得的数据结果表明，随着化学计量指数(1+α)从1.005变化到1.0525的区间内，样品的光学特性发生显著变化。随着(1+α)值逐渐减小，发射红光颜色加 深，峰值发生红移，相应色坐标变长，半峰宽变化较微弱。
综上所述，本发明提供了通式为[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy的荧光材料，其中，通过改变M、稀土元素、铝和硅的不同配比，可以调节荧光材料的发光颜色。同时，按照本发明的荧光材料可以与钇铝石榴石、硅酸盐、磷酸盐基质的黄、绿色荧光粉组合，获得高显色性、稳定性强的白光LED，这在商业实际应用方面具有重要十分的意义。

Claims (14)

  1. 一种荧光材料，所述荧光材料包括通式(I)的化合物：
    [M1-γ,(∑RE-1)γ]1+α(∑RE-2)zM’bAlcSidNnXy   (I)；
    其中，
    M选自由二价金属Ca,Sr,Ba,Mg,Zn及其组合组成的组；
    M’选自由一价金属Li,Na及其组合组成的组；
    X为F元素；
    所述∑RE-1选自由Eu、Mn及其组合组成的组；所述∑RE-2选自由Ce,Pr,La,Tb,Er及其组合组成的组；
    n＝2/3(1+α)+z+1/3b+4/3d+c-1/3y；
    0＜α≤0.2；
    0≤b≤1.0；
    0.01＜c≤3.0；
    0≤d≤2.8；
    0.005≤γ≤0.15；
    0≤z≤0.05；
    0≤y≤0.05。
  2. 根据权利要求1所述的荧光材料，其中所述荧光材料包括通式(I-1)的化合物：[M1-γ,(∑RE-1)γ]1+α(∑RE-2)zAlcSidNnXy   (I-1)；
    其中，
    ∑RE-2选自由Pr,La,Tb,Er及其组合组成的组；并且
    b＝0。
  3. 根据权利要求1所述的荧光材料，其中：
    M选自由Ca、Sr、Ba、Zn及其组合组成的组；并且
    ∑RE-2选自由Pr,La,Tb,Er及其组合组成的组。
  4. 根据权利要求1-3中任一项所述的荧光材料，其中，0.001≤α≤0.06。
  5. 根据权利要求1或2所述的荧光材料，所述荧光材料选自由如下化合物组成的组：
    (Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012；
    (Sr0.961,Ca0.019,Eu0.02)1.0334Al0.1Si2.2N3.7132F0.0263；
    (Sr0.96,Ba0.02,Eu0.02)1.0334Al0.1Si2.2N3.713F0.0267；
    (Sr0.88Zn0.1,Eu0.02)1.0334Al0.1Si2.2N3.7164F0.0167；
    (Sr0.96,Eu0.04)1.024Pr0.005Al0.1Si2.2N3.7167F0.012；
    (Sr0.96,Eu0.04)1.024La0.02Al0.1Si2.2N3.7317F0.012；
    (Sr0.96,Eu0.04)1.024Tb0.005Al0.1Si2.2N3.7167F0.012；
    (Sr0.975,Mn0.005,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
    (Sr0.965,Mn0.015,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
    (Sr0.95,Mn0.03,Eu0.02)1.024Al0.1Si2.5N4.112F0.012；
    (Sr0.975,Eu0.025)1.0191Al0.1Si2.2N3.7095F0.0096；
    (Sr0.975,Eu0.025)1.0287Al0.1Si2.2N3.7143F0.01433；
    (Sr0.975,Eu0.025)1.0382Al0.1Si2.2N3.719F0.0191；
    (Sr0.975,Eu0.025)1.0478Al0.1Si2.2N3.7238F0.0239；
    (Sr0.98,Eu0.02)1.0287Al0.1Si1.9N3.314F0.01433；
    (Sr0.98,Eu0.02)1.0287Al0.1Si2.0N3.448F0.01433；
    (Sr0.98,Eu0.02)1.0287Al0.1Si2.2N3.7143F0.01433；
    (Sr0.98,Eu0.02)1.0287Al0.1Si2.5N4.1144F0.01433；
    (Sr0.975,Eu0.025)1.0287Al0.08Si2.2N3.694F0.01433；
    (Sr0.493,Ca0.493,Eu0.014)1.0287Al1,0Si1.0N2.9319F0.0287；
    (Sr0.96,Eu0.04)1.0287Al0.1Si2.2N3.7143F0.01433；
    (Sr0.92,Eu0.08)1.0525Al0.1Si2.2N3.7259F0.0263；
    (Sr0.88,Eu0.12)1.0525Al0.1Si2.2N3.7259F0.0263。
  6. 根据权利要求1或3所述的荧光材料，其中所述荧光材料选自由如下化合物组成的组：
    (Sr0.99,Eu0.01)1.005Li1.0Al3N4F0.01；
    (Sr0.975,Eu0.025)1.024Li0.05Al0.1Si2.2N3.7287F0.012；
    (Sr0.975,Eu0.025)1.024Li0.1Al0.1Si2.2N3.7453F0.012；
    (Sr0.86,Mg0.1,Eu0.04)1.024Li0.2Al0.1Si2.2N3.7754F0.012；
    (Sr0.86,Mg0.1,Eu0.04)1.024Li0.3Al0.1Si2.2N3.8117F0.012；
    (Sr0.975,Eu0.025)1.0191Li0.05Al0.1Si2.2N3.7262F0.0096；
    (Sr0.975,Eu0.025)1.0239Li0.05Al0.1Si2.2N3.7286F0.012；
    (Sr0.975,Eu0.025)1.0287Li0.05Al0.1Si2.2N3.731F0.01433；
    (Sr0.975,Eu0.025)1.0334Li0.05Al0.1Si2.2N3.7333F0.0167。
  7. 一种制备如权利要求1-6中任一项所述的荧光材料的方法，包括：
    将金属氮化物或其单质与氟化锶或氟化锂，以及，可选地，锰单质混合，其中将各原料按照权利要求1-6中任一项所述的荧光材料的元素摩尔配比称量，并混合均匀形成混合物料；以及
    将所述混合物料在氮、氢混合气体的还原气氛下，于950～1700℃的温度，焙烧3～10小时。
  8. 根据权利要求7所述的方法，其中所述金属氮化物选自由氮化铝，氮化硅，氮化锂，稀土氮化物组成的组。
  9. 根据权利要求7所述的方法，其中，所述混合物料在氮、氢混合气体的还原气氛下，于950～1580℃的温度，焙烧5～6小时。
  10. 一种荧光材料组合物，包括：
    如权利要求1-6中任一项所述的荧光材料；以及
    绿色荧光粉；
    其中，所述荧光材料与所述绿色荧光粉的重量比约为4：96～20：80。
  11. 如权利要求10所述的荧光材料组合物，其中所述绿色荧光粉是钇铝石榴石、硅酸盐中的任一种。
  12. 如权利要求11所述的荧光材料组合物，其中所述绿色荧光粉是分子式为[Lu0.4415Y0.45Ce0.05Ba0.0585]2.8Al5(O0.995,F0.01)11.7的钇铝石榴石。
  13. 如权利要求11所述的荧光材料组合物，其中所述绿色荧光粉是分子式为Y0.7Sr0.613Ba0.96Si0.875O3.5:Eu2+的硅酸盐。
  14. 如权利要求12或13所述的荧光材料组合物，其中所述荧光材料是：
    (Sr0.975,Eu0.025)1.024Al0.1Si2.2N3.712F0.012。
PCT/CN2016/073063 2015-02-11 2016-02-01 固体光源用荧光材料、其制造方法及包含该荧光材料的组合物 WO2016127843A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510072036.5 2015-02-11
CN201510072036.5A CN105985772B (zh) 2015-02-11 2015-02-11 固体光源用荧光材料、其制造方法及包含该荧光材料的组合物

Publications (1)

Publication Number Publication Date
WO2016127843A1 true WO2016127843A1 (zh) 2016-08-18

Family

ID=56614143

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/073063 WO2016127843A1 (zh) 2015-02-11 2016-02-01 固体光源用荧光材料、其制造方法及包含该荧光材料的组合物

Country Status (2)

Country Link
CN (1) CN105985772B (zh)
WO (1) WO2016127843A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6575500B2 (ja) * 2016-12-15 2019-09-18 日亜化学工業株式会社 窒化物蛍光体の製造方法
CN108730790A (zh) * 2017-04-19 2018-11-02 大连利德照明研发中心有限公司 荧光粉转换型植物生长用灯丝灯
CN108165266B (zh) * 2018-03-23 2019-01-08 旭宇光电（深圳）股份有限公司 一种氟氮化物荧光粉及包含该荧光粉的发光器件
CN110387236B (zh) * 2019-07-22 2020-04-21 旭宇光电（深圳）股份有限公司 荧光红粉材料及其制备方法、含有荧光红粉材料的发光装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007120216A2 (en) * 2005-11-22 2007-10-25 Gelcore Llc Charge compensated nitride phosphors for use in lighting applications
CN101175835A (zh) * 2005-05-24 2008-05-07 三菱化学株式会社 荧光体及其应用
CN101501161A (zh) * 2006-08-04 2009-08-05 奥斯兰姆有限公司 氮化硅酸盐类荧光材料和具有这类荧光材料的光源
CN101679863A (zh) * 2007-04-17 2010-03-24 奥斯兰姆有限公司 发射红光的发光体和包括该发光体的光源
CN102066522A (zh) * 2008-05-19 2011-05-18 英特曼帝克司公司 以氮化物为基础的红色磷光体
CN102282641A (zh) * 2008-12-15 2011-12-14 英特曼帝克司公司 在红绿蓝(rgb)照明系统中的以氮化物为基础的红色发光磷光体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005019376A1 (ja) * 2003-08-22 2005-03-03 National Institute For Materials Science 酸窒化物蛍光体と発光器具
JP5540322B2 (ja) * 2009-03-26 2014-07-02 独立行政法人物質・材料研究機構 蛍光体、その製造方法、発光器具および画像表示装置
US8597545B1 (en) * 2012-07-18 2013-12-03 Intematix Corporation Red-emitting nitride-based calcium-stabilized phosphors
CN103555325A (zh) * 2013-11-01 2014-02-05 江苏罗化新材料有限公司 一种氮化物红色荧光粉及其制备方法
CN104087293B (zh) * 2014-07-23 2016-03-23 中国科学院上海硅酸盐研究所 红色荧光体及其碳热还原氮化制备方法及应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101175835A (zh) * 2005-05-24 2008-05-07 三菱化学株式会社 荧光体及其应用
WO2007120216A2 (en) * 2005-11-22 2007-10-25 Gelcore Llc Charge compensated nitride phosphors for use in lighting applications
CN101501161A (zh) * 2006-08-04 2009-08-05 奥斯兰姆有限公司 氮化硅酸盐类荧光材料和具有这类荧光材料的光源
CN101679863A (zh) * 2007-04-17 2010-03-24 奥斯兰姆有限公司 发射红光的发光体和包括该发光体的光源
CN102066522A (zh) * 2008-05-19 2011-05-18 英特曼帝克司公司 以氮化物为基础的红色磷光体
CN102282641A (zh) * 2008-12-15 2011-12-14 英特曼帝克司公司 在红绿蓝(rgb)照明系统中的以氮化物为基础的红色发光磷光体

Also Published As

Publication number Publication date
CN105985772B (zh) 2019-08-30
CN105985772A (zh) 2016-10-05

Similar Documents

Publication Publication Date Title
Huang et al. Ultra-high color rendering warm-white light-emitting diodes based on an efficient green-emitting garnet phosphor for solid-state lighting
KR101150389B1 (ko) 질소 산화물발광재료, 그 제조방법 및 응용
KR101331392B1 (ko) 형광체 및 그 제조방법, 및 상기 형광체를 사용한 발광장치
JP4617323B2 (ja) 新しい組成の黄色発光Ｃｅ３＋賦活シリケート系黄色蛍光体、その製造方法及び前記蛍光体を包含する白色発光ダイオード
JP6101700B2 (ja) Ｌｅｄ赤色蛍光体及び該蛍光体を含有する発光デバイス
JPWO2006106883A1 (ja) 蛍光体、蛍光体シートおよびその製造方法、並びに当該蛍光体を用いた発光装置
TWI424045B (zh) A phosphor, a phosphor sheet, and a phosphor, and a light-emitting device using the phosphor
Hakeem et al. Structural and photoluminescence properties of La1-xNaCaGa3PZrO12 doped with Ce3+, Eu3+, and Tb3+
TWI530550B (zh) Nitrogen oxide orange-red fluorescent substance, including its light-emitting film or light-emitting sheet and light-emitting device
CN103881706B (zh) 一种氮氧化物荧光粉、其制备方法及含该荧光粉的发光装置
WO2016127843A1 (zh) 固体光源用荧光材料、其制造方法及包含该荧光材料的组合物
JP5752257B2 (ja) 窒素化合物発光材料及びそれによって製造された白色ｌｅｄ照明光源
CN112094645A (zh) 一种掺杂Eu2+的蓝光荧光材料及其制备方法和白光LED发光装置
CN106634997A (zh) 一种复合磷酸盐荧光体及其应用
WO2018001368A1 (zh) 氮化物荧光体及包含其的发光装置
US20170275532A1 (en) Fluorescent material, a manufacturing method thereof, and a photo-luminescent composition containing the fluorescent material
CN110240900B (zh) 一种Eu2+掺杂的窄带绿色发光材料、制备方法及照明与显示光源
CN104962286A (zh) 石榴石结构的复相荧光材料及其制备方法
CN112608742A (zh) 一种铕激活的β-Al2O3缺陷结构蓝色荧光粉及其制备方法
KR101176212B1 (ko) 알카리 토류 포스포러스 나이트라이드계 형광체와 그 제조방법 및 이를 이용한 발광장치
CN102373062B (zh) 一种适于白光led应用的氟硅酸盐红色荧光粉及其制备方法
CN111607397A (zh) 一种Eu2+-Eu3+共掺杂硅酸盐荧光粉及其制备方法和应用
CN114410302B (zh) 一种近红外荧光粉及其光学装置
CN106634996A (zh) 荧光体及其应用
CN108034423B (zh) 一种Mn2+离子掺杂的硅酸盐红色荧光粉、制备方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16748644

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1)EPC DATED 27.11.2017 (EPO FORM 1205A).

122 Ep: pct application non-entry in european phase

Ref document number: 16748644

Country of ref document: EP

Kind code of ref document: A1