• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for preparing a phosphorus, phosphorus, lighting fixture and backlighting device The present invention relates to a process for preparing a phosphorus enriched with mn4 + of formula i ax [mfy]: mn + 41 including contact of a mixture. of a compound of formula ax [mfy], a compound of formula ax and a source of mn "comprising a fluorine manganese compound with a fluorine-containing oxidizing agent in gaseous form at an elevated temperature to form phosphorus enriched with mn4 + where a is li, na, k, rb, cs, or a combination thereof, m is si, ge, sn, ti, zr, al, ga, in, sc, hf, y, la, nb , ta, bi, gd or a combination thereof x is f, cl, br, i, hf2 or a combination thereof x is the absolute value of the ion charge [mfy] y is 5, 6 or 7; and n is 2, 3, or 4.
    公开号:BR102015009499A2
    申请号:R102015009499-0
    申请日:2015-04-28
    公开日:2018-02-14
    发明作者:Edward Murphy James；Achyut Setlur Anant；Joseph Lyons Robert
    申请人:General Electric Company；
    IPC主号:
    专利说明:

    (54) Title: PROCESS TO PREPARE A MATCH, PHOSPHORUS, LIGHTING EQUIPMENT AND RETRO LIGHTING DEVICE (51) Int. CL: C09K 11/08; C09K 11/57; C09K 11/61; C09K 11/62; C09K 11/64; (...) (52) CPC: C09K 11/0838, C09K 11/57, C09K 11/61, C09K 11/62, C09K 11/64, C09K 11/66, C09K 11/77, H01L 33/502 ( 30) Unionist Priority: 01/05/2014 US 14 / 267,449 (73) Holder (s): GENERAL ELECTRIC COMPANY (72) Inventor (s): JAMES EDWARD MURPHY; ANANT ACHYUT SETLUR; ROBERT JOSEPH LYONS (74) Attorney (s): PAOLA CALABRIA MATTIOLI DANTAS (57) Summary: PROCESS TO PREPARE A MATCH, MATCH, LIGHTING DEVICE AND RETRO LIGHTING DEVICE The present invention relates to a process for preparing an enriched match with Mn4 + of formula I Ax [MFy]: Mn + 4 1 which includes contacting a mixture of a compound of formula AX [MFy], a compound of formula AX and a source of Mn comprising a fluoromanganese compound, with a oxidizing agent containing fluorine in gaseous form, at an elevated temperature, to form phosphorus enriched with Mn4 + where A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof; X is F, Cl, Br, I, HF2 or a combination thereof; x is the absolute value of the ion charge [MFy]; y is 5, 6 or 7; and n is 2, 3, or 4.
    1/20 “PROCESS FOR PREPARING A MATCH, PHOSPHORUS, LIGHTING DEVICE AND BACKLIGHT DEVICE” Cross-Reference to Related Orders [001] This patent application relates to the US patent application concurrently under the number of attorney file 270388-1, the disclosure of which in its entirety is incorporated by reference in this document.
    Background [002] Red-emitted phosphors based on complex fluoride materials activated by Mn 4+ , such as those described in US Patent No. 7,358,542, US 7,497,973 and US 7,648,649, can be used in combination with yellow / green emission matches such as YAG: Ce or other garnet compositions to achieve a warm white light (CCTs <5000 K at the black body locus, the chromatic reproduction index (CRI)> 80) forms a blue LED, equivalent to that produced by current fluorescent, incandescent and halogen lamps. These materials absorb blue light more strongly and emit efficiently between about 610 to 635 nm with little deep red / NIR emission. Therefore, the luminous efficacy is maximized compared to the red matches that have significant emission in the deepest red where the optical sensitivity is weak. Quantum efficiency can exceed 85% under blue excitation (440 to 460 nm).
    [003] Methods for preparing matches typically require hydrofluoric acid as a solvent. For example, the patent document WO 2007/100824 describes the preparation of complex fluoride matches using aqueous HF as a solvent. The processes use significant amounts of this highly toxic material and alternatives that eliminate HF or that at least reduce the amount of HF are
    2/20 economically advantageous.
    Brief description [004] Briefly, in one aspect, the present invention relates to an HF-free process for preparing a phosphorus enriched with Mn 4+ of formula I
    A x [MF y ]: Mn +4 I and
    Aé Li, Na, K, Rb, Cs or a combination thereof;
    M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof;
    x is the absolute value of the ion charge [MF y ]; y is 5, 6 or 7; and n is 2 or 3.
    [005] The process includes contacting a mixture of a compound of formula A x [MF y ], a compound of formula AX, where X is F, Cl, Br, I, HF 2 or a combination thereof and a source of Mn + n which comprises a fluorine-manganese compound with an oxidizing agent containing fluorine in gaseous form, at an elevated temperature, to form the phosphorus enriched with Mn 4+ .
    [006] In another aspect, the present invention relates to a process to prepare a phosphorus enriched with Mn 4+ selected from (A) A 2 [MF 5 ]: Mn 4+ , where M is selected from from Al, Ga, In and combinations thereof;
    (B) A 3 [MF 6 ]: Mn 4+ , where M is selected from Al, Ga, In and combinations thereof;
    (C) Zn 2 [MF 7 ]: Mn 4+ , where M is selected from Al, Ga, In and combinations thereof;
    3/20 (D) A [ln 2 F 7 ]: Mn 4+ ;
    (E) A 2 [MF 6 ]: Mn 4+ , where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    (F) E [MF 6 ]: Mn 4+ , where E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    (G) Ba 0 65Zro.35F 2 .7o: Mn 4+ ;
    (H) A 3 [ZrF 7 ]: Mn 4+ ; and combinations thereof in solid solution; in which Aé Li, Na, K, Rb, Cs or a combination thereof. [007] The process includes contacting a mixture of a host compound of phosphorus, a compound of formula AX or EX 2 and a source of Mn + n comprising a fluorine-manganese compound; with an oxidizing agent containing fluorine in gaseous form, at an elevated temperature, to form phosphorus enriched with Mn 4+ ;
    wherein the host compound is selected from the group consisting of (a) A 2 [MF 5 ], where M is selected from Al, Ga, In and combinations thereof;
    (b) A 3 [MF 6 ], where M is selected from Al, Ga, In and combinations thereof;
    (c) Zn 2 [MF 7 ], where M is selected from Al, Ga, In and combinations thereof;
    (d) A [ln 2 F 7 ];
    (e) A 2 [MF 6 ], where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    (f) E [MF 6 ], where E is selected from Mg, Ca, Sr, Ba, Zn and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    4/20 (g) Bao.65Zro.35F2.70; θ (h) A 3 [ZrF 7 ]; and combinations thereof in solid solution;
    A is Li, Na, K, Rb, Cs or a combination thereof.
    Figures [008] These and other characteristics, aspects and advantages of the present invention will be better understood when the following detailed description is read, with reference to the accompanying drawings, in which similar characters represent similar parts throughout the drawings, in which:
    Figure 1 is a schematic cross-sectional view of a lighting apparatus according to an embodiment of the invention;
    Figure 2 is a schematic cross-sectional view of a lighting apparatus according to another embodiment of the invention;
    Figure 3 is a schematic cross-sectional view of a lighting apparatus according to yet another embodiment of the invention;
    Figure 4 is a side perspective view in section of a lighting apparatus according to an embodiment of the invention;
    Figure 5 is a schematic perspective view of a surface mounted device (SMD) backlight LED.
    Detailed description [009] In a process of the present invention, the mixture of starting materials may come into contact with the oxidizing agent containing fluorine in dry or solvent-free conditions. The process does not use HF, as no solvent is required. Under some conditions, HF can be produced as a by-product of the process, but the amount generated is much less than the amount that would be used in a process that includes HF as the solvent.
    5/20 [010] The mixture includes the host compound of matches enriched with Mn 4+ , which is the compound of formula Ax [MFy] for matches of formula I, or host compounds (a) to (h) for matches of formula (A) to (H). Examples of the compound of formula Ax [MFy] include K2 [SiF6], K2 [TiF6], Cs2 [TiF6], Rb2 [TiF6], Cs2 [SiF6], Rb2 [SiF6], Na2 [TiF6], Na2 [ZrF6], K3 [ZrF7], K3 [BiF6], K3 [YF6], K3 [LaF6], K3 [GdF6], K3 [NbF7] and K3 [TaF7], where the phosphorus of formula I is K2 [SiF6]: Mn 4 + , K2 [TiF 6 ]: Mn 4+ , Cs2 [TiF6]: Mn 4+ , Rb2 [TiF 6 ]: Mn 4+ , Cs2 [SiF6]: Mn 4+ , Rb2 [SiF 6 ]: Mn 4+ , Na2 [TiF6]: Mn 4+ , Na2 [ZrF 6 ]: Mn 4+ , K3 [ZrF7]: Mn 4+ , K3 [BiF 6 ]: Mn 4+ , K3 [YF6]: Mn 4+ , K3 [LaF 6 ]: Mn 4+ , K3 [GdF6]: Mn 4+ , K3 [NbF 7 ]: Mn 4+ , or K 3 [TaF 7 ]: Mn 4+ . In certain embodiments, the coordination center M is Si, Ge, Sn, Ti, Zr or a combination thereof. More particularly, the coordination center is Si, Ge, Ti or a combination thereof, counterion A in formula I is Na, K, Rb, Cs or a combination of the same and y is 6.
    [011] The compound of formula AX or EX 2 is a source of A + cations for phosphorus. Examples of materials suitable for AX include KF and KHF 2 .
    [012] Fluorine-manganese compounds suitable for use as the source of Mn n + include sources of Mn 2+ and sources of Mn 3+ . Examples of sources of Mn 2+ include K2MnF4, KMnF3, MnF2, manganese (II) acetate, manganese (II) oxide, manganese (II) carbonate, manganese (II) nitrate and combinations thereof. Examples of sources of Mn 3+ include K2MnF 5 -H 2 O, KMnF 4 and MnF 3 , manganese acetate (III), manganese oxide (III) and combinations thereof. Hydrated forms of Mn n + sources can produce low concentrations of HF.
    [013] Quantities of the starting material can be determined by the stoichiometry of the reaction to form the phosphorus. Deviations from nominal stoichiometry are possible, as known in the art. For example, the preparation of K 2 SiF e : Mn 4+ containing x mol% of Mn is
    6/20 shown in Equation I.
    2xKF + xMnF 3 + (1-x) K 2 SiF 6 + (x / 2) F 2 = K ^ Sh.x.MnxJFe (I) [014] To prepare one mole of phosphorus using MnF 3 as the source of Mn, the relative quantities of the starting materials are:
    Mois starting material
    KF 2x
    MnF 3 1x
    K 2 SiF 6 (1-x) [015] In particular embodiments, the phosphorus of formula I is K 2 SiF 6 : Mn 4+ and the source of Mn n + is combined with the host compound K2SiFe and KF to produce the enriched phosphorus with Mn 4+ . The source of Mn n + can be K2MnF 6 , MnF 2 , MnF 3 or a combination thereof.
    [016] The mixture can be converted to phosphorus enriched with Mn 4+ through contact with an oxidizing agent that contains fluorine in gaseous form at an elevated temperature. The temperature can vary between about 200 ° C and about 700 ° C, particularly between about 35 ° C and about 600 ° C during contact and, in some embodiments, between about 200 ° C and about 700 ° Ç. In various embodiments of the present invention, the temperature is at least 100 ° C, particularly, at least 225 ° C and more particularly, at least 350 ° C. The mixture is placed in contact with the oxidizing agent for a period of time sufficient to convert it to phosphorus enriched with Mn 4+ . Time and temperature are interrelated and can be adjusted together, for example, by increasing the time while reducing the temperature or increasing the temperature, while reducing the time. The contact step can include multiple contact periods, of varying time and temperature, and the materials can be homogenized again between periods to improve treatment uniformity. In particular embodiments, the mixture is brought into contact
    7/20 with the oxidizing agent for a period of at least eight hours and at a temperature of at least 250 ° C, for example, at about 425 ° C for about four hours and then at a temperature of about 56 ° C, for about four hours.
    [017] The oxidizing agent containing fluorine can be F 2 , HF, SF 6 , BrF 5 , NH 4 HF 2 , NH 4 F, KF, AIF 3i SbF 5 , CIF 3 , BrF 3 , KrF, XeF 2 , XeF 4, NF 3, SiF 4, PbF 2, ZnF 2, SnF 2, CdF 2 or a combination thereof. In particular embodiments, the oxidizing agent that contains fluorine is F 2 . The amount of oxidizing agent in the atmosphere can be varied, particularly in conjunction with the variation in time and temperature. If the oxidizing agent containing fluorine is F 2 , the atmosphere may include at least 0.5% F 2 , although a lower concentration may be effective in some embodiments. In particular, the atmosphere can include at least 5% F 2 and more particularly, at least 20% F 2 . The atmosphere may additionally include nitrogen, helium, neon, argon, krypton, xenon and combinations with the oxidizing agent that contains fluorine. In particular embodiments, the atmosphere contains about 20% F 2 and about 80% nitrogen.
    [018] The way of contacting the mixture with the oxidizing agent containing fluorine is not essential and can be done in any way sufficient to convert the mixture to a phosphorus that has the desired properties. In some embodiments, the chamber containing the mixture can be dosed and then sealed so that an overpressure develops as the chamber is heated, and in others, the mixture of fluorine and nitrogen flows through the annealing process ensuring more uniform pressure. In some embodiments, an additional dose of the fluoride-containing oxidizing agent may be introduced after a period of time.
    [019] In another aspect, the present invention relates to a
    8/20 process that includes contact with a mixture of a phosphorus precursor and a flux compound with an oxidizing agent that contains fluorine in gaseous form at an elevated temperature, to form phosphorus enriched with Mn 4+ . Phosphor precursors that are transformed into phosphorus may be deficient in A + relative to the phosphorus product enriched with Mn 4+ , that is, where the ratio [A + ] / ([Mn n + ] + [M]) is lower than than or equal to 2, but is not limited to the same. Examples include compounds of formula I, which include potassium-deficient compounds, particularly K 2 SiF 6 deficient in K: Mn 4+ and Mn 2+ - and Mn 3+ - which contain precursors of formula III
    A m [MF z ]: Mn n + III.
    being that
    Aé Li, Na, K, Rb, Cs or a combination thereof;
    M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof;
    m is the absolute value of the ion charge [MF Z ];
    <z <7; and n is 2 or 3.
    [020] Precursors of formula III may be a single phase material or may contain multiple phases having the average composition of formula III.
    [021] The flow compound is selected from compounds of the formula AX, EX 2 MF 2 or MF 3 where M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof. Materials suitable for use as flow compounds include potassium, sodium and rubidium monofluorides and bifluorides, KF and KHF 2 , NaF and NaHF 2 , RbF and RbHF 2 , BiF 3 , AIF 3 , YF 3i LaF 3 , GdF 3 , GaF 3 , LNF 3, SCF 3, SnF 2 and PbF 2. In particular embodiments, the flow material is KF or KHF 2 or a combination thereof. The flow material can be removed from the phosphorus product by
    9/20 washing medium with a suitable solvent, such as acetic acid.
    [022] The color stability and quantum efficiency of phosphors prepared by a process, according to the present invention, can be improved by treating the phosphorus in particulate form with a saturated solution of a composition of formula II
    A x [MF y ] II in aqueous hydrofluoric acid, as described in US Patent Document No. 8,252,613. For example, K 2 SiF 6 : Mn 4+ can be treated with a solution of K 2 SiF 6 in HF at room temperature to improve the color stability and quantum efficiency of phosphorus. The temperature at which the phosphorus comes into contact with the solution varies from about 20 ° C to about 50 ° C. The time required to produce phosphorus ranges from about one minute to about five hours, particularly, about five minutes to about an hour. The concentration of hydrofluoric acid in aqueous HF solutions varies from about 20% w / w to about 70% w / w, particularly from about 40% w / w to about 70% w / w. Less concentrated solutions can result in lower phosphorus yields.
    [023] Matches enriched with Mn 4+ prepared by a process, according to the present invention, can present good color stability after exposure to the flow of light. A lighting fixture that incorporates a phosphor enriched with Mn 4+ prepared by a process according to the present invention can have a color change of S1.5 MacAdam ellipses after operating for at least 2,000 hours at a current density LEDs greater than 2 A / cm 2 , an LED wall connector efficiency greater than 40% and a plate temperature greater than 25 ° C, preferably where the color change of the MacAdam ellipse is <1. Under accelerated test conditions, the fixture may experience a color change of <2 ellipses from MacAdam after operating for 30 minutes in
    10/20 an LED current density greater than 70 A / cm 2 , an LED wall connector efficiency greater than 18% and a plate temperature greater than 25 ° C. Phosphor stability outside an LED package as measured by% loss of phosphor intensity after exposure to light flux of at least 80 p / cm 2 at a temperature of at least 50 ° C; % loss of intensity of stable color matches can be <4% after 21 hours.
    [024] A lighting apparatus or assembly that emits light or a lamp 10 according to an embodiment of the present invention is shown in Figure 1. The light apparatus 10 includes a source of semiconductor radiation, shown as a light-emitting diode integrated circuit. (LED) 12 and conductors 14 electrically attached to the LED integrated circuit. The conductors 14 can be thin wires supported by a thicker conductor structure (s) 16 or the conductors can be self-supporting electrodes and the conductor structure can be dispensed with. The conductors 14 supply the current to the integrated circuit of LED 12 and, in this way, cause it to emit radiation.
    [025] The lamp can include any source of blue or UV semiconductor light that is capable of producing white light when its emitted radiation is directed over the phosphor. In one embodiment, the semiconductor light source is a blue emitting LED enriched with various impurities. Thus, the LED can comprise a semiconductor diode based on any suitable semiconductor layers III to V, II to VI or IV to IV and which has an emission wavelength of about 250 to 550 nm. In particular, the LED can contain at least one semiconductor layer comprising GaN, ZnSe or SiC. For example, the LED can comprise a semiconductor nitride compound represented by the formula lnjGajAl k N (where 0 <i; 0 <j; 0 <ke I + j + k = 1) which has an emission wavelength greater than about 250 nm and less than about 550 nm. In particular achievements, the circuit
    Integrated 11/20 is a blue or near UV emitting LED that has a peak emission wavelength of about 400 to about 500 nm. Such LED semiconductors are known in the art. The radiation source is described in this document as an LED for convenience. However, as used herein, the term is intended to cover all sources of semiconductor radiation that include, for example, semiconductor laser diodes. Additionally, although the general discussion of the exemplary structures of the invention discussed in this document is directed towards light sources based on inorganic LEDs, it should be understood that the LED integrated circuit can be replaced by another source of radiation, unless otherwise noted and that any reference to the semiconductor, semiconductor LED or LED integrated circuit is merely representative of any suitable radiation source, which includes, but is not limited to, organic light-emitting diodes.
    [026] In the lighting apparatus 10, the composition of phosphorus 22 is coupled according to radiation to the LED integrated circuit 12. According to radiation, it means that the elements are associated with each other so that the radiation from one is transmitted to the other . The phosphorus composition 22 is deposited on LED 12 by any suitable method. For example, a water-based suspension of the phosphor (s) can be formed and applied as a phosphor layer to the LED surface. In such a method, a silicon spray in which phosphor particles are randomly suspended is placed around the LED. This method is merely an example of possible positions of the composition of phosphorus 22 and LED 12. Thus, the composition of phosphorus 22 can be coated on or directly on the light-emitting surface of the integrated circuit of LED 12 by coating and drying the phosphorus suspension on the LED integrated circuit 12. In the case of a silicone based suspension, the suspension is cured at an appropriate temperature. Both the
    12/20 enclosure 18 as well as encapsulant 20 must be transparent to allow white light 24 to be transmitted through these elements. Although it is not intended to be limiting, in some embodiments, the average particle size of the phosphorus composition ranges from about 1 to about 50 microns, particularly from about 15 to about 35 microns.
    [027] In other embodiments, the composition of phosphorus 22 is interspersed with the encapsulating material 20, instead of being formed directly on the LED integrated circuit 12. The phosphorus (in the form of powder) can be interspersed within a single region of the encapsulating material 20 or over the entire volume of encapsulating material. The blue light emitted by the LED integrated circuit 12 mixes with the light emitted by the phosphorus composition 22 and the emitted light appears as white light. If the phosphor is interleaved within the encapsulant material 20, then a phosphor powder can be added to a polymer or silicone precursor, charged around the LED integrated circuit 12, and then the polymer precursor can be cured to solidify the polymer or silicone material. Other known methods of interleaving can also be used, such as transfer loading.
    [028] In yet another embodiment, the phosphorus composition 22 is coated on the surface of the housing 18, instead of being formed on the LED integrated circuit 12. The phosphorus composition is preferably coated on the internal surface of the housing 18, although phosphorus can be coated on the outer surface of the shell, if desired. The phosphorus composition 22 can be applied over the entire surface of the wrapper or just over the top of the wrapper surface. The blue / UV light emitted by the LED integrated circuit 12 mixes with the light emitted by the phosphorus composition 22 and the emitted light appears as white light. Of course, the phosphorus can be located in any two or three locations or any other location
    13/20 suitable, such as, separated from the enclosure or integrated into the LED.
    [029] Figure 2 illustrates a second structure of the system, according to the present invention. The corresponding numbers in Figures 1 to 4 (for example, 12 in Figure 1 and 112 in Figure 2) refer to corresponding structures in each of the Figures, unless otherwise stated. The structure of the embodiment in Figure 2 is similar to that of Figure 1, except that the composition of phosphorus 122 is interspersed with the encapsulating material 120, instead of being formed directly on the integrated circuit of LED 112. The phosphorus (in the form of powder) it can be interleaved within a single region of the encapsulating material or throughout the entire volume of the encapsulating material. The radiation (indicated by the arrow 126) emitted by the LED integrated circuit 112 mixes with the light emitted by the phosphor 122 and the mixed light appears as white light 124. If the phosphor is interleaved within the encapsulating material 120, then a powder of phosphorus can be added to the polymer precursor and charged around the 112 LED integrated circuit. The polymer or silicone precursor can then be cured to solidify the polymer or silicone. Other known methods of interleaving can also be used, such as transfer molding.
    [030] Figure 3 illustrates a third possible structure of the system, according to the present invention. The structure of the embodiment shown in Figure 3 is similar to that of Figure 1, except that the composition of phosphorus 222 is coated on the surface of the envelope 218, instead of being formed on the integrated circuit of LED 212. The composition of phosphorus 222 is preferably coated on the inner surface of the envelope 218, although the phosphorus may be coated on the outer surface of the envelope, if desired. The phosphorus composition 222 can be coated over the entire surface of the envelope or just over the top of the envelope surface. The 226 radiation emitted by the LED integrated circuit 212 mixes with the light emitted
    14/20 by the composition of phosphorus 222 and the mixed light appears as white light 224. Of course, the structures of Figures 1 to 3 can be combined and the phosphorus can be located in any two or three locations or in any other suitable location, such as like, separated from the envelope or integrated into the LED.
    [031] In any of the above structures, the lamp can also include a plurality of diffuse particles (not shown) that are incorporated into the encapsulating material. The diffuse particles may comprise, for example, aluminum oxide or titanium dioxide. The diffuse particles effectively diffuse the directional light emitted from the LED integrated circuit, preferably with a negligible amount of absorption.
    [032] As shown in a fourth structure in Figure 4, the LED integrated circuit 412 can be mounted in a reflective round cavity 430. The round cavity 430 can be produced from or coated with a dielectric material, such as oxide aluminum, titanium dioxide or other dielectric powders known in the art or be coated with a reflective metal, such as aluminum or silver. The remainder of the structure of the Figure 4 embodiment is the same as that of any of the previous figures and can include two conductors 416, a conductive wire 432 and an encapsulating material 420. The reflective round cavity 430 is supported by a first conductor 416 and the conductor wire 432 is used to electrically connect the LED integrated circuit 412 with the second conductor 416.
    [033] Another structure (particularly for backlight applications) is a surface mounted device (SMD) of the type of a LED light 550, for example, as illustrated in Figure 5. This SMD is a type of side emitter and has a light-emitting window 552 in a protruding portion of a 554 light guide member. An SMD package may comprise an LED integrated circuit as defined above and a
    15/20 phosphor material that is stimulated by the light emitted by the LED integrated circuit. Other backlight devices include, but are not limited to, TVs, computers, smartphones, tablets and other portable devices that have visualization that includes a semiconductor light source and a phosphor enriched with Mn 4+ prepared by a process according to present invention.
    [034] When used with an LED emitted from 350 to 550 nm and one or more suitable matches, the resulting lighting system will produce a light that has a white color. A lamp 10 can also include diffuse particles (not shown), which are incorporated into the encapsulating material. The diffuse particles may comprise, for example, aluminum oxide or titanium dioxide. The diffuse particles effectively diffuse the directional light emitted from the LED integrated circuit, preferably with a negligible amount of absorption.
    [035] In addition to phosphorus enriched with Mn 4+ , the composition of phosphorus 22 may include one or more other phosphors. When used in a lighting fixture in combination with radiation emitting blue LED or near UV in the range of about 250 to 550 nm, the resulting light emitted by the assembly will be a white light. Other matches like green, blue, yellow, red, orange or matches of other colors can be used in the mix to customize the white color of the resulting light and produce specific spectral power distributions. Other materials suitable for use in the phosphorus composition 22 include electroluminescent polymers, such as polyfluorenes, preferably poly (9,9-dioctylfluorene) and copolymers thereof, such as poly (9,9'-dioctylfluorene-co-bis-N, N '- (4-butylphenyl) diphenylamine) (F8-TFB); poly (vinylcarbazole) and polyphenylenovinylene and their derivatives. In addition, the light-emitting layer may include a blue, yellow, orange, green or red phosphorescent dye or metal complex or a combination of
    16/20 same. Materials suitable for use as a phosphorescent dye include, but are not limited to, tris (1-phenylisoquinoline) iridium (III) (red dye), tris (2-phenylpyridine) iridium (green dye) and iridium (III) bis (2- (4,6difluorfenyl) pyridinate-N, C2) (blue dye). Phosphorescent and fluorescent metal complexes commercially available from ADS (American Dyes Source, Inc.) can also be used. ADS green dyes include ADS060GE, ADS061GE, ADS063GE, and ADS066GE, ADS078GE, and ADS090GE. Blue ADS dyes include ADS064BE, ADS065BE, and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077RE.
    [036] Matches suitable for use in the composition of phosphorus 22 include, but are not limited to:
    ((Sr ^ z (Ca, Ba, Mg, Zn) z ) i- <x + P ) (Li, Na, K, Rb) w Ce x ) 3 (Ali. Y Síy) O4 + y3 + (xp) Fi. y .3 ( x- P) , 0 <x <0.10, 0 <y <0.5, 0 <z <0.5, 0 <p <x;
    (Ca, Ce) 3 Sc 2 Si 3 0i 2 (CaSiG);
    (Sr, Ca, Ba) 3 Ali.xSixO4 + xFi. x : Ce 3 (SASOF)); (Ba, Sr, Ca) 5 (PO 4 ) 3 (Ct, F, Br, OH): Eu 2+ , Mn 2+ ;
    (Ba, Sr, Ca) BPO 5 : Eu 2+ , Mn 2+ ; (Sr, Ca) i0 (PO4) 6 * vB2O3: Eu 2+ (where 0 <v <1); Sr2Si 3 O 8 * 2SrCI 2 : Me 2+ ; (Ca, Sr, Ba) 3MgSi2O8: Eu 2+ , Mn 2+ ; BaAleO 13 : Me 2+ ; 2SrO * 0.84P2O5 * 0.16B2O3: Me 2+ ; (Ba, Sr, Ca) MgAI10Oi7: Eu 2+ , Mn 2+ ;
    (Ba, Sr, Ca) AI 2 O4: Eu 2+ ; (Y, Gd, Lu, Sc, La) BO3: Ce 3+ , Tb 3+ ; ZnS; Cu + , Cr; ZnS: Cu + , AI 3+ ; ZnS: Ag + , Cr; ZnS Ag + , AI 3+ ; (Ba, Sr, Ca) 2Sii.çO4 ^; Eu 2+ (where 0 <ξ <0.2); (Ba, Sr, Ca) 2 (Mg, Zn) Si2O7: Eu 2+ ; (Sr, Ca, Ba) (AI, Ga, ln) 2S4: Eu 2+ ;
    (Y, Gd, Tb, La, Sm, Pr, Lu) 3 (AI, Ga) 5 . Oi2- the 3/2 - a: Ce 3+ (where 0 <a ^ 0.5); (Ca, Sr) 8 (Mg, Zn) (SiO4) 4Cl2: Eu 2+ , Mn 2+ ; Na2Gd 2 B 2 O7: Ce 3+ , Tb 3+ ;
    (Sr, Ca, Ba, Mg, Zn) 2 P 2 O 7 : Eu 2+ , Mn 2+ ; (Gd, Y, Lu, La) 2 O 3 : Eu 3+ , Bi 3+ ;
    (Gd, Y, Lu, La) 2 O 2 S: Eu 3+ , Bi 3+ ; (Gd, Y, Lu, La) VO4: Eu 3+ , Bi 3+ ; (Ca, Sr) S: Eu 2+ , Ce 3+ ; SrY2S 4 : Me 2+ ; CaLa2S4: Ce 3+ ; (Ba, Sr, Ca) MgP2O 7 : Eu 2+ , Mn 2+ ;
    17/20 (Y, Lu) 2 WO 6 : Eu 3+ , Mo 6+ ; (Ba, Sr, Ca) pSi, Nu: Eu 2+ (where 2β + 4γ = 3μ); Ca3 (SiO 4 ) CI 2 : Eu 2+ ; (Lu> ScIYITb) 2.u.vCevCai + uLipMg2-pPp (SiIGe) 3.pO12.u / 2 (where 0.5 <uá1, 0 <v <0.1, and 0íp ^ 0.2); (Υ, Ιυ, 0ά) 2.φ03φ5ί4Ν6 + φ0ι-φ: 0β 3+ , (where 0 <φ <0.5); (Lu, Ca, Li, Mg, Y), α-SiAION enriched with Eu 2+ and / or Ce 3+ ; (Ca, Sr, Ba) SiO2N 2 : Eu 2+ , Ce 3+ ; p-SiAION: Eu 2+ , 3.5MgO * 0.5MgF2 * GeO2: Mn 4+ ; Cai_c. f Ce c EufAI 1 + c Si 1 . c N 3i (where 0 <c ^ 0.2, 0 <f <0.2); Cai.h-rCe h Eu r Ali-h (Mg, Zn) h SiN 3 , (where 0hh <0.2, 0 <r <0.2); Cai_ 2s .tCe s (Li, Na) s EutAISiN 3] (where 0 ^ s <0.2, 0 <f <0.2, s + t>0); and Ca 1 . ff . z ^ Ce <T (Li, Na) z Eu ^ AI 1 + CT . z Sii ^ + z N 3 , (where 0 <σ <0.2, 0 <χ <0.4, 0 <φ <0.2).
    [037] The ratio of each individual phosphor in the phosphor mixture may vary depending on the characteristics of the desired light output. The relative proportions of the individual matches in the various phosphor mixtures of the realization can be adjusted in such a way that, when their emissions are mixed and used in an LED light device, a visible light of predetermined x and y values is produced in the CIE chromaticity diagram . As stated, white light is preferably produced. Such a white light can, for example, have an x value in the range of about 0.20 to about 0.55 and a y value in the range of about 0.20 to about 0.55. As stated, however, the exact identity and quantities of each phosphorus in the phosphorus composition can be varied, according to the needs of the end user. For example, the material can be used for LEDs that are intended for backlighting a liquid crystal device (LCD). In this application, the LED color point would be properly tuned based on the desired white, red, green and blue colors after passing through a combination of LCD / color filters.
    [038] Matches enriched with Mn 4 * prepared by a process according to the present invention can be used in applications other than those described above. For example, the material can
    18/20 be used as a match in a fluorescent lamp, in a cathode ray tube, in a plasma display device or in a liquid crystal device (LCD). The material can also be used as a scintillator in an electromagnetic calorimeter, in a gamma ray camera, in a CT scanner or in a laser. These uses are merely exemplary and are not limiting.
    Examples:
    General Procedures
    Stability Tests
    High Light Flow Conditions [039] A laser diode emitting at 446 nm was coupled to an optical fiber with a collimator at its other end. The output power was 310 mW and the beam diameter in the sample was 700 microns. This is equivalent to a flow of 80 W / cm 2 on the sample surface. The spectral power distribution spectrum (SPD), which is a combination of radiation dispersed from the laser and the emission from the stimulated phosphorus, is collected with an integrating sphere of 1 meter (diameter) and the data are processed with the software of spectrometer (Specwin). At two-minute intervals, the integrated laser power and phosphorus emission were recorded over a period of about 21 hours integrating the SPD from 400 nm to 500 nm and from 550 nm to 700 nm, respectively. The first 90 minutes of the measurement are discarded to avoid effects due to the thermal stabilization of the laser. The percentage of loss of intensity due to laser damage is calculated as follows:
    Loss of intensity (%) = 1OO (Poímond - Potendo iniàaí}
    Initial power [040] Although only the emitting power of the phosphor is plotted, the integrated power of the laser emission, as well as its peak position, has been
    19/20 monitored to ensure that the laser remains stable (variations of less than 1%) during the experiment.
    EXAMPLE 1 2xKF + xMnF2 + (1-x) K2SiF6 + xF2 = K2 (Si1-x, Mnx) F6 [041] In a plastic bottle, 0.164g of MnF 2 + 0.227g of KF + 11.79g of K 2 SiF 6 were combined. Grinding media were added and the mixture was ground by a roller mill for 1 hour. The mixture powder was added to a crucible and initially subjected to a flame at 425 ° C and then subjected to a flame at 560 ° C in an atmosphere of 20% F 2 /80% N 2 for 8 hours. The annealed material was washed in a 48% HF (aq) solution saturated with K 2 SiF 6 . The washed material was vacuum filtered, rinsed with acetic acid and acetone and then dried under vacuum for 2 hours.
    Table 1: Example No. MnF 2 KF MnFj KjMnFe K 2 SiFe Weighttotal weight inmol 92,934 58.10 111.93 247.12 220.27 analyze 0.995 0.990 0.995 0.995 0.995 current weightin mol 93,401 58.68 112.49 248.36 221.38 9 1 molar ratio 0.032 0.0704 0.0000 0.0000 0.9680 1 Weight(grams) 0.164 0.227 0.000 0.000 11,786 12.18 2 molar ratio 0.000 0.0704 0.0320 0.0000 0.9680 2 Weight(grams) 0.000 0.227 0.198 0.000 11,786 12.21 3 molar ratio 0.000 0.0000 0.0000 0.0320 0.9680 3 Weight(grams) 0.000 0.000 0.000 0.437 11,786 12.22
    EXAMPLE 2 2xKF + xMnF3 + (1-x) K2SlF6 + (X / 2) F2 = K2 (Si1-x, Mnx) F6 [042] In a plastic bottle, 0.198g of MnF3 + 0.227g of KF + 11 , 79g of K2SIFF6 were combined in a flask of material
    20/20 plastic. Then, the procedure described in example 1 was followed.
    EXAMPLE 3 YKF + K2-y (Si1-x, Mnx) F6-2y + (y / 2) F2 = K2 (Si1-x, Mnx) F6 [043] In a plastic bottle, 0.437g of K 2 MnF 6 + 11.79 g of K 2 SiF 6 were combined in a plastic bottle. Grinding media were added and the mixture was molded in a roller mill for 1 hour. The mixture powder was added to a crucible and initially subjected to a flame at 350 ° C and a second flame at 560 ° C in an atmosphere of 20% F 2 /80% N 2 for 8 hours. The annealed material was washed in a 48% HF (aq) solution saturated with K 2 SiF 6 . The washed material was vacuum filtered, rinsed with acetic acid and acetone and then dried under vacuum for 2 hours.
    [044] Plates pressed from the powders of Examples 1 to 3 after being subjected to the first and second flame, but before washing, were manufactured. The plates were irradiated with ultraviolet light. All samples emitted the characteristic red light of K 2 SiF 6 : Mn 4+ . The emission spectrum of each sample was essentially identical to that of a phosphorus K 2 SiF 6 : Mn 4+ .
    [045] Although only certain aspects of the invention have been illustrated and described in this document, many modifications and changes will occur by those skilled in the art. It should, therefore, be understood that the appended claims are intended to cover all those modifications and changes while they are within the scope and true spirit of the invention.
    1/4
    权利要求:
    Claims (19)
    [1]
    Claims
    1. PROCESS TO PREPARE A PHOSPHORUS, enriched with Mn 4+ of formula I,
    A x [MF y ]: Mn +4 I characterized by the fact that the process comprises contacting a mixture of a compound of formula A x [MF y ], a compound of formula AX and a source of Mn + n comprising a fluorine-manganese compound, with an oxidizing agent containing fluorine in gaseous form, at an elevated temperature, to form phosphorus enriched with Mn 4+ ; on what
    Aé Li, Na, K, Rb, Cs, or a combination thereof;
    M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof;
    X is F, Cl, Br, I, HF 2 or a combination thereof; x is the absolute value of the ion charge [MF y ]; y is 5, 6 or 7; and n is 2, 3, or 4.
    [2]
    2. PROCESS, according to claim 1, characterized by the fact that the phosphorus enriched with Mn 4+ is K 2 SiF6: Mn 4+ .
    [3]
    3. PROCESS, according to claim 1, characterized by the fact that the compound of formula A x [MF y ] is K 2 SiFe.
    [4]
    4. PROCESS, according to claim 1, characterized by the fact that the compound of formula AX is KF, KHF 2 , or a combination thereof.
    [5]
    5. PROCESS, according to claim 1, characterized by the fact that a source of Mn + n is selected from K 2 MnF 6 , K 2 MnF 5 H 2 O, KMnF 4 , K 2 MnF 4 , KMnF 3 , MnF 2 , MnF 3 MnF 4 , and combinations thereof.
    [6]
    6. PROCESS, according to claim 1,
    2/4 characterized by the fact that a source of Mn + n is K 2 MnF 6 , MnF 2l MnF3 or a combination thereof.
    [7]
    7. PROCESS, according to claim 1, characterized by the fact that the oxidizing agent containing fluorine is F 2 .
    [8]
    8. PROCESS, according to claim 1, characterized by the fact that it additionally comprises treating phosphorus in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid, after coming into contact with the oxidizing agent it contains fluorine
    A x [MF y ] II.
    [9]
    9. PHOSPHORUS, enriched with Mn 4+ prepared by a process, characterized by the fact that it is in accordance with claim 1.
    [10]
    10. LIGHTING EQUIPMENT, characterized by the fact that it comprises a semiconductor light source; and phosphorus enriched with Mn 4+ prepared by a process according to claim 1.
    [11]
    11. NATION BACKLIGHT DEVICE, characterized by the fact that it comprises a semiconductor light source; and a phosphorus enriched with Mn 4+ prepared by a process according to claim 1.
    [12]
    12. PROCESS TO PREPARE A PHOSPHORUS, enriched with Mn 4+ , characterized by the fact that the process comprises contact with a mixture of a phosphorus host compound, a compound of formula AX or EX 2 , and a source of Mn + n which comprises a fluorine-manganese compound; with an oxidizing agent containing fluorine in gaseous form, at an elevated temperature, to form phosphorus enriched with Mn 4+ ;
    in which the host compound is selected from the group consisting of
    3/4 (a) A2 [MFg], where M is selected from Al, Ga, In and combinations thereof;
    (b) A3 [MFe], where M is selected from Al, Ga, In and combinations thereof;
    (c) Zn2 [MF 7 ], where M is selected from Al, Ga, In and combinations thereof;
    (d) A [ln 2 F 7 ];
    (e) A 2 [MF 6 ], where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    (f) E [MF 6 ], where E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof; and where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
    (g) Bao.e5Zro.35F2.7o: θ (h) A 3 [ZrF 7 ]; and combinations thereof in solid solution;
    Aé Li, Na, K, Rb, Cs or a combination thereof.
    [13]
    13. PROCESS, according to claim 12, characterized by the fact that the oxidizing agent containing fluorine is F 2 .
    [14]
    14. PHOSPHORUS, enriched with Mn 4+ prepared by a process, characterized by the fact that it is in accordance with claim 12.
    [15]
    15. LIGHTING EQUIPMENT, characterized by the fact that it comprises a semiconductor light source; and phosphorus enriched with Mn 4+ prepared by a process according to claim 12.
    [16]
    16. BACKLIGHTING DEVICE, characterized by the fact that it comprises a semiconductor light source; and a phosphorus enriched with Mn 4+ prepared by a process according to claim 12.
    [17]
    17. PROCESS TO PREPARE A MATCH, enriched with Mn 4+ of formula I,
    4/4
    A x [MF y ]: Mn +4 ο process comprising contact with a mixture of a phosphorus precursor and a flow compound selected from compounds of the formula AX, EX 2 , MF 2 , or MF 3 or a combination of them, with an oxidizing agent containing fluorine in gaseous form at an elevated temperature, to form the enriched phosphorus Mn 4+ ;
    characterized by the fact that
    Aé Li, Na, K, Rb, Cs or a combination thereof;
    E is Mg, Ca, Sr, Ba, Zn and combinations thereof;
    M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd or a combination thereof;
    X is F, Cl, Br, I, HF 2 or a combination thereof; x is the absolute value of the ion charge [MF y ]; and y is 5, 6 or 7.
    [18]
    18. PROCESS, according to claim 17, characterized by the fact that the flow compound is of formula AX.
    [19]
    19. PROCESS, according to claim 19, characterized by the fact that the compound of formula AX is KF, KHF 2 or a combination thereof.
    1/3
    类似技术:
    公开号 | 公开日 | 专利标题
    BR102015009499A2|2018-02-14|PROCESS FOR PREPARING A MATCH, MATCH, LIGHT APPLIANCE AND BACKLIGHT DEVICE
    BR102015008716A2|2018-10-30|process for preparing mn4 + doped phosphorus
    AU2017200092B2|2018-05-31|Color stable red-emitting phosphors
    US20210340443A1|2021-11-04|Color stable red-emitting phosphors
    US9399732B2|2016-07-26|Processes for preparing color stable manganese-doped phosphors
    KR20170019418A|2017-02-21|Color stable redemitting phosphors
    同族专利:
    公开号 | 公开日
    US20150315462A1|2015-11-05|
    MY171134A|2019-09-27|
    AU2015202034A1|2015-11-19|
    EP2940100A1|2015-11-04|
    EP2940100B1|2020-01-01|
    AU2015202034B2|2018-06-14|
    JP2015212374A|2015-11-26|
    MX364533B|2019-04-29|
    CA2888731A1|2015-11-01|
    TW201602311A|2016-01-16|
    KR20150126305A|2015-11-11|
    KR101913895B1|2018-10-31|
    JP6571374B2|2019-09-04|
    TWI640604B|2018-11-11|
    CN105038774B|2019-06-04|
    US9546318B2|2017-01-17|
    CN105038774A|2015-11-11|
    MX2015005581A|2016-02-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2447359A|1944-12-01|1948-08-17|Tennessee Corp|Production of sodium fluosilicate|
    US3576756A|1968-06-12|1971-04-27|Mallinckrodt Chemical Works|Fluocomplexes of titanium, silicon, tin and germanium, activated by tetravalent manganese|
    GB1360690A|1973-02-16|1974-07-17|Gen Electric Co Ltd|Luminescent materials|
    US7524480B2|2004-09-10|2009-04-28|Show A Denko K.K.|Process for producing manganese fluoride|
    US7648649B2|2005-02-02|2010-01-19|Lumination Llc|Red line emitting phosphors for use in led applications|
    US7358542B2|2005-02-02|2008-04-15|Lumination Llc|Red emitting phosphor materials for use in LED and LCD applications|
    US7497973B2|2005-02-02|2009-03-03|Lumination Llc|Red line emitting phosphor materials for use in LED applications|
    US8465166B2|2007-04-20|2013-06-18|Konklijke Philips Electronics N.V.|White emitting light source and luminescent material with improved colour stability|
    WO2009012301A2|2007-07-16|2009-01-22|Lumination Llc|Red line emitting complex fluoride phosphors activated with mn4+|
    CN101939857B|2008-02-07|2013-05-15|三菱化学株式会社|Semiconductor light emitting device, backlight, color image display device and phosphor to be used for them|
    WO2009119486A1|2008-03-25|2009-10-01|国立大学法人群馬大学|Fluorescent material, process for producing the same, and white-light-emitting diode employing the fluorescent material|
    JP5239043B2|2008-07-18|2013-07-17|シャープ株式会社|Light emitting device and method for manufacturing light emitting device|
    JP5682104B2|2008-09-05|2015-03-11|三菱化学株式会社|Phosphor and method for producing the same, phosphor-containing composition and light emitting device using the phosphor, and image display device and lighting device using the light emitting device|
    JP2010093132A|2008-10-09|2010-04-22|Sharp Corp|Semiconductor light emitting device, and image display and liquid crystal display using the same|
    US8057706B1|2010-07-27|2011-11-15|General Electric Company|Moisture-resistant phosphor and associated method|
    JP5527130B2|2010-09-17|2014-06-18|三菱電機株式会社|Lighting device and lighting fixture provided with the lighting device|
    JP4974310B2|2010-10-15|2012-07-11|三菱化学株式会社|White light emitting device and lighting apparatus|
    US8252613B1|2011-03-23|2012-08-28|General Electric Company|Color stable manganese-doped phosphors|
    MY167700A|2011-04-08|2018-09-21|Shinetsu Chemical Co|Preparation of complex fluoride and complex fluoride phosphor|
    KR101535164B1|2011-12-16|2015-07-09|코닌클리케 필립스 엔.브이.|Mn-activated hexafluorosilicates for led applications|
    WO2013121355A1|2012-02-16|2013-08-22|Koninklijke Philips N.V.|Coated narrow band red-emitting fluorosilicates for semiconductor leds|
    US9765257B2|2012-03-12|2017-09-19|Nitto Denko Corporation|Emissive compacts and method of making the same|
    US9698314B2|2013-03-15|2017-07-04|General Electric Company|Color stable red-emitting phosphors|US9868898B2|2013-03-15|2018-01-16|General Electric Company|Processes for preparing color stable red-emitting phosphors|
    US9385282B2|2014-06-12|2016-07-05|General Electric Company|Color stable red-emitting phosphors|
    US9567516B2|2014-06-12|2017-02-14|General Electric Company|Red-emitting phosphors and associated devices|
    US10563121B2|2014-06-12|2020-02-18|Current Lighting Solutions, Llc|Red-emitting phosphors and associated devices|
    CN109219646A|2016-06-02|2019-01-15|通用电气公司|Emit the phosphor and relevant apparatus of feux rouges|
    US9371481B2|2014-06-12|2016-06-21|General Electric Company|Color stable red-emitting phosphors|
    JP2016210986A|2015-05-07|2016-12-15|学校法人日本大学|Method of producing rare earth-free phosphor and rare earth-free phosphor|
    EP3380581B1|2015-11-26|2020-07-15|General Electric Company|Processes for synthesizing red-emitting phosphors and related red-emitting phosphors|
    CN105505384B|2015-12-03|2017-12-19|河北利福光电技术有限公司|A kind of narrow band red light fluorescent powder and preparation method thereof|
    KR20170085168A|2016-01-13|2017-07-24|삼성전자주식회사|Fluoride phosphor, manufacturing method of the same, and light emitting device|
    CN105733572A|2016-03-24|2016-07-06|中山大学|Red fluoride fluorescent powder as well as preparation method and application thereof|
    US9605199B1|2016-03-31|2017-03-28|General Electric Company|Oxy-bromide phosphors and uses thereof|
    JP2018002813A|2016-06-29|2018-01-11|株式会社東芝|Fluophor and light-emitting device|
    CN106318381B|2016-08-18|2018-06-19|温州大学|A kind of Mn4+Sodium bifluoride red light material of doping and preparation method thereof|
    EP3538624A1|2016-10-12|2019-09-18|Merck Patent GmbH|Mn4+-activated luminescence material as conversion luminescent material for led solid state light sources|
    JP2019167277A|2018-03-24|2019-10-03|国立大学法人 新潟大学|Production method of red fluoride phosphor|
    CN110295042A|2018-03-24|2019-10-01|国立大学法人新泻大学|The manufacturing method of fluoride red-emitting phosphors and its host crystal|
    US10764975B2|2018-03-30|2020-09-01|Facebook Technologies, Llc|Pulse-width-modulation control of micro light emitting diode|
    CN109294565B|2018-11-15|2022-02-11|中山大学|High-performance narrow-band fluorescent powder and preparation method thereof|
    CN112779003A|2019-11-11|2021-05-11|南京大学|Manganese-halogen fluorescent powder material, preparation method thereof and light-emitting device using manganese-halogen fluorescent powder material|
    FR3106832A1|2020-02-03|2021-08-06|Centre National De La Recherche Scientifique|Dry process of synthesis of a phosphor by treatment in a fluorine atmosphere|
    CN111454719A|2020-05-28|2020-07-28|云南民族大学|double perovskite fluoride red luminescent material for white light LED|
    CN113214825A|2021-04-26|2021-08-06|云南民族大学|Multi-fluoride red-light material for solid-state lighting LED and preparation method and application thereof|
    法律状态:
    2018-02-14| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-30| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2022-02-22| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 7A ANUIDADE. |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/267,449|2014-05-01|
    US14/267,449|US9546318B2|2014-05-01|2014-05-01|Process for preparing red-emitting phosphors|
    [返回顶部]