US20190048258A1 - Coated manganese doped phosphors - Google Patents

Coated manganese doped phosphors Download PDF

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US20190048258A1
US20190048258A1 US15/674,495 US201715674495A US2019048258A1 US 20190048258 A1 US20190048258 A1 US 20190048258A1 US 201715674495 A US201715674495 A US 201715674495A US 2019048258 A1 US2019048258 A1 US 2019048258A1
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Prior art keywords
solution
formula
phosphor
particles
suspension
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US15/674,495
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Fangming Du
Clark David NELSON
Sara Anne Krosschell
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Current Lighting Solutions LLC
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General Electric Co
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Priority to US15/674,495 priority Critical patent/US20190048258A1/en
Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DU, FANGMING, KROSSCHELL, SARA ANNE, NELSON, CLARK DAVID
Priority to TW107127612A priority patent/TWI798246B/zh
Priority to KR1020207005699A priority patent/KR102386043B1/ko
Priority to MYPI2019007366A priority patent/MY190695A/en
Priority to CN201880051228.XA priority patent/CN111133077B/zh
Priority to PCT/US2018/046129 priority patent/WO2019032909A1/en
Priority to EP18845284.1A priority patent/EP3628053A4/en
Priority to JP2019570070A priority patent/JP7353986B2/ja
Priority to US16/621,499 priority patent/US11060023B2/en
Publication of US20190048258A1 publication Critical patent/US20190048258A1/en
Assigned to CURRENT LIGHTING SOLUTIONS, LLC F/K/A GE LIGHTING SOLUTIONS, LLC reassignment CURRENT LIGHTING SOLUTIONS, LLC F/K/A GE LIGHTING SOLUTIONS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GENERAL ELECTRIC COMPANY
Assigned to ALLY BANK, AS COLLATERAL AGENT reassignment ALLY BANK, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: CURRENT LIGHTING SOLUTIONS, LLC
Assigned to ALLY BANK, AS COLLATERAL AGENT reassignment ALLY BANK, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: CURRENT LIGHTING SOLUTIONS, LLC
Assigned to ALLY BANK, AS COLLATERAL AGENT reassignment ALLY BANK, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: CURRENT LIGHTING SOLUTIONS, LLC
Assigned to CURRENT LIGHTING SOLUTIONS, LLC, FORUM, INC. reassignment CURRENT LIGHTING SOLUTIONS, LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: ALLY BANK
Assigned to CURRENT LIGHTING SOLUTIONS, LLC, FORUM, INC. reassignment CURRENT LIGHTING SOLUTIONS, LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: ALLY BANK
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/611—Chalcogenides
    • C09K11/613—Chalcogenides with alkali or alkakine earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/615—Halogenides
    • C09K11/616—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/674—Halogenides
    • C09K11/675—Halogenides with alkali or alkaline earth metals

Definitions

  • Mn 4+ complex fluoride materials activate
  • One aspect of the specification presents a process for preparing a population of coated phosphor particles.
  • the process includes combining particles of a phosphor of formula I: A x [MF y ]:Mn 4+ with a first solution including a compound of formula II: A X [MF y ] to form a suspension, 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 an absolute value of a charge of the [MF y ] ion; and y is 5, 6 or 7.
  • the process further includes combining a second solution including a source A + ions with the suspension.
  • a process for preparing a population of coated phosphor particles includes combining particles of K 2 [SiF 6 ]:Mn 4+ with a first solution including K 2 [SiF 6 ] to form a suspension and combining a second solution including KF with the suspension.
  • FIG. 1 is a schematic cross-sectional view of a lighting apparatus, in accordance with one embodiment of the present disclosure.
  • FIG. 2 is a schematic view of a surface-mounted device (SMD), in accordance with one embodiment of the present disclosure.
  • SMD surface-mounted device
  • Approximating language may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about,” is not limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, or 20 to 80, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • Some embodiments provide a process for preparing a population of coated phosphor particles.
  • the process includes combining particles of a phosphor of formula I: A x [MF y ]:Mn 4+ with a first solution including a compound of formula II: A x [MF y ] to form a suspension and combining a second solution including a source of A + ions to the suspension.
  • the process may result the population of coated phosphor particles having a core including the phosphor of formula I and a coating disposed on the core.
  • the coating may include the compound of formula II.
  • Both, the phosphor of formula I and the compound of formula II, are complex fluorides.
  • Complex fluorides have a host lattice containing one coordination center surrounded by fluoride ions acting as ligands, and charge-compensated by counter ions (A) as required.
  • A counter ions
  • the coordination center is Si
  • the counter ion is K.
  • Complex fluorides are generally represented as a combination of simple, binary fluorides. The square brackets in the chemical formula for the complex fluorides (occasionally omitted for simplicity) indicate that the complex ion present in that particular complex fluoride is a new chemical species, different from the simple fluoride ion.
  • the phosphor of formula I is a manganese (Mn 4+ ) doped complex fluoride.
  • the phosphor of formula I is a phosphor that emits red light, and may also be referred to as ‘red-emitting’ phosphor, and these terms are used interchangeably throughout the specification.
  • the Mn 4+ dopant or activator acts as an additional coordination center, substituting a part of the coordination center, for example, Si, forming a luminescent center.
  • the manganese doped phosphor of formula I: A 2 [MF 6 ]:Mn 4+ may also be represented as A 2 [(M, Mn)F 6 ].
  • the host lattice (including the counter ions) may further modify the excitation and emission properties of the activator ion.
  • the counter ion A in formula I and formula II is Li, Na, K, Rb, Cs, or a combination thereof.
  • A is Na, K, or a combination thereof.
  • the coordination center M is Si, Ge, Ti, Zr, Hf, Sn, Al, Ga, In, Sc, Y, Bi, La, Gd, Nb, Ta, or a combination thereof.
  • M is Si, Ge, Ti, or a combination thereof.
  • A is K, and M is Si.
  • Suitable examples of the compound of formula II include K 2 [SiF 6 ], K 2 [TiF 6 ], K 2 [SnF 6 ], Cs 2 [TiF 6 ], Rb 2 [TiF 6 ], Cs 2 [SiF 6 ], Rb 2 [SiF 6 ], Na 2 [TiF 6 ], Na 2 [ZrF 6 ], K 3 [ZrF 7 ], K 3 [BiF 7 ], K 3 [YF 7 ], K 3 [LaF 7 ], K 3 [GdF 7 ], K 3 [NbF 7 ] and K 3 [TaF 7 ].
  • the compound of formula II is K 2 SiF 6 .
  • Suitable examples of the phosphor of formula I include K 2 [SiF 6 ]:Mn 4+ , K 2 [TiF 6 ]:Mn 4+ , K 2 [SnF 6 ]:Mn 4+ , Cs 2 [TiF 6 ]:Mn 4+ , Rb 2 [TiF 6 ]:Mn 4+ , Cs 2 [SiF 6 ]:Mn 4+ , Rb 2 [SiF 6 ]:Mn 4+ , Na 2 [TiF 6 ]:Mn 4+ , Na 2 [ZrF 6 ]:Mn 4+ , K 3 [ZrF 7 ]:Mn 4+ , K 3 [BiF 7 ]:Mn 4+ , K 3 [YF 7 ]:Mn 4+ , K a [LaF 7 ]:Mn 4+ , K 3 [GdF 7 ]:Mn 4+ , K 3 [NbF 7 ]:Mn 4+ or
  • the amount of manganese in the phosphor of formula I may range from about 0.1 weight percent (wt %) to about 4 wt %, (from about 1.2 mole percent (mol %) to about 16.5 mol %), based on a total weight of the phosphor of formula I. In some embodiments, the amount of manganese ranges from about 0.3 wt % to about 3.3 wt % (from about 2 mol % to about 13.4 mol %), and in certain embodiments, from about 0.65 wt % to about 3.0 wt % (from about 2.6 mol % to about 12.2 mol %).
  • the amount of manganese ranges from about 0.5 wt % to about 2.76 wt % (about 3 mol % to about 11.2 mol %). In some embodiments, the amount of manganese ranges from about 0.9 wt % to about 2.5 wt % (from about 3.5 mol % to about 10 mol %), and in certain embodiments, from about 0.9 wt % to about 1.4 wt % (about 3.5 mol % to about 5.5 mol %).
  • the particles of the phosphor of formula I are treated to enhance performance and stability (quantum efficiency, thermal stability, humidity stability, flux stability, and color stability) prior to the step of combining the phosphor of formula I with the first solution.
  • the particles of the phosphor of formula I are contacted with a fluorine-containing oxidizing agent in gaseous form at an elevated temperature. The treatment process is described in U.S. Pat. No. 8,906,724.
  • the first solution includes a solution of the compound of formula II in aqueous hydrofluoric acid.
  • the process includes forming the first solution by dissolving the compound of formula II in aqueous hydrofluoric acid.
  • the first solution is a saturated solution of the compound of formula II in aqueous hydrofluoric acid.
  • the first solution is a nearly-saturated solution of the compound of formula II in aqueous hydrofluoric acid.
  • a nearly-saturated solution is one that contains 1-10% solvent in excess of the amount required to make a saturated solution.
  • a nearly-saturated solution is composed of K 2 SiF 6 dissolved in aqueous HF.
  • a saturated solution is prepared by adding K 2 SiF 6 to the aqueous HF to form a suspension and filtering to remove excess solids. Then approximately 1-5 vol % aqueous HF is added to the saturated solution, to form a nearly saturated solution.
  • the second solution includes a solution of the source of A ions in aqueous hydrofluoric acid.
  • the source of A + ions may include an organic or inorganic compound.
  • the source of A + ions may be a compound selected from a halide, sulphate, phosphate, acetate, and combinations thereof.
  • the source of A + ions includes KF, KHF 2 , KCl, KBr, KI, K 2 SO 4 , K 3 PO 4 , CH 3 COOK, or a combination thereof.
  • the process includes forming the second solution by dissolving an amount of the source of A + ions in aqueous hydrofluoric acid.
  • the second solution includes KF.
  • a concentration of aqueous hydrofluoric acid used in the first solution, the second solution or both the first solution and the second solution may range from about 20 weight percent (wt %) to about 70 wt %.
  • the first solution, the second solution or both include aqueous hydrofluoric acid having a concentration in a range from about 30 wt % to about 60 wt %.
  • a small quantity of other acids may be included in the first, second or both solutions if desired, such as hexafluorosilicic acid.
  • the amounts of the constituents i.e., the compound of formula II and the source of A + ions in the corresponding first and second solutions may be suitable for carrying out the desirable chemical reaction, and thereby forming a desirable coating on the particles of the phosphor of formula I.
  • a molar ratio of the source of A + ions in the second solution to the compound of formula II in the first solution is in a range from about 1:1 to about 1:20.
  • the molar ratio of the source of A + ions in the second solution to the compound of formula II in the first solution is in a range from about 1:2 to about 1:10.
  • the step of combining the second solution with the suspension may be carried out with a suitable rate for a desirable result.
  • the combining step is carried out by combining the second solution with the suspension with a rate of less than 100 milliliters/minute.
  • the rate of combining the second solution with the suspension is in a range from about 0.1 milliliter/minute to about 10 milliliters/minute.
  • the process may include disposing the precipitate on the surfaces of the particles of the phosphor of formula I, and thereby forming a coating on the particles.
  • the coating includes the compound of formula II.
  • the coating is free of manganese. As used herein, the term “free of manganese” means that the manganese concentration on the surfaces of the particles is less than 0.1 wt %.
  • the combining step may be carried out at an elevated temperature, for example up to about 100 degrees Celsius. In certain embodiments, the combining step is carried out at room temperature ( ⁇ 25 degrees Celsius).
  • the suspension is subjected to an agitated motion.
  • the agitated motion refers to stirring of the suspension.
  • the process includes continuously subjecting the suspension to the agitated motion for the entire step of combining the second solution with the suspension. The agitated motion may enable to dispose the formed precipitate on substantially all the particles of the phosphor of formula I to form a coating, and thereby form the population of coated particles.
  • the process may further include filtering the suspension after completing the step of combining the second solution with the suspension to obtain the product particles.
  • the process may further include washing the product particles followed by drying to obtain the population of coated phosphor particles.
  • the population of coated phosphor particles is obtained in powder form.
  • the thickness of the coating may depend on various process parameters, for example, one or more of the amounts of the constituents of the first solution and the second solution and the rate of combining the second solution with the suspension, and may be controlled by tailoring these parameters.
  • the population of coated phosphor particles may have a particle size distribution having a D50 particle size in a range from about 0.1 micron to about 80 microns. In some embodiments, the coated phosphor particles have a particle size distribution having a D50 particle size in a range from about 1 micron to about 50 microns. In some embodiments, a D50 particle size of the coated phosphor particles is sub-micron size.
  • a process for preparing a population of coated phosphor particles includes combining particles of K 2 SiF 6 :Mn 4+ with a first solution including K 2 SiF 6 to form a suspension and combining a second solution including KF with the suspension.
  • the first solution may include a nearly-saturated solution of K 2 SiF 6 in aqueous hydrofluoric acid.
  • the second solution may include solution of KF in aqueous hydrofluoric acid.
  • the coating may protect the particles of phosphor of formula I from degradation.
  • the coated phosphor particles have a stability higher than that of the particles of the phosphor of formula I (i.e., uncoated particles).
  • Stability of phosphor particles may refer to stability of the phosphor particles in a high temperature and high humidity environment.
  • stability of a phosphor material may be analyzed by measuring a change in quantum efficiency of the phosphor material after exposing the phosphor material to the high temperature and high humidity environment.
  • the term “high temperature and high humidity environment (HTHH)” refers to an environment having at least 50 percent relative humidity (with respect to an environment having no humidity) and at least 50 degrees' Celsius temperature.
  • the HTHH environment has at least 60 percent relative humidity and 60 degrees' Celsius temperature. In some embodiments, the HTHH environment has at least 80 percent relative humidity and 80 degrees' Celsius temperature. In some embodiments, the HTHH environment has about 90 percent relative humidity and 60 degrees' Celsius temperature. In some embodiments, a change in quantum efficiencies after exposing the coated phosphor particles is lower than that of a change in quantum efficiencies of the particles (uncoated) of the phosphor.
  • the coated phosphor particles may have a stability higher than the stability of particles of the phosphor of formula I in the high temperature and high humidity environment.
  • FIG. 1 illustrates a lighting apparatus or lamp 10 , in accordance with some embodiments.
  • the lighting apparatus 10 includes a light emitting diode (LED) chip 12 , and leads 14 electrically attached to the LED chip 12 .
  • the leads 14 may comprise thin wires supported by a thicker lead frame(s) 16 or the leads 14 may comprise self supported electrodes and the lead frame may be omitted.
  • the leads 14 provide current to LED chip 12 and thus cause it to emit radiation.
  • the LED chip 12 may be a blue emitting LED chip having a peak emission wavelength from about 400 nanometers to about 500 nanometers.
  • a phosphor composition 20 including a population of coated phosphor particles (prepared by the process described herein above in some embodiments) is disposed on a surface 11 of the LED chip 12 , and is radiationally coupled to the LED chip 12 .
  • the phosphor composition 20 can be deposited on the surface 11 of the LED chip 12 by any appropriate method, for example using a slurry prepared mixing silicone and the population of the coated phosphor particles.
  • the light emitted by the LED chip 12 mixes with the light emitted by the population of coated phosphor particles to produce desired emission (indicated by arrow 15 ).
  • the LED chip may be replaced by an organic light emissive structure or other radiation source, unless otherwise noted, and that any reference to an LED chip or semiconductor is merely representative of any appropriate radiation source.
  • the LED chip 12 may be encapsulated within an envelope 18 , which encloses the LED chip 12 and an encapsulant material (not shown in FIG. 1 ) disposed in a portion 19 of the lighting apparatus 10 .
  • the envelope 18 may be formed of, for example, glass or plastic.
  • the LED chip 12 may be enclosed by the encapsulant material.
  • the encapsulant material may be a low temperature glass, or a polymer or resin known in the art, for example, an epoxy, silicone, epoxy-silicone, acrylate or a combination thereof.
  • the lighting apparatus 10 may only include the encapsulant material without the envelope 18 .
  • a population of the coated phosphor particles may be interspersed within the encapsulant material, instead of being disposed on the LED chip 12 (referring to FIG. 1 ).
  • the phosphor composition that includes the coated phosphor particles may be coated onto a surface of the envelope 18 , instead of being disposed on the LED chip 12 .
  • the lighting apparatus 10 may include a plurality of LED chips (not shown in figures). These various configurations may be combined, with the phosphor composition located in any two or more locations or in any other suitable location, such as separately from the envelop 18 or integrated into the LED chip 12 .
  • one or more additional luminescent materials such as phosphors or mixtures of phosphors or other materials, may be used in the phosphor composition or different parts of the lighting apparatus 10 , for example disposed on or below or in the phosphor composition 20 ( FIG. 1 ) or any other location in the lighting apparatus 10 .
  • the lighting apparatus 10 may also include a plurality of particles (not shown) to scatter or diffuse the emitted light. These scattering particles would generally be embedded in the encapsulant material.
  • the scattering particles may include, for example, particles made from Al 2 O 3 (alumina) or TiO 2 (titania). The scattering particles may effectively scatter the light emitted from the LED chip 12 , preferably with a negligible amount of absorption.
  • Some embodiments include a backlight apparatus that includes a surface mounted device (SMD) type light emitting diode 50 , e.g. as illustrated in FIG. 2 .
  • SMD surface mounted device
  • This SMD is a “side-emitting type” and has a light-emitting window 52 on a protruding portion of a light guiding member 54 .
  • An SMD package may comprise an LED chip as defined above, and a phosphor composition including a population of coated phosphor particles as described above.
  • lighting apparatus can be provided producing red light or white light having high luminosity, and high CRI values for a low range of color temperatures of interest (2500 K to 4000 K) for general illumination.
  • Additional luminescent materials capable of emitting green, blue, yellow, red, orange, or other color radiation may be used in the phosphor composition (for example, a blend) or the lighting apparatus to customize the white color of the resulting light and produce specific spectral power distributions.
  • the additional luminescent material emits green radiation.
  • Suitable additional phosphors for use in the phosphor composition include, but are not limited to:
  • the phosphor composition includes a blend of compound of formula I with a narrow blue-green phosphor with peak wavelength ranging from (475-510 nm, FWHM 30 nm or below) and a yellow-orange phosphor with peak wavelength (550-615 nm). This blend can yield a combination of high lumen equivalent and CRI greater than 95 and R9 greater than 95.
  • the phosphor blend includes K 2 SiF 6 :Mn 4+ (PFS), along with (Y,Gd,Tb,La,Sm,Pr,Lu) 3 (Al,Ga) 5 ⁇ a O 12 ⁇ 3/2a :Ce 3+ (wherein 0 ⁇ a ⁇ 0.5), particularly Y 3 Al 5 O 12 :Ce 3+ (YAG), and Li 2 CaSiO 4 :Eu 2+ .
  • Spectral weight of each of the phosphors in the blend ranges from about 0.01 to 0.7.
  • the blend calculations and corresponding luminosity, CRI and R9 values for three different CCT values of 3000K, 3500K and 4000K are shown in Table 1.
  • phosphor composition examples include electroluminescent polymers such as polyfluorenes, preferably poly(9,9-dioctyl fluorene) and copolymers thereof, such as poly(9,9′-dioctylfluorene-co-bis-N,N′-(4-butylphenyl)diphenylamine) (F8-TFB); poly(vinylcarbazole) and polyphenylenevinylene and their derivatives.
  • the phosphor composition may include a blue, yellow, orange, green or red phosphorescent dye or metal complex, or combinations thereof.
  • phosphorescent dye 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)pyridinato-N,C2) (blue dye).
  • fluorescent and phosphorescent metal complexes from ADS (American Dyes Source, Inc.) may 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.
  • the additional luminescent material includes a green light emitting quantum dot (QD) material.
  • the green light emitting QD material may include a group II-VI compound, a group III-V compound, a group IV-IV compound, a group IV compound, a group I-III-VI 2 compound, or a mixture thereof.
  • group II-VI compounds include CdSe, CdTe, CdS, ZnSe, ZnTe, ZnS, HgTe, HgS, HgSe, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS.
  • CdZnSe, CdZnTe CdHgS, CdHgSe, CdHgTe, HgZnS. HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, or combinations thereof.
  • Group III-V compounds may be selected from the group consisting of GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs, and combinations thereof.
  • group IV compounds include Si, Ge, SiC, and SiGe.
  • group I-III-VI 2 chalcopyrite-type compounds include CuInS 2 , CuInSe 2 , CuGaS 2 , CuGaSe 2 , AgInS 2 , AgInSe 2 , AgGaS 2 , AgGaSe 2 and combinations thereof.
  • QD materials for use as the additional luminescent material may be a core/shell QD, including a core, at least one shell coated on the core, and an outer coating including one or more ligands, preferably organic polymeric ligands.
  • Exemplary materials for preparing core-shell QDs include, but are not limited to, Si, Ge, Sn, Se, Te, B, C (including diamond).
  • Exemplary core-shell QDs include, but are not limited to, CdSe/ZnS, CdSe/CdS, CdSe/CdS/ZnS, CdSeZn/CdS/ZnS, CdSeZn/ZnS, InP/ZnS, PbSe/PbS, PbSe/PbS, CdTe/CdS, and CdTe/ZnS.
  • the QD materials typically include ligands conjugated to, cooperated with, associated with, or attached to their surface.
  • the QDs may include a coating layer comprising ligands to protect the QDs from environmental conditions including elevated temperatures, high intensity light, external gasses, and moisture, control aggregation, and allow for dispersion of the QDs in the host binder material.
  • the ratio of each of the individual luminescent material, for example coated phosphor particles and the additional luminescent materials may vary depending on the characteristics of the desired light output.
  • the relative proportions of individual luminescent materials in a lighting apparatus may be adjusted such that when their emissions are blended and employed in the lighting apparatus, there is produced visible light of predetermined x and y values on the CIE chromaticity diagram created by the International Commission on Illumination (CIE).
  • CIE International Commission on Illumination
  • the lighting apparatus emits white light.
  • the exact identity and amount of each luminescent material for use in a lighting apparatus can be varied according to the needs of the end user.
  • the lighting apparatus and/or backlight apparatus may be used for general illumination and display applications. Examples include chromatic lamps, plasma screens, xenon excitation lamps, UV excitation marking systems, automotive headlamps, home and theatre projectors, laser pumped devices, point sensors, liquid crystal display backlight units, televisions, computer monitors, smartphones, tablet computers and other handheld devices that have a display including a semiconductor light source as described herein.
  • the list of these applications is meant to be merely exemplary and not exhaustive.
  • a saturated solution composed of K 2 SiF e dissolved in 49% HF was prepared by adding 4.2 g K 2 SiF 6 per 100 ml 49% HF to form a suspension which was vacuum filtered to remove excess solids. Approximately 2 vol % 49% HF was added to the saturated solution, to form a nearly saturated solution.
  • the saturated solution (160 ml) was added to K 2 SiF 6 :Mn 4+ phosphor powder (40 g) in a Nelgen bottle, and the resulting suspension was stirred for about 10 minutes.
  • the yellow supernatant solution was decanted and the saturated solution (160 ml) was added to the Nelgen bottle and stirred for about 10 mins. This process of decanting and adding the saturation solution was repeated one more time.
  • the product was vacuum filtered, rinsed with acetone, and then dried under vacuum.
  • the saturated solution (160 ml) was added to K 2 SiF 6 :Mn 4+ phosphor powder (40 g) in a Nelgen bottle, and the resulting suspension was stirred for about 10 minutes.
  • the yellow supernatant solution was decanted and the saturated solution (160 ml) was added to the Nelgen bottle and stirred for about 10 mins. This process of decanting and adding the saturation solution was repeated one more time.
  • a saturated solution of KF in 49% HF was added to the suspension at a rate of 1.5 ml/min followed by stirring for about 10 mins. The supernatant was almost colorless.
  • the product was vacuum filtered, rinsed with acetone, and then dried under vacuum.
  • Example 1-4 and Comparative Examples 1-4 were dispersed into silicone (Sylguard 184) to form corresponding slurries, and these slurries were used to make the corresponding tapes.
  • silicone Sylguard 184.
  • Each slurry was prepared by mixing 0.5 g of each sample (prepared in Examples 1-4 and Comparative Examples 1-4) with 1.5 g of Sylguard 184. These slurries were tape cast followed by curing at 90 degrees Celsius for 35 min to obtain self-standing tapes.
  • the tapes were measured for quantum efficiency (QE) at excitation wavelength 450 nm by using a quantum efficiency measuring system. These tapes were then placed into a high temperature and high humidity (HTHH) chamber (80 degrees Celsius, 85% relative humidity). After exposure to HTHH environment for a duration of 48 hours, QEs of the tapes were again measured at excitation wavelength 450 nm. Table 2 shows percentage change in QEs (or drop in QE) of tapes prepared using samples of Examples 1-4 and Comparative Examples 1-4 on exposure to HTHH environment for 48 hours
  • Table 2 shows that the changes in QEs of the samples of Examples 1-4 were comparatively lower ( ⁇ half) than the changes in QEs of the samples of Comparative Examples 1-4 (having uncoated phosphor particles) after HTHH exposure for 48 hours. These results showed that the coated phosphor particles (samples of Examples 1-4) had comparatively higher stability in the HTHH environment than that of the uncoated phosphor particles of Comparative Examples 1-4.

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TW107127612A TWI798246B (zh) 2017-08-10 2018-08-08 經塗覆之摻雜錳的磷光體
US16/621,499 US11060023B2 (en) 2017-08-10 2018-08-09 Coated manganese doped phosphors
EP18845284.1A EP3628053A4 (en) 2017-08-10 2018-08-09 LUMINOPHORES DOPED WITH COATED MANGANESE
MYPI2019007366A MY190695A (en) 2017-08-10 2018-08-09 Coated manganese doped phosphors
CN201880051228.XA CN111133077B (zh) 2017-08-10 2018-08-09 涂覆的锰掺杂磷光体
PCT/US2018/046129 WO2019032909A1 (en) 2017-08-10 2018-08-09 MANGANESE DOPED LUMINOPHORES COATED
KR1020207005699A KR102386043B1 (ko) 2017-08-10 2018-08-09 코팅된 망간이 도핑된 인광체
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