process for preparing mn4 + doped phosphorus

专利摘要:
“process for preparing mn 4+ doped phosphorus” a process for preparing a mn4+ doped phosphorus of formula i ax [mfy]:mn+4 i includes combining, in an acidic solution, an a+ cation, an anion of formula mfy, and an mnn+ source comprising a fluoromanganese compound, precipitating an mnn+-containing phosphorus precursor from the acidic solution, and contacting the mnn+-containing phosphorus precursor with an oxidizing agent that contains fluorine in gaseous form at an elevated temperature to forming mn4+-doped phosphorus; wherein 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 the absolute value of the ion charge [mfy] ; y is 5, 6 or 7; and n is 2 or 3.
公开号:BR102015008716A2
申请号:R102015008716
申请日:2015-04-17
公开日:2018-10-30
发明作者:Achyut Setlur Anant；Edward Murphy James；Joseph Lyons Robert
申请人:Gen Electric；
IPC主号:

专利说明:

(54) Title: PROCESS TO PREPARE MATCH DOPED WITH MN4 + (51) Int. Cl .: C09K 11/61; H01L 33/50 (30) Unionist Priority: 01/05/2014 US 14 / 267,434 (73) Holder (s): GENERAL ELECTRIC COMPANY (72) Inventor (s): ROBERT JOSEPH LYONS; ANANT ACHYUT SETLUR; JAMES EDWARD MURPHY (85) National Phase Start Date:
04/17/2015 (57) Summary: PROCESS FOR
PREPARING PHOSPHORUS DOPED WITH MN 4+ A process for preparing a phosphorus doped with Mn4 + of formula I Ax [MFy]: Mn + 4 I includes combining, in an acid solution, an A + cation, an anion of formula MFy and a source of Mnn + which comprises a fluoromanganese compound, precipitating a phosphorus precursor containing Mnn + from the acidic solution and contacting the phosphorus precursor containing Mnn + with an oxidizing agent containing fluorine in gas at an elevated temperature to form the doped phosphorus 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 the absolute value of the ion charge [MFy]; y is 5, 6 or 7; and n is 2 or 3.
1/19 “PROCESS TO PREPARE PHOSPHORUS DOPED WITH Mn ⁴⁺ ” Cross Reference to Related Orders [001] This application is related to the United States Patent Application, filed concurrently with this document, under the number of attorney file n ^e 270388-2, the disclosure of which is incorporated herein in its entirety as a reference.
Background [002] Red emission matches based on complex fluoride materials activated by Mn ⁴⁺ , such as those described in documents n ^and US 7,358,542, US 7,497,973 and US 7,648,649, can be used in conjunction with matches green / yellow emission, such as YAG: Ce or other garnet compositions, to achieve warm white light (CCTs <5,000 K in color rendering index (CRI)> 80, blackbody locus) from a blue LED, equivalent to that produced by halogen, incandescent and fluorescent lamps. Those materials that absorb blue light emit strongly and efficiently between about 610 and 635 nm, with shallow emission of NIR / red. Therefore, the luminous efficacy is maximized, compared to the red matches that have significant emission in the deepest red, where the eye's sensitivity is weak. The quantum yield can exceed 85% under blue excitation (440 at 460 nm).
[003] Methods for preparing matches typically require hydrofluoric acid as a solvent. For example, the document WO 2007/100824 ^and n describes the preparation of complex fluoride phosphors using aqueous HF as solvent. The processes use significant amounts of this highly toxic material, and alternatives that eliminate HF, or that at least reduce the amount, are economically advantageous.
Brief description [004] Briefly, in one aspect, the present invention relates to an HF-free process for preparing a phosphorus doped with Mn ⁴⁺ of formula I
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2/19
Αχ [MF _y ]: Mn ⁺⁴ I 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 the absolute value of the ion charge [MFy];
- y is 5, 6 or 7; and
- n is 2 or 3.
[005] The process includes combining, in an acidic solution, an A + cation, an anion of the formula MFy and a source of Mn ^{n +} which comprises a fluoromanganese compound; precipitating a phosphorus precursor containing Mn ^{n +} from the acid solution; and contacting the phosphorus precursor that contains Mn ^{n +} with an oxidizing agent that contains fluorine in gaseous form, at an elevated temperature, to form the phosphorus doped with Mn4 +.
[006] In particular embodiments, a solution from a source of Mn ^{n +} in aqueous fluorosilicic acid is added to a solution of KF in water to precipitate the phosphorus precursor containing Mn ^{n +} , K2SiF6: Mn2 + or K2SiF6: Mn3 +.
Figures [007] These and other functions, aspects and advantages of the present invention will become better understood when the following detailed description is read, with reference to the attached Figures, in which similar characters represent similar parts throughout the Figures, 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;
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3/19
Figure 3 is a schematic cross-sectional view of a lighting apparatus, in accordance with yet another embodiment of the invention;
Figure 4 is a side perspective view 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 [008] In the processes of the present invention, an acid solution is the medium in which the A + cation, the anion of formula MFy and the source of Mn ^{n +} are combined to form the precursor containing Mn ^{n +} . Suitable acid solutions are those solutions in which both the anion of formula MFy and the fluoroanion Mn ^{n +} of the precursor are stable. The acid can be of formula Hx [MF _y ]; examples of suitable acids include H2SIF6, FhGeFe, H2TIF6 and combinations thereof. In particular embodiments, the acid is fluorosilicic acid.
[009] A + cations can be supplied as a salt, the corresponding anion for A ⁺ can be fluoride, chloride, acetate, chloride, oxalate, dihydrogen phosphate or a combination thereof, particularly fluoride. Examples of suitable materials include KF, KHF, LiF, L1HF2, NaF, NaHF2, RbF, RbHF2, CsF, CSHF2 and combinations thereof. In particular embodiments, the anion is fluoride. The anion of formula MF _y can be obtained from the acid of formula H _x [MF _y ], or a compound, such as CS2SIFF6 or MgSiF6-6H2O, can be used. Fluoromanganese compounds suitable for use as the source of Mn ^{n +} yield the fluoroanion Mn ^{n +} when dissolved in the acidic solution. Examples of suitable 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 suitable sources of Mn ³⁺ include K2MnF5-H2O, KMnF4 and MnF3, manganese acetate (III), manganese oxide (III) and combinations thereof. Hydrated forms of Mn ^{n +} sources can produce
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4/19 low HF concentrations. Sources of Mn ⁴⁺ , such as MnF4, foMnFô and MnCte, can also be used, but may have limited stability or solubility in solutions that do not contain HF, which lead to a reduction in manganese.
[010] The anion of formula MF _y and the source of Mn ^{n +} are combined with an cation A ⁺ and an anion of formula MFy in the acidic solution, and the phosphorus precursor containing Mn ^{n +} is precipitated. The fluoride or bifluoride anion, or a combination thereof, may also be present in the solution; a convenient source of the A + cation and the fluoride or bifluoride anion can be the fluoride or bifluoride salt of A ⁺ , AF or AHF2. In particular embodiments, the source of Mn ^{n +} is combined with the acid, which can also provide the anion of formula MFy, and the A + cation is added to it. In some cases, the A + cation is dissolved in a basic solution, for example, an aqueous solution of an A + carbonate or hydroxide. The order of addition is not necessarily the same in all embodiments, and in some cases, the KF solution can be added to the acid solution. The quantities of raw materials for MF _y , anion, fluoroanion Mn ^{n +} and AF are determined by the stoichiometry of the reaction to form the precursor.
[011] The precursor may be a complex fluoride phosphorus containing Mn ^{n +} of formula III
Am [MF _z ]: Mn ^{n +}
III where A, M and n are as defined above,
- m is the absolute value of the ion charge [MF _Z ]; and
- 4 <z <7.
[012] An example of a phosphorus precursor that contains Mn ^{n +} that can be formed as an intermediate in a process, according to the present invention, is K2SIFF6 that contains Mn ³⁺ .
[013] In particular embodiments, the phosphorus of formula I is K2SiF6: Mn ⁴⁺ , and the source of Mn ^{n +} is combined with the anion SíFô and KF to yield the
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5/19
K2SÍF6 containing Mn ^{n +} . For example, the source of Mn ^{n +} can be dissolved in aqueous fluorosilicic acid and added to a KF solution in water to precipitate the phosphorus precursor containing Mn ^{n +} , K2SiF6: Mn ²⁺ or K2SiF6: Mn ³⁺ .
[014] In some embodiments, phosphorus doped with Mn ⁴⁺ of formula I is moderately soluble in the aqueous acidic solution and precipitates by formation. If the phosphorus is not sufficiently insoluble in the medium to precipitate, a weak solvent can be added to the solution, causing the phosphorus to precipitate. Solvents suitable for use as the weak solvent are those that are not attacked by Mn ^{n +} and include alcohols, ketones, carboxylic acids and phosphoric acid, particularly acetone.
[015] The phosphorus precursor that contains Mn ^{n +} can be converted into phosphorus doped with Mn ⁴⁺ by contacting an oxidizing agent that contains fluorine in gaseous form at an elevated temperature. The temperature can vary from about 200 ° C to about 700 ° C, particularly from about 350 ° C to about 600 ° C during contact, and, in some embodiments, from about 200 ° C to about 700 ° C. 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 phosphorus precursor is contacted with the oxidizing agent for a period of time sufficient to convert it into a phosphorus doped with Mn ⁴⁺ . Time and temperature are interrelated, and can be adjusted together, for example, by increasing the time while reducing the temperature, or by increasing the temperature while reducing the time. The contact stage can include multiple contact periods, time and temperature variations, and the precursor can be re-homogenized between periods to improve treatment uniformity. In particular embodiments, the phosphorus precursor is contacted with the oxidizing agent for a period of at least eight hours and a temperature of at least 250 ° C, for example, at about 425 ° C, for about four hours and then , in a
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6/19 temperature of about 560 ° C, for about four hours.
[016] The oxidizing agent containing fluorine can be F2, HF, SF6, BrFs, NH4HF2, NHLF, KF, AIF3, SbFs, CIF3, BrFs, KrF, XeF ₂ , XeF ₄ , NF3, SiF ₄ , PbF ₂ , ZnF2 , SnF2, CdF2 or a combination thereof. In particular embodiments, the oxidizing agent that contains fluorine is F2. The amount of oxidizing agent in the atmosphere can be varied, particularly along with the variation in time and temperature. When the oxidizing agent containing fluorine is F2, the atmosphere can include at least 0.5% F2, although a lower concentration may be effective in some embodiments. In particular, the atmosphere can include at least 5% F2 and, more particularly, at least 20% F2. 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% F2 and about 80% nitrogen.
[017] The way of contacting the phosphorus precursor containing Mn ^{n +} with the oxidizing agent containing fluorine is not critical, and can be done in any way sufficient to convert the phosphorus precursor into a phosphorus that has the desired properties. In some embodiments, the chamber containing the precursor can be dosed and then sealed in such a way that an overpressure develops as the chamber is heated, and in others, the mixture of fluorine and nitrogen is drained through the process. annealing that guarantees a more uniform pressure. In some embodiments, an additional dose of the fluoride-containing oxidizing agent may be introduced after a period of time.
[018] A flow material can be mixed with the precursor containing Mn ^{n +} , before annealing. The use of a flux may be desirable when the phosphorus precursor containing Mn ^{n +} is deficient in A ⁺ , in relation to phosphorus doped with product Mn ⁴⁺ , that is, when the ratio [A ⁺ ] / ([Mn ^{n +} ] + [M]) is less than or equal to 2, but is not limited to it. Suitable flow materials containing A + for use as a flow include compounds of formula ΑΧ, EX2, MF2 or
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7/19
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, particularly potassium monofluorides and bifluorides , sodium and rubidium, KF and KHF2, NaF and NaHF2, RbF and RbHF2 and combinations thereof. In particular embodiments, the flow material containing A ⁺ is KF or KHF2 or a combination thereof. The flow material can be removed from the phosphorus product by washing with a suitable solvent, such as acetic acid.
[019] Color stability and quantum yield 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
Ax [MFy]
II in aqueous hydrofluoric acid, as described in document n ^and US 8,252,613. For example, K2SiF6: Mn ⁴⁺ can be treated with a solution of K2S1F6 in HF at room temperature to improve color stability and the quantum yield of phosphorus. The temperature at which the phosphorus is contacted 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 about 40% w / w to about 70% w / w. Less concentrated solutions can result in low phosphorus yields.
[020] Phosphorus precursors containing Mn ^{n +} used in processes according to the present invention, and phosphorus doped with Mn ⁴⁺ produced by them are complex fluoride materials. In the context of the present invention, the term complex fluoride material means a coordinating compound, which contains at least one
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8/19 coordination, surrounded by fluoride ions that act as binders, and with charge compensation by counterions, as needed. In one example, K2SiF6: Mn ⁴⁺ , the coordination center is Si and the counterion is K. Complex fluorides are occasionally written as a combination of simple, binary fluorides, but such a representation does not indicate the coordination number for the ligands to around the coordination center. The square brackets (occasionally omitted for simplicity) indicate that the complex ion they contain is a new chemical species, different from the simple fluoride ion. The activating ion (Mn ⁴⁺ ) also acts as a coordination center, which replaces the part of the centers of the host network, for example, Si. The host network (which includes counterions) can further modify the excitation and emission properties of the activating ion.
[021] In some embodiments, phosphors doped with Mn ⁴⁺ that can be prepared by a process, according to the present invention, are selected from the group consisting of (A) A2 [MF5]: Mn ⁴⁺ , in that M is selected from Al, Ga, In and combinations thereof;
(B) A3 [MF6]: Mn ⁴⁺ , where M is selected from Al, Ga, In and combinations thereof;
(C) Zn2 [MF7]: Mn ⁴⁺ , where M is selected from Al, Ga, In and combinations thereof;
(D) A [ln ₂ F ₇ ]: Mn ⁴⁺ ;
(E) A2 [MF6]: Mn ⁴⁺ , where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
(F) E [MF6]: 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) Bao, 65Zro, 35F2.7o: Mn ⁴⁺ ;
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9/19 (H) A ₃ [ZrF ₇ ]: Mn ⁴⁺ ;
where A is Li, Na, K, Rb, Cs or a combination thereof.
[022] Examples of Mn ⁴⁺ doped matches that can be prepared by a process according to the present invention include K2 [SiF6]: Mn ⁴⁺ , K2 [TiF6]: 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 [BiF6]: Mn ⁴⁺ , K3 [YF6]: Mn ⁴⁺ , K3 [LaF ₆ ]: Mn ⁴⁺ , K3 [GdF6]: Mn ⁴⁺ , K3 [NbF ₇ ]: Mn ⁴⁺ , K ₃ [TaF ₇ ]: Mn ⁴⁺ . In particular embodiments of 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 thereof, and y is 6.
[023] Matches doped with Mn ⁴⁺ prepared by a process according to the present invention can exhibit good color stability after exposure to the flow of light. A lighting fixture that incorporates a phosphorus doped with Mn ⁴⁺ prepared by a process according to the present invention may have a color change of <1.5 ellipses of MacAdam after operating for at least 2,000 hours at a current density of LED greater than 2 A / cm ² , an LED power efficiency greater than 40% and a plate temperature greater than 25 ° C, preferably where the color change in the MacAdam ellipse is <1. Under In the accelerated test conditions, the lighting fixture may have a color change of <2 ellipses from MacAdam, after operating for 30 minutes at an LED current density greater than 70 A / cm ² , an LED power 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 w / cm ² at a temperature of at least 50 ° C; % loss of intensity of stable color matches can be <4% after 21 hours.
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10/19 [024] A lighting apparatus or light emitting assembly or lamp 10, according to the realization of this invention, is shown in Figure 1. The lighting apparatus 10 includes a semiconductor radiation source, shown as a light-emitting diode (LED) 12, and cables 14 electrically attached to the LED chip. The cables 14 can be thin wires supported by a thicker wire structure (s) 16, or the cables can be self-supporting electrodes, and the cable structure can be omitted. The cables 14 supply current to the LED chip 12 and then cause it to emit radiation.
[025] The lamp can include any semiconductor source of UV or blue light that is capable of producing white light when its emitted radiation is directed on the phosphor. In one embodiment, the semiconductor light source is a blue emission LED doped with various impurities. Then, the LED can comprise a semiconductor diode based on any suitable semiconductor layers ll-V, ll-VI or IV-IV and which have 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 composed of nitride represented by the formula IniGajAlkN (where 0 <i; 0 <j; 0 <kel + j + k = 1) which has an emission wavelength greater than about 250 nm and less than about 550 nm. In particular embodiments, the chip 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 encompass all semiconductor radiation sources that include, for example, conductive laser diodes. Additionally, although the general discussion of the exemplary structures of the invention discussed in the present
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11/19 document is directed towards light sources based on inorganic LEDs, it should be understood that the LED chip can be replaced by another source of radiation, unless otherwise noted, and any reference to semiconductor , Semiconductor LED or LED chip 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 phosphorus composition 22 is radioactively coupled to the LED chip 12. Radioactively coupled means that the elements are associated with each other, so the radiation from one is transmitted to the other. The phosphorus composition 22 is deposited on LED 12 by any appropriate 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 slurry, in which the phosphor particles are randomly suspended, is placed around the LED. This method is merely an example of possible positions of composition of phosphorus 22 and LED 12. Then, the composition of phosphorus 22 can be coated on or directly on the light-emitting surface of the LED chip 12 by coating and drying the suspension of phosphor on the LED chip 12. In the case of a silicone based suspension, the suspension is cured at an appropriate temperature. Both wrap 18 and encapsulant 20 should be transparent to allow white light 24 to be transmitted through those elements. Although not intended to be limiting, in some embodiments, the median 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 spread within the encapsulating material 20, instead of being formed directly on the LED chip 12. The phosphorus (in powder form) can be spread
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12/19 within a single region of the encapsulating material 20 or over the entire volume of the encapsulating material. The blue light emitted by the LED chip 12 mixes with the light emitted by the phosphorus composition 22, and the mixed light appears as white light. If the phosphor is to be spread into the encapsulant material 20, then a phosphor powder can be added to a silicone or polymer precursor, loaded around the LED chip 12, and then the polymer precursor can be cured to solidify the silicone or polymer material. Other known methods of phosphorus intercalation can also be used, such as transfer loading.
[028] In yet another embodiment, the phosphorus composition 22 is coated on a surface of the envelope 18, instead of being formed on the LED chip 12. The phosphorus composition is preferably coated on the inner surface of the envelope 18, although the phosphorus can be coated on the outer surface of the wrap, if desired. The phosphorus composition 22 can be coated on the entire surface of the wrap or just an upper portion of the surface of the wrap. The blue / UV light emitted by the LED chip 12 mixes with the light emitted by the phosphorus composition 22, and the mixed light appears as white light. Certainly, the phosphor can be located in any one of the two or all three locations or in any other suitable location, such as separately from the wrapper or integrated into the LED.
[029] Figure 2 illustrates a second structure of the system, according to the present invention. Corresponding numbers from 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 stated otherwise. The structure of the realization of Figure 2 is similar to that of Figure 1, except that the composition of phosphorus 122 is spread within the encapsulating material 120, instead of being formed directly on the LED chip 112. The phosphorus (in the form of dust) can be spread within a single region of the material
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13/19 encapsulant or over the entire volume of encapsulating material. The radiation (indicated by the arrow 126) emitted by the LED chip 112 mixes with the light emitted by the phosphor 122, and the mixed light appears as the white light 124. If the phosphor must be spread within the encapsulating material 120, then a powder phosphorus can be added to a polymer precursor and loaded around the 112 LED chip. The silicone or polymer precursor can then be cured to solidify the polymer or silicone. Other known methods of phosphorus intercalation 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 a surface of the envelope 218, instead of being formed on the LED chip 212. The composition of phosphorus 222 is preferably coated on the inner surface of the envelope 218, although the phosphorus can be coated on the outer surface of the envelope, if desired. The phosphorus composition 222 can be coated on the entire surface of the envelope, or just an upper portion of the surface of the envelope. The radiation 226 emitted by the LED chip 212 mixes with the light emitted by the composition of phosphorus 222, and the mixed light appears as white light 224. Certainly, the structures of Figures 1 to 3 can be combined, and the phosphor can be located in any of the two or all three locations, or in any other suitable location, such as separately from the envelope, or integrated into the LED.
[031] In any of the above structures, the lamp can also include a plurality of scattered particles (not shown), which are embedded in the encapsulating material. The dispersed particles can comprise, for example, alumina or titania. The scattered particles effectively disperse the directional light emitted from the LED chip, preferably with an insignificant amount of absorption.
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14/19 [032] As shown in a fourth structure in Figure 4, the LED chip 412 can be mounted in a reflective cup 430. The cup 430 can be produced from, or coated with a dielectric material, such as alumina, titania , 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 may include two cables 416, a conductive wire 432 and an encapsulating material 420. The reflective cup 430 is supported by the first cable 416 and the conductor wire 432 is used to electrically connect the LED chip 412 to the second cable 416.
[033] Another structure (particularly for backlight applications) is a surface-mounted device-type 550 light-emitting diode (“SMD”), for example, as illustrated in Figure 5. This SMD is a type of emission side and has a 552 light-emitting window on a protruding portion of a 554 light-conducting member. An SMD package may comprise an LED chip, as defined above, and a phosphor material, which is excited by the light emitted from the LED chip. Other backlight devices include, but are not limited to, TVs, computers, smart phones, tablet computers and other portable devices that have a display that includes a semiconductor light source and a phosphor doped with Mn4 + prepared by a process, from according to the present invention.
[034] When used with an LED that emits from 350 to 550 nm and one or more other appropriate matches, the resulting lighting system will produce a light that has a white color. Lamp 10 may also include scattered particles (not shown), which are embedded in the encapsulating material. The dispersed particles can comprise, for example, alumina or titania. The scattered particles effectively disperse the directional light emitted from the LED chip, preferably with an insignificant amount of absorption.
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15/19 [035] In addition to phosphorus doped with Mn ⁴⁺ , the composition of phosphorus 22 may include one or more other phosphors. When used in a lighting fixture together with near-blue or blue LED emission radiation in the range of about 250 to 550 nm, the resulting light emitted by the array will be white light. Other matches, such as green, blue, yellow, red, orange or other colored matches can be used in the mix to customize the white color of the resulting light and produce distributions of specific spectral power. Other materials suitable for use in the composition of phosphorus 22 include electroluminescent polymers, such as polyfluorenes, preferably poly (9,9dioctyl fluorene) and copolymers thereof, such as poly (9,9'-dioctylfluorene-cobis-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 metal or dye complex or a combination thereof. Materials suitable for use as the 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- (4,6-difluorephenyl) pyridinate-N, C2) (blue dye). The 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. ADS blue dyes include ADS064BE, ADS065BE and ADS070BE. ADS red dyes include ADS067RE, ADS068RE, ADS069RE, ADS075RE, ADS076RE, ADS067RE and ADS077RE.
[036] Matches suitable for use in phosphorus 22 composition include, but are not limited to:
- ((Sn-z (Ca, Ba, Mg, Zn) z) i- (x + w) (Li, Na, K, Rb) wCex) 3 (Ali-ySiy) O4 + y3 + (xw) Fi- _y -3 (xw), 0 <x <0.10, 0 <y <0.5, 0 <z <0.5, 0 <w <x;
- (Ca, Ce) 3Sc2Si ₃ 0i2 (CaSiG);
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16/19
- (Sr, Ca, Ba) 3Ali-xSixO4 ₊ xFi-x: Ce ³⁺ (SASOF));
- (Ba, Sr, Ca) 5 (PO4) 3 (CI, F, Br, OH): Eu ²⁺ , Mn ²⁺ ;
(Ba, Sr, Ca) BPOs: Eu ²⁺ , Mn ²⁺ ; (Sr, Ca) io (P04) 6 * vB ₂ 03: Eu ²⁺ (where 0 <v <1);
SrzSÍ3O8 * 2SrCI ₂ : Eu ²⁺ ; (Ca, Sr, Ba) 3MgSi2O8: Eu ²⁺ , Mn ²⁺ ; BaAI80i ₃ : Me ²⁺ ;
2SiO * 0.84P ₂ 05 * 0.16B ₂ 0 ₃ : Me ²⁺ ; (Ba, Sr, Ca) MgAlioOi7: Eu ²⁺ , Mn ²⁺ ; (Ba, Sr, Ca) AI2O4: Eu ²⁺ ; (Y, Gd, Lu, Sc, La) BO3: Ce ³⁺ , Tb ³⁺ ; ZnS: Cu ⁺ , C | -; ZnS: Cu ⁺ , AI ³⁺ ; ZnS: Ag ⁺ , C | -; ZnS: Ag ⁺ , AI ³⁺ ; (Ba, Sr, Ca) 2Siii; O4-2 £: Eu ²⁺ (where 0 <ξ <0.2); (Ba, Sr, Ca) 2 (Mg, Zn) Si ₂ O7: Eu ²⁺ ; (Mr.Ca.BaXAI.Ga.ln ^ S ^ Eu ² *; (Y.Gd.Tb.La.Sm.Pr.LubíAI.Gajs ^ O ^ - ^ Ce ³ * (where 0 <to <0, (Ca, Sr) 8 (Mg, Zn) (SiO4) 4Cl2: Eu ²⁺ , Mn ²⁺ ; Na2Gd ₂ B ₂ O ₇ : Ce ³⁺ , Tb ³⁺ ;
(Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O7: 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⁺ ; SrY2S4: Me ²⁺ ; CaLa2S4: Ce ³⁺ ; (Ba, Sr, Ca) MgP2O7: Eu ²⁺ , Mn ²⁺ ; (Y.Lu ^ WCfcEu ^ .Mo ⁶ *; (Ba, Sr, Ca) pSi, Nu: Eu ²⁺ (where 2β + 4 _ζ = 3 _μ ); Ca3 (SiO4) CI ₂ : Eu ²⁺ ; ( Lu, Sc, Y, Tb) 2-ihvCevCai + uLiwMg2 ^ Pw (Si, Ge) 3 «Oi2-uc (where -0.5 <υ <1, 0 <to <0.1, and 0 <w <0.2); (Y, Lu, Gd) 2- (pCa (pSÍ4N & KpCi- (p: Ce ³⁺ , (where 0 <φ <0.5); (Lu, Ca, Li, Mg, Y), α-SiAION doped with Eu ² * and / or Ce ³⁺ ; (Ca, Sr, Ba) SiO2N ₂ : Eu ²⁺ , Ce ³⁺ ; p-SiAIOISLEu ² *, 3,5MgO * 0,5MgF2 * GeO2: Mn ⁴⁺ ; Cai <-fCecEufAli + tSii <N3, (where 0 <χ <0.2, 0 <φ <0.2); Cai4HCehEuiAli-h (Mg, Zn) hSiN3, (where 0 <η <0.2 , 0 <p <0.2); Cai- _2s -tCe _s (Li, Na) sEutAISiN3, (where 0 <σ <0.2, 0 <φ <0.2, σ + τ>0); and Cai ^ ^ CeaíLi.NaXEu ^ li + o-zSiw / Ns, (where 0 <σ <0.2, 0 <χ <0.4, 0 <φ <0.2).
[037] The ratio of each of the individual matches in the phosphor mixture may vary, depending on the desired characteristics of the 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 lighting device, there is visible light produced from predetermined x and y values in the chromaticity diagram CIE. As determined, white light is preferably produced. This white light can, for example, have a
Petition 870180023957, of March 26, 2018, p. 24/34
17/19 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 determined, however, the exact amounts and identity 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 intended for liquid crystal display (LCD) lighting. In this application, the color point of the LED would be properly adjusted based on the desired colors white, red, green and blue, after passing through a combination of color filter / LCD.
[038] Matches doped 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 be used as a phosphor in a fluorescent lamp, in a cathode ray tube, in a plasma display device or in a liquid crystal display (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 without limitation.
Examples
General Procedures
Stability Testing
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 power output 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 excited phosphorus, is collected with an integral sphere of 1 meter (diameter) and the data processed with the software spectrometer (Specwin). At two-minute intervals, the power
Petition 870180023957, of March 26, 2018, p. 25/34
18/19 integrated from the laser and the emission of phosphorus were registered for a period of about 21 hours integrating the SPD from 400 nm to 500 nm and 550 nm to 700 nm respectively. The first 90 minutes of the measurement are discarded to avoid the effects due to the thermal stabilization of the laser. The percentage of loss of intensity due to laser damage is calculated as follows:
[040] Although only the power of the emitter from the phosphorus is illustrated graphically, the integrated power of the laser emission, as well as its peak position, was monitored to ensure that the laser remained stable (variations of less than 1%) during the experiment.
Comparative Example 1 - Preparation of K2SIF6: Mn ⁴⁺ [041] A phosphorus of potassium fluorosilicate doped with Mn, K2SiF6: Mn4 +, obtained from a commercial source, which contains 0.84% by weight of Mn, based on total weight, it was annealed at 540 ° C in 0.07 MPa (10 psi) under an atmosphere of 20% F2 / 80% N2, for 8 hours. The annealed phosphorus powder was treated with a saturated solution of K2SIFF6 by placing the powder (~ 10 g) in a Teflon beaker containing 100 ml of a saturated solution of K2SIFF6 (initially produced by adding approximately 17 g of K2SIFF6 in 40% HF at room temperature, stirring and filtering the solution). The suspension was stirred slowly, and the residue is filtered and dried in vacuo. The dry filtrate was washed with acetone 3 to 5 times and heated at 100 ° C for 10 minutes to remove HF.
Example 1 - Preparation of K2MNF5 »H2O [042] A solution of hydrochloric acid (45 ml of 37% HCI) was gradually added to a slurry of potassium bifluoride (15.62 g of KHF2) and potassium permanganate (15 , 8 g of KMnCXQ in 10.5 ml of 48 to 49% HF. After the addition was completed, the temperature was raised to 70 ° C
Petition 870180023957, of March 26, 2018, p. 26/34
19/19 to complete the reaction and expel dissolved CI2. The contents of the flask were vacuum filtered. The filtrate was rinsed with glacial acetic acid to remove KHF2, and with acetone, three times, then dried in a vacuum desiccator. Yield: 23 grams of pink-pink hMO foMnFs.
Example 2 - Preparation of Mn ³⁺ containing K2S1F6 [043] A solution of K2CO3 (5.56 g) and KHF2 (3.78 g) in 20 ml of water was added gradually to a solution of faMnFshhO (0.266 g) which quickly agitates in 35% H2SIF6 (10 ml). The resulting K2SIFF slurry was vacuum filtered, rinsed with glacial acetic acid to remove trace KF and KHF2, rinsed three times with acetone, and then dried in a vacuum desiccator.
Example 3 - Preparation of K2SIF6 containing Mn ⁴⁺ from K2SIF6 containing Mn ³⁺ [044] An oven chamber containing K2SIFF containing Mn3 + from Example 2 was evacuated and then filled with an atmosphere containing 20 % fluorine gas and 80% nitrogen gas, and heated to 500 ° C. The oven was kept at that temperature for about 8 hours, then the oven was cooled. The emission spectrum of the product was essentially identical to that of K2SiF6: Mn4 + material from Comparative Example 1.
[045] Although only certain functions of the invention have been illustrated and described in this document, many modifications and changes will occur to those skilled in the art. It must, therefore, be understood that the appended claims are intended to cover all such modifications and changes, as they are in the true spirit of the invention.
Petition 870180023957, of March 26, 2018, p. 27/34
1/3

权利要求:
Claims (13)
[1]
Claims
1. PROCESS TO PREPARE PHOSPHORUS DOPED WITH Mn ⁴⁺ , of formula I,
Ax [MFypMn * ⁴ I characterized by the process comprising combining an A ⁺ cation, an anion of formula MF _y and a source of Mn ^{n +} comprising a fluoromanganese compound in an acidic solution;
- precipitating a phosphorus precursor containing Mn ^{n +} from the acidic solution; and
- contact the phosphorus precursor that contains Mn ^{n +} with an oxidizing agent that contains fluorine in gaseous form, at an elevated temperature, to form the phosphorus doped with Mn ⁴⁺ ;
on what
- 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 the absolute value of the ion charge [MF _y ];
- y is 5, 6 or 7; and
- n is 2 or 3.
[2]
2. PROCESS according to claim 1, characterized in that it further comprises combining a fluoride or bifluoride anion or a combination thereof, with the A ⁺ cation, the anion of formula MF _y and the source of Mn ^{n +} .
[3]
PROCESS according to any one of claims 1 to 2, characterized in that the phosphorus doped with Mn ⁴⁺ is K2SiF6: Mn ⁴⁺ .
[4]
PROCESS according to any one of claims 1 to 3, characterized in that the anion of formula [MF _y ] is SiF6.
[5]
5. PROCESS, according to any of the claims
Petition 870180023957, of March 26, 2018, p. 28/34
2/3
1 to 4, characterized in that the A ⁺ cation is derived from KF, KHF2, or a combination thereof.
[6]
6. PROCESS, according to any one of claims 1 to 5, characterized in that the source of Mn ^{n +} is selected from foMnFshhO, KMnF4, K2MnF4, KMnF3, MnF2, MnF3 and combinations thereof.
[7]
7. PROCESS according to any one of claims 1 to 6, characterized in that the source of Mn ^{n +} is faMnFshhO.
[8]
PROCESS according to any one of claims 1 to 7, characterized in that the acidic solution is aqueous fluorosilicic acid.
[9]
PROCESS according to any one of claims 1 to 8, characterized in that the oxidizing agent containing fluorine is F2.
[10]
PROCESS according to any one of claims 1 to 9, characterized in that the step of contacting the phosphorus precursor containing Mn ^{n +} with the oxidizing agent containing fluoride further comprises contacting the phosphorus precursor containing Mn ^{n +} with the oxidizing agent which contains fluorine and a compound of the formula AX, where X is F, Cl, Br, I, HF2 or a combination thereof.
[11]
PROCESS according to any one of claims 1 to 10, characterized in that it comprises
- combining a solution comprising fluorosilicic acid and the source of Mn ^{n +} with a potassium fluoride compound selected from KF, KHF2 and combinations thereof;
- precipitating a phosphorus precursor containing Mn ^{n +} ; and
- exposing the phosphorus precursor containing Mn ^{n +} to an atmosphere comprising at least 20% fluorine gas, at an elevated temperature, to form the phosphorus doped with Mn ⁴⁺ ;
where the source of Mn ^{n +} comprises a compound of fluoromanganese and potassium, selected from foMnFshhO, KMnF4, MnF3
Petition 870180023957, of March 26, 2018, p. 29/34
3/3 and combinations thereof.
[12]
12. A process according to any one of claims 1 to 11, characterized in that the phosphorus is treated in particulate form with a saturated solution of a composition of formula II in aqueous hydrofluoric acid
Ax [MFy] II.
[13]
13. PROCESS according to any one of claims 1 to 12, characterized in that the phosphorus doped with Mn ⁴⁺ is selected from the group consisting of:
(A) A2 [MF5]: Mn ⁴⁺ , where M is selected from Al, Ga, In and combinations thereof;
(B) A3 [MF6]: Mn ⁴⁺ , where M is selected from Al, Ga, In and combinations thereof;
(C) Zn2 [MF7]: Mn ⁴⁺ , where M is selected from Al, Ga, In and combinations thereof;
(D) A [ln ₂ F ₇ ]: Mn ⁴⁺ ;
(E) A2 [MF6]: Mn ⁴⁺ , where M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof;
(F) E [MF6]: 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) Bao, 65Zro, 35F2.7o: Mn ⁴⁺ ; and (H) A3 [ZrF ₇ ]: Mn ⁴⁺ ; and
A is Li, Na, K, Rb, Cs or a combination thereof.
Petition 870180023957, of March 26, 2018, p. 30/34
1/3

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2021-11-23| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2022-02-08| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 7A ANUIDADE. |

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