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WO2008065567A1 - Systeme d'eclairage comprenant un hétéropolyoxométalate - Google Patents

Systeme d'eclairage comprenant un hétéropolyoxométalate Download PDF

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Publication number
WO2008065567A1
WO2008065567A1 PCT/IB2007/054631 IB2007054631W WO2008065567A1 WO 2008065567 A1 WO2008065567 A1 WO 2008065567A1 IB 2007054631 W IB2007054631 W IB 2007054631W WO 2008065567 A1 WO2008065567 A1 WO 2008065567A1
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Prior art keywords
phosphor
light
group
radiation
emitting
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PCT/IB2007/054631
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English (en)
Inventor
Thomas JÜSTEL
Hans-Helmut Bechtel
Joachim Opitz
Henning Ohland
Detlef Uwe Wiechert
Dominik Uhlich
Helga Bettentrup
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Philips Intellectual Property & Standards Gmbh
Koninklijke Philips Electronics N.V.
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Publication of WO2008065567A1 publication Critical patent/WO2008065567A1/fr

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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
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7737—Phosphates
    • C09K11/7738—Phosphates with alkaline earth metals
    • C09K11/7739—Phosphates with alkaline earth metals with halogens
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7768—Chalcogenides with 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • 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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909—Post-treatment of the connector or wire bonding area
    • H01L2224/8592—Applying permanent coating, e.g. protective coating

Definitions

  • the present invention generally relates to an illumination system comprising a radiation source and a luminescent material comprising a phosphor.
  • the invention also relates to a luminescent material for use in such illumination system.
  • the invention relates to an illumination system and a luminescent material for the generation of specific colored light, including white light, by luminescent down conversion and additive color mixing based a radiation source emitting in the near UV or blue range of the electromagnetic spectrum.
  • a light- emitting diode as a radiation source is especially contemplated.
  • illumination systems comprising visible colored red, green and blue light emitting diodes as radiation sources are used single or in clusters for all kind of applications where rugged, compact, lightweight, high efficiency, long- life, low voltage sources of white or colored illumination are needed.
  • Such applications comprise inter alia illumination of small LCD displays in consumer products such as cellular phones, digital cameras and hand held computers.
  • Pertinent uses include also status indicators on such products as computer monitors, stereo receivers, CD players, VCRs, and the like.
  • Indicators are also used in instrument panels in aircraft, trains, ships, cars, etc. Multi-color combinations of pluralities of visible colored light emitting LEDs in addressable arrays containing hundreds or thousands of LED components are found in large area displays such as full color video walls and also as high brightness large-area outdoor television screens.
  • arrays of amber, red, and blue-green emitting LEDs are increasingly used as traffic lights or in effect lighting of buildings.
  • LEDs are however typically subject to low yield and are considered difficult to fabricate with uniform emission characteristics from batch to batch.
  • the LEDs can exhibit large wavelength variations across the wafer within a single batch, and in operation can exhibit strong wavelength and emission variations with operation conditions such as drive current and temperature. Therefore, when generating white light with an arrangement comprising visible colored light emitting diodes, there has been such a problem that white light of the desired tone cannot be generated due to variations in the tone, luminance and other factors of the visible colored light emitting diodes.
  • Another known way to provide white or colored light illumination is used in illumination systems wherein the color of light emitting diodes emitting in the UV to blue range of the electromagnetic spectrum is converted by means of a luminescent material comprising a phosphor.
  • Phosphor-converted "white" LED systems have been based in particular on the dichromatic (BY) approach, mixing yellow and blue colors, in which case the yellow secondary component of the output light may be provided by a yellow phosphor and the blue component may be provided by a phosphor or by the primary emission of a blue LED.
  • white illumination systems have been based on the trichromatic (RGB) approach, i.e. on mixing three colors, namely red, green and blue, in which case the red and green component may be provided by a phosphor and the blue component by the primary emission of a blue-emitting LED.
  • phosphors comprising europium(III) as activators in any kind of host lattice are already known to satisfy the criteria of absorption in the near UV of the electromagnetic spectrum.
  • Example given, US2006/0028117 Al discloses a red phosphor which includes a compound represented by (Li ( 2-z)- ⁇ M x )(A ⁇ 4) y :Eu z , Sniq and a flux wherein M is K, M Na, Ca, Sr, or Ba, A is Mo or W, 0 ⁇ x ⁇ 2, 0.5 ⁇ y ⁇ 5, 0.01 ⁇ z ⁇ 1.5, and 0.001 ⁇ q ⁇ -1.0, which is excellent in emission efficiency by a long wavelength UV excitation source and has a fine and uniform particle size.
  • the present invention provides an illumination system comprising a radiation source and a luminescent material comprising at least one first phosphor capable of absorbing a part of the radiation emitted by the radiation source and emitting radiation of a wavelength different from that of the absorbed radiation, wherein said at least one phosphor is an europium(III)-activated hetero-polyoxometallate of general formula A a RE b M m ⁇ 3m+3/2b+a-i/2 ⁇ F x , wherein A is as least one alkaline metal selected from the group of lithium, sodium, potassium, rubidium and cesium, RE is at least one rare earth metal selected from the group of yttrium, lanthanum and gadolinium, M is a metal selected from the group of molybdenum and tungsten or a combination thereof and wherein O ⁇ a ⁇ 1, 1 ⁇ b ⁇ 3, 2 ⁇ m ⁇ 6 and 0 ⁇ x ⁇ 2.
  • Such an illumination system provides an efficient and longliving way of illumination.
  • the efficiency of an illumination system using a source of primary radiation and a phosphor, which converts primary radiation into secondary radiation, is especially dependent on the efficiency of the radiation conversion process.
  • a radiation conversion process in general may be characterized by a number of parameters, including extinction coefficient, excitation, and emission spectrum, Stokes' shift, quantum efficiency and lumen efficiency.
  • An extinction coefficient is a wavelength-dependent measure of the absorbing power of a phosphor.
  • An excitation spectrum is the dependence of emission intensity on the excitation wavelength, measured at a single constant emission wavelength.
  • An emission spectrum is the wavelength distribution of the emission, measured after excitation with a single constant excitation wavelength.
  • Stokes shift is generally defined as the displacement of spectral lines or bands of luminescent radiation to a longer emission wavelength than the excitation lines or bands.
  • Quantum efficiency QE is the ratio of the number of photons emitted to the number of photons absorbed by a phosphor.
  • the illumination system according to the invention exhibits luminescence with a quantum efficiency that is improved in comparison to the prior art systems.
  • This increase in efficiency is due to the fact that the phosphors according to the invention have excitation bands in the bluish-green and blue range of the electromagnetic spectrum, extending into the UVA and UVB range. Due to excitation spectrum in the blue and bluish-green range, the phosphors described in the invention have a very small Stokes shift, if the wavelength of exciting radiation source is matched to the phosphor excitation wavelength.
  • the quantum loss caused by the conversion of a primary photon emitted by the radiation source into a secondary yellow to red photon can thus be minimized. As a consequence less of the energy delivered to the lamp is wasted as heat and the luminous efficiency is increased.
  • radiation sources their excitation spectrum permits the phosphors to be efficiently excited by any wavelength-limited light sources, such as common lasers and arc lamps as well as inorganic or organic light emitting diodes.
  • a radiation source for the present invention is a light-emitting diode.
  • the emission produced by a light-emitting diode typically has excellent monochromaticity, because of its narrow spectral half- width of its emission spectrum.
  • the radiation source is a light emitting diode, having a peak emission wavelength in the range of 370 to 480 nm as a radiation source.
  • Such an illumination system will provide white light in operation.
  • the blue light emitted by the LED excites the phosphor, causing it to emit yellow, amber or red light.
  • the blue light emitted by the LED is transmitted through the phosphor and is mixed with the yellow to amber or red light emitted by the phosphor. The viewer perceives the mixture of blue and amber or red light as white light.
  • the luminescent material may comprise also at least one second phosphor.
  • the luminescent material comprises a phosphor blend of a phosphor according to the invention and at least one second phosphor a high quality white light illumination system with good color rendering at the required color temperature will be obtained.
  • the second phosphor is a green to yellow-emitting phosphor.
  • green to yellow-emitting phosphor are phosphors selected from the group comprising (Bai_ x Sr x )2Si ⁇ 4:Eu, wherein 0 ⁇ x ⁇ 1, SrGa2S4:Eu, SrSi2N2 ⁇ 2:Eu, RE 3 Al 5 O ⁇ Ce, wherein RE comprises yttrium, and all lanthanoide metals.
  • the second phosphor is a blue to green-emitting phosphor.
  • phosphors selected from the group comprising BaMgAIi 0 On Eu, Ba 5 SiO 4 (Cl 5 Br) 6 :Eu, CaLn 2 S 4 Ce, wherein Ln comprises lanthanum and the lanthanoide metals, and (Sr,Ba,Ca) 5 (P ⁇ 4)3Cl:Eu.
  • the second phosphor is a red-emitting phosphor.
  • phosphors selected from the group of Eu(II)-activated phosphors, comprising (Cai_ x Sr x )S:Eu, wherein 0 ⁇ x ⁇ 1 and (Sri_ x _ y Ba x Ca y ) 2 - z Si 5 - a Al a N 8 - a O a :Eu z wherein 0 ⁇ a ⁇ 5, 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l and 0 ⁇ z ⁇ l.
  • a luminescent material comprising at least one first phosphor capable of absorbing a part of the light emitted by the radiation source and emitting light of a wavelength different from that of the absorbed light, wherein said at least one phosphor is an europium(III)-activated hetero- polyoxometallate of general formula A a REb-zM m ⁇ 3 m +3/2b+a-i/2 ⁇ F x :Eu z , wherein A is as least one alkaline metal selected from the group of lithium, sodium, potassium, rubidium and cesium, RE is at least one rare earth metal selected from the group of yttrium, lanthanum and gadolinium, M is a metal selected from the group of molybdenum and tungsten or a combination thereof and wherein O ⁇ a ⁇ l, l ⁇ b ⁇ 3, 2 ⁇ m ⁇ 6, 0 ⁇ x ⁇ 2 and 0.002 ⁇ z ⁇ 0.8
  • the new luminescent material matches every single ideal requirement for use in illumination systems, i.e.
  • the key feature of the phosphor according to the invention is its hetero- polyoxometallate host lattice.
  • the stable crystal structure of the host lattice is free of non-stoichiometric defects, and is therefore stable with regard to external influence such as heat and ultraviolet to blue radiation.
  • the phosphors according to the invention are highly resistant to photo-bleaching and photo-degradation. Resistance to thermally enhanced photodegradation is of importance, as light-emitting diodes under operation can become very hot and any material surrounding the LED will also become hot. The heat can damage a conventional phosphor in the surrounding of a LED, degrading its ability to down-convert the LED's light.
  • the phosphors according to the invention are heat resistant and suited for applications up to 500 0 C.
  • hetero-polyoxometallate phosphors part of the rare earth metal selected from the group of yttrium, lanthanum and gadolinium may be replaced by indium or bismuth, otherwise part of the metal selected from the group of molybdenum and tungsten or a combination thereof may be replaced by phosphor, vanadium or niobium.
  • the luminescent material according to the invention comprises at least one phosphor capable of absorbing a part of light emitted by a radiation source and emitting light of wavelength different from that of the absorbed light; wherein said at least one phosphor is an europium(III)-activated hetero-polyoxometallate of general formula A a REb-zM m ⁇ 3m+3/2b+a-i/2 ⁇ F x :Eu z , wherein A is as least one alkaline metal selected from the group of lithium, sodium, potassium, rubidium and cesium, RE is at least one rare earth metal selected from the group of yttrium, lanthanum and gadolinium, M is a metal selected from the group of molybdenum and tungsten or a combination thereof and wherein 0 ⁇ a ⁇ 1, 1 ⁇ b ⁇ 3, 2 ⁇ m ⁇ 6, 0 ⁇ x ⁇ 2 and 0.002 ⁇ z ⁇ 0.8.
  • This class of phosphors is based on europium(III)-activated luminescence of a hetero-oxypolymetallate structure.
  • the molecular structures of hetero- polyoxometallates are derivable from the basic iso-polyoxometallate structure types, wherein part of the central metal atom is substituted by a hetero metal.
  • polyoxometallates are inorganic metal-oxygen clusters comprising defined oligomeric or polymeric structural units. Iso-polyoxometallates can be described as binary oxide anions [M m Oy] p ⁇ .
  • Hetero-polyoxometallates having the formula [X* x M m O y ] p ⁇ contain one or more heteroatoms.
  • heteroatoms can in general be nonmetals, semimetals or metals.
  • Formal replacement of MO y structural units by heteroatoms makes it possible to introduce rare earth metal ions into the solid-state host lattice of an iso- po lyoxometallate .
  • Hetero-polyoxometallates have a crystal structure typically containing one or more central "heteroatoms" surrounded by a framework of metal atoms bonded to oxygen atoms.
  • a suitable heteroatom typically is tetrahedrally bonded to the framework metal atoms ("M”) through oxygen atoms ("O").
  • the framework metals typically are bonded to a central X atom octahedrally through oxygen atoms and are bonded further to other framework M metals through oxygen atoms.
  • the M metal also may have a non-bridging "terminal" oxygen atom. Based on the oxidation state of the heteroatoms and M metal atoms, a heteropolyacid cage host lattice will bear a negative charge (a "polyoxoanion”) that is balanced with a charge-balancing number of suitable alkali metal cations.
  • Framework M metals are selected from the transition metals molybdenum and tungsten and combinations thereof.
  • a mixture of M metals may be used, although a major portion of W atoms is preferred.
  • Part of the metal selected from the group of molybdenum and tungsten or a combination thereof may be replaced by phosphor, vanadium or niobium.
  • the heteroatoms, X, used in polyoxometallates according to the invention are rare earth metals selected from the group of yttrium, lanthanum and gadolinium.
  • Lanthanum is the preferable X heteroatom used in this invention, either alone or in combination with yttrium and gadolinium.
  • Part of the rare earth metal selected from the group of yttrium, lanthanum and gadolinium may be replaced by indium or bismuth.
  • lithium polyoxometallates demonstrate a substantial increase in intensity over polyoxometallates containing other cation species, see Fig. 9.
  • Replacing molybdate by tungstate in polyoxometallates can also provide a substantial increase in excitation in the blue range of the spectrum, see Fig. 5, for specific embodiment La 2 Mo m -nWnOi 2 :Eu.
  • dopant ion europium is used either alone or in combination with samarium as co-activators.
  • the proportion z of the dopant ions alone or in combination with a co-activator is preferably in a range of 0.002 ⁇ z ⁇ 0.8.
  • luminance decreases because the number of excited emission centres of photoluminescence decreases and, when z is greater than 0.8, density quenching occurs.
  • Density quenching refers to the decrease in emission intensity that occurs when the concentration of an activation agent added to increase the luminance of the luminescent material is increased beyond an optimum level.
  • one or more MO units of the hetero polyoxoanion, [M m O y ] p were substituted by a number of rare earth cations to yield a series OfAXM 2 OgIEu and X 2 M 3 Oi 2 :Eu, the luminescent properties of which were investigated by excitation, emission and reflection spectroscopy.
  • Red-emitting phosphors according to the invention with especially favorable characteristics are phosphors of composition LiLaW 2 Og: 50%Eu, La 2 W3 ⁇ i 2 :40%Eu, La 2 Mo 3 Oi 2 :40%Eu und La 2 MOi 5W 1 5 Oi 2 :5%Eu, La 2 Mo 0 3W 2 7 Oi 2 :50%Eu..
  • Phosphors of this composition have a quantum efficiency of 80 to 95% at 465 nm excitation. Due to the introduction of heteroatoms into the crystal structure, europium (I ⁇ I)-activated hetero-polyoxometallates have a different charge distribution and polarity than the corresponding non-substituted isopolyoxometallate.
  • the type and amount of the heteroatom species present in the phosphor compound dictate the local bonding environments of europium(II) in the oxygen-dominant host lattice and determine the characteristics of its excitation and emission spectra.
  • europium(III)-activated hetero-polyoxometallate phosphors are especially responsive to broad energetic portions of the electromagnetic spectrum within the UV- and visible blue portion of the electromagnetic spectrum.
  • An essential factor is, that the excitation wavelength of the luminescent material is positioned in the range of long-wavelength UVA (370 to 400 nm) and especially in the blue visible light (450 to 480 nm) range, see Fig. 2 to 6. Therefore these phosphors are sufficiently excited by all blue to violet light emitting diodes in the market.
  • the excitation spectrum of the phosphors in the blue/violet range is centered on 455 to 465 nm, blue- LEDs emitting in that wavelength range are preferably combined with the phosphors according to the invention.
  • the strong absorption of UV-A radiation and/or blue light is attributed to the enhancement of the weak 4f-4f absorption lines of Eu(III) at around 370 to 410 nm ( 7 F 6 - 5 D 3 ) and 450 to 480 nm ( 7 F 6 - 5 D 2 ).
  • This is achieved by using host lattices comprising tungstate or molybdate moieties comprising lanthanum alone or in combination with yttrium and gadolinium.
  • the forbidden character of the 4f-4f transitions of Eu(III) is relaxed to a certain extent, which results in an enhanced absorption strength of these transitions.
  • the reflection spectrum OfLa 2 Mo 24 W 0 6 Oi 2 :Eu shows in an exemplary way, that the absorption of the 4f-4f transitions at 395, 465 and 530 nm has been enhanced.
  • Each phosphor of the europium(III)-activated hetero-polyoxometallate type emits a narrow-banded amber, or red fluorescence, when excited by radiation of the UVA or blue range of the electromagnetic spectrum.
  • FIG. 2 of the drawings accompanying this specification the emission (and excitation) spectra of a typical phosphor according to the invention is given.
  • the phosphors according to the invention have an emission spectrum with a peak wavelength typically at 610 to 620 nm.
  • the luminescent material has ideal characteristics for converting primary UVA/ blue radiation of nitride semiconductor light emitting diodes into white or colored yellow, amber and red light.
  • Table 1 lists up emission maxima of exemplary phosphors comprising the hetero-polyoxometallate compositions according to the invention:
  • Hetero-polyoxometallates are prepared by techniques known to the art. In a typical procedure, hetero-polyoxometallates are prepared by a method starting from suitable amounts of molybdate and tungstate at low pH (typically ⁇ 1). Regulation of the pH may determine the host lattice of the polyoxoanions.
  • a source for a M metal such as a molybdate and/or tungstate
  • a source for the hetero-element such as a soluble phosphate
  • a soluble alkaline metal compound is added to the resulting product, which forms a precipitate of the hetero-polyoxometallate. The precipitate is filtered, dried and fired.
  • X-ray diffraction data of LiLaW 2 O 8 :Eu as shown in Fig. 10 are consistent with the structure OfNaLaW 2 O 8 with certain small deviations of position and intensity due to the substitution of lithium for sodium and lanthanum and europium for tungsten
  • X-ray diffraction data of La 2 W 3 ⁇ i 2 :Eu as shown in Fig. 11 are consistent with the structure OfLa 2 WsOi 2 with certain small deviations of position and intensity due to the substitution of lanthanum and europium for tungsten.
  • an illumination system comprising a radiation source and a luminescent material comprising at least one first phosphor capable of absorbing a part of the radiation emitted by the radiation source and emitting radiation of a wavelength different from that of the absorbed radiation, wherein said at least one phosphor is an europium(III)-activated hetero-polyoxometallate of general formula A a REb-zM m ⁇ 3 m +3/2b+a-i/2 ⁇ F x :Eu z is provided.
  • Such luminescent material is useful in any configuration of an illumination system comprising a source of primary radiation.
  • Radiation sources include preferably semiconductor optical radiation emitters and other devices that emit optical radiation in response to electrical excitation.
  • Semiconductor optical radiation emitters include light emitting diode LED chips, light emitting polymers (LEPs), laser diodes (LDs), organic light emitting devices (OLEDs), polymer light emitting devices (PLEDs), etc.
  • radiation-emitting sources such as those found in discharge lamps and fluorescent lamps, such as mercury low and high-pressure discharge lamps, sulfur discharge lamps, and discharge lamps based on molecular radiators as well as in X-ray tubes are also contemplated for use as radiation sources with the present inventive luminescence converter.
  • the radiation source is a light- emitting diode.
  • Any configuration of an illumination system which includes a light- emitting diode, or an array of light-emitting diodes and a luminescent material according to the invention is contemplated in the present invention, to achieve a specific colored or white light when irradiated by a LED emitting primary UV or blue light as specified above.
  • Possible configurations useful to combine the luminescent material to a light emitting diode or an array of light emitting diodes comprise epitaxy-up devices as well as flip chip LED devices.
  • FIG. 1 shows a schematic view of a chip type light emitting diode with a coating 3 comprising the luminescent material.
  • the device comprises chip type light emitting diode 1 as a radiation source.
  • the light- emitting diode die is positioned in a reflector cup lead frame 2.
  • the die 1 is connected via a bond wire 7 to a first terminal 6, and directly to a second electric terminal 6.
  • the recess of the reflector cup is filled with a coating material 3, which contains a luminescent material according to the invention to form a coating layer, which is embedded in the reflector cup.
  • the phosphors 4, 5 are applied either separately or in a blend.
  • the coating material typically comprises a polymer for encapsulating the phosphor or phosphor blend.
  • the phosphor or phosphor blend should exhibit high stability properties against the encapsulant.
  • the polymer is optically clear to prevent significant light scattering.
  • a variety of polymers are known in the LED industry for making LED lamps.
  • the polymer is selected from the group consisting of epoxy and silicone resins.
  • Adding the phosphor mixture to a liquid that is a polymer precursor can perform encapsulation.
  • the phosphor mixture can be a granular powder. Introducing phosphor particles into polymer precursor liquid results in formation of a slurry (i.e. a suspension of particles). Upon polymerization, the phosphor mixture is fixed rigidly in place by the encapsulation.
  • both the luminescent material and the LED die are encapsulated in the polymer.
  • the transparent coating material may comprise light-diffusing particles, advantageously so-called diffusers.
  • diffusers are mineral fillers, in particular CaF2, TiC>2, SiC>2, CaCO ⁇ or BaSC>4 or else inorganic pigments. These materials can be added in a simple manner to the above-mentioned resins. In operation, electrical power is supplied to the die to activate the die.
  • the die When activated, the die emits the primary light, e.g. blue light. A portion of the emitted primary light is completely or partially absorbed by the luminescent material. The luminescent material then emits secondary light, i.e., the converted light having a longer peak wavelength, in response to absorption of the primary light. The remaining unabsorbed portion of the emitted primary light is transmitted through the luminescent material, along with the secondary light.
  • the primary light e.g. blue light.
  • the luminescent material then emits secondary light, i.e., the converted light having a longer peak wavelength, in response to absorption of the primary light.
  • the remaining unabsorbed portion of the emitted primary light is transmitted through the luminescent material, along with the secondary light.
  • the reflector directs the unabsorbed primary light and the secondary light in a general direction as output light.
  • the output light is a composite light that is composed of the primary light emitted from the die and the secondary light emitted from the luminescent layer.
  • the color temperature or color point of the output light of an illumination system according to the invention will vary depending upon the spectral distributions and intensities of the secondary light in comparison to the primary light.
  • the color temperature or color point of the primary light can be varied by a suitable choice of the light emitting diode.
  • the color temperature or color point of the secondary light can be varied by a suitable choice of the phosphor blend in the luminescent material.
  • the thickness and the relative phosphor contents in the luminescent material may be configured to convert a desired percentage of primary light that is incident on the luminescent material.
  • the output light of the illumination system may have a spectral distribution such that it appears to be "white” light.
  • white light refers to light that stimulates the red, green, and blue sensors in the human eye to yield an appearance that an ordinary observer would consider “white”. Such light may be biased to the red (commonly referred to as warm white light) or to the blue (commonly referred to as cool white light).
  • the device can advantageously be produced by choosing the luminescent material, comprising a red-emitting europium(III)-activated hetero- polyoxometallate according to the invention, such that a blue radiation emitted by a blue light emitting diode is converted into complementary red wavelength ranges, to form warm white light.
  • the light emitting device thus emits light having a plurality of wavelength components, due to (a) light emitted from the diode that passes (unabsorbed) through the phosphor layer, and (b) red light resulting from down- conversion of phosphor-absorbed, diode-emitted light.
  • the result is a light-emitting device that emits warm white light.
  • a white-light emitting illumination system can advantageously be produced by choosing a luminescent material, that comprises a phosphor blend of a phosphor according to the invention and one or more second phosphors, such that a blue radiation emitted by the blue light emitting diode is converted into complementary wavelength ranges, to form polychromatic, especially trichromatic (RGB) white light.
  • a luminescent material that comprises a phosphor blend of a phosphor according to the invention and one or more second phosphors, such that a blue radiation emitted by the blue light emitting diode is converted into complementary wavelength ranges, to form polychromatic, especially trichromatic (RGB) white light.
  • Second phosphors suitable for use in the phosphor blend are Eu(II)- activated phosphors, such as (Cai_ x Sr x )S:Eu, wherein 0 ⁇ x ⁇ 1 and (Sri_ x _ y Ba x Ca y ) 2 _ z Si 5 _ a Al a N 8 -aO a :Eu z wherein 0 ⁇ a ⁇ 5, 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l and 0 ⁇ z ⁇ l, as well as SrSiEu 2+ ; CaSiEu 2+ ; CaS:Eu 2+ ,Mn 2+ , as well as (Zn,Cd)S:Ag + ; Mg 4 GeO 5 5 F:Mn 4+ ; Y 2 O 2 SiEu 2+ , ZnSiMn 2+ for red emission, and further phosphor materials having emission spec
  • typical phosphors comprise a material selected from (Bai_ x Sr x )2 SiO ⁇ Eu, wherein 0 ⁇ x ⁇ 1, SrGa2S4:Eu, SrSi2N2 ⁇ 2:Eu, RE 3 Al 5 Oi 2 :Ce, wherein RE comprises yttrium, and all lanthanoide metals, and other phosphor materials having emission spectra in the green region of the visible spectrum upon excitation as described herein.
  • blue or bluish green emitting phosphor particles may be included in the phosphor blend in addition to the red-and green-emitting phosphors; suitable emitting phosphor may comprise, e.g.
  • the phosphor composition comprises a type of phosphor particles that is selected to produce yellow light upon excitation.
  • the typical phosphor suitable for use in the phosphor blend comprise (Y,Gd) 3 Al 5 Oi 2 :Ce,Pr and other phosphor materials having emission spectra in the yellow region of the visible spectrum upon excitation as described herein.
  • Table 2 shows examples of useful combinations of LEDs and phosphor blends in the luminescent material. Table 2:
  • a white-light emitting illumination system can be realized by admixing the inorganic luminescent material comprising a mixture of two phosphors to produce the luminescence conversion layer.
  • second phosphor (5) yellow- emitting (Y,Gd)3Al 5 Oi2:Ce is chosen.
  • Part of a blue radiation emitted by a 465 nm InGaN light emitting diode is shifted by the inorganic luminescent material LiLaW2 ⁇ g:Eu into the amber to red spectral region and, consequently, into a wavelength range which is complementarily colored with respect to the color blue.
  • the light emitting device thus emits light having a plurality of wavelength components, due to (a) blue light that passes (unabsorbed) through the luminescence material, (b) amber to red light resulting from down-conversion of first phosphor-absorbed light, and c) yellow light resulting from down-conversion of second phosphor-absorbed light.
  • a human observer perceives the combination of blue primary light and the polychromatic secondary light of the phosphor blend as white light.
  • Fig. 8 shows the emission spectrum of pcLED with a luminescent material comprising LiLaW 2 ⁇ g:Eu and (Y,Gd) 3 Al 5 Oi 2 :Ce in combination with a blue-emitting LED having maximum emission at 465 nm.
  • the correlated color temperature CCT the color rendering index, the associated color point and the lumen efficiency of this exemplary pcLED have been measured.
  • Table 3 summarizes lumen efficiency (LE.), color rendering (Ra 8 ) and color point (x,y) of white LEDs for various combinations of a blue emitting InGaN LED, (465 nm),
  • an illumination system that emits output light having a spectral distribution such that it appears to be colored, e.g. "yellow to red", is provided.
  • Applications of this embodiment include security lighting as well as signal lighting for cars and traffic.
  • a yellow to red -light emitting illumination system can advantageously be produced by choosing the luminescent material comprising an amber to red emitting europium(III)-activated hetero-polyoxometallate phosphor, such that a blue radiation emitted by the blue light emitting diode is converted into complementary wavelength ranges, to form dichromatic yellow to red light.
  • the color output of the LED - phosphor system is very sensitive to the thickness of the phosphor layer, if the phosphor layer is thick and comprises an excess of an amber to red europium(III) activated hetero-polyoxometallate phosphor, then a lesser amount of the blue LED light will penetrate through the thick phosphor layer. The combined LED - phosphor system will then appear yellow to red, because it is dominated by the yellow to red secondary light of the phosphor. Therefore, the thickness of the phosphor layer is a critical variable affecting the color output of the system.
  • colored yellow to red light is produced by means of the luminescent materials that comprise a europium(III)-activated hetero- polyoxometallate phosphor.
  • the luminescent materials that comprise a europium(III)-activated hetero- polyoxometallate phosphor.
  • Part of the blue radiation emitted by a 465 nm InGaN light emitting diode is shifted by the luminescent material into the amber to red spectral region and, consequently, into a wavelength range which is complementarily colored with respect to the color blue.
  • the hue (color point in the CIE chromaticity diagram) of the colored light thereby produced can be varied by a suitable choice of the phosphor in respect of mixture and concentration.
  • a human observer perceives the combination of blue primary light and the excess secondary light of the amber to red -emitting phosphor as yellow to red light.
  • the composite luminescence converters may be manufactured from phosphor materials other than the phosphors cited. Any conventional phosphor material may be used in place of these phosphors. Therefore, the spirit and scope of the appended claims should not be limited to the foregoing description.
  • Fig. 1 is a schematic view of a dichromatic white phosphor converted LED lamp comprising a luminescent material according to the present invention positioned in the pathway of radiation emitted by a LED chip.
  • Fig. 2 shows the excitation and emission spectra of a luminescent material according to the invention
  • Fig. 3 shows the excitation spectrum OfLiLaW 2 OgIEu in dependence of the concentration of Eu(III).
  • Fig. 4 shows the excitation spectrum of La 2 W 3 Oi 2 IEu in dependence of the concentration of Eu(III).
  • Fig. 5 shows the excitation spectrum of La 2 (Mo,W)3 ⁇ i2:Eu in dependence of the concentration of W(VI).
  • Fig. 6 shows the excitation spectrum of La 2 M ⁇ 3 ⁇ i2:Eu in dependence of the concentration of Eu(III).
  • Fig. 7 shows the reflection spectrum of La 2 Mo 2 4W 0
  • Fig. 10 shows the x-ray diffraction pattern OfLiLaW 2 OgIEu in comparison to NaLaW 2 Og
  • Fig. 11 shows the x-ray diffraction pattern of La 2 WsOi 2 IEu in comparison to La 2 W 3 Oi 2 .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention concerne un système d'éclairage comprenant une source de rayonnement et un matériau luminescent contenant au moins un premier luminophore apte à absorber une partie du rayonnement émis par la source de rayonnement et à émettre un rayonnement d'une longueur d'onde différente de celle du rayonnement absorbé. Ledit luminophore au moins est un hétéro-polyoxométallate activé par europium(III) de formule générale AaREb-zMmO3m+3/2b+a- 1/2xFx:Euz, dans laquelle A représente au moins un métal alcalin choisi dans le groupe constitué par le lithium, le sodium, le potassium, le rubidium et le césium; RE représente au moins un métal des terres rares choisi dans le groupe constitué par l'yttrium, le lanthane et le gadolinium; M représente un métal choisi dans le groupe constitué par le molybdène et le tungstène ou une combinaison de ceux-ci; et dans laquelle 0 ≤ a ≤ 1, 1 ≤ b ≤ 3, 2 ≤ m ≤ 6, 0 ≤ x < 2 et 0,002< z < 1,0. La présente invention permet d'obtenir des sources lumineuses présentant une luminosité et un rendu de couleurs élevés, en particulier en association avec une diode électroluminescente servant de source de rayonnement. Le luminophore hétéro-polyoxométallate activé par europium(III) émettant du rouge peut être excité efficacement par un rayonnement primaire dans la gamme UV proche à bleu du spectre électromagnétique.
PCT/IB2007/054631 2006-11-27 2007-11-14 Systeme d'eclairage comprenant un hétéropolyoxométalate WO2008065567A1 (fr)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
US9172006B2 (en) 2010-03-16 2015-10-27 Koninklijke Philips N.V. Lighting apparatus
WO2013158993A1 (fr) * 2012-04-20 2013-10-24 Rensselaer Polytechnic Institute Fluorophores à émission à largeur de raie spectrale étroite avec bord d'excitation à large bande jusqu'à la région de longueur d'onde bleue et comprenant celle-ci
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WO2015082209A1 (fr) * 2013-12-03 2015-06-11 Osram Opto Semiconductors Gmbh Mélange de substances luminescentes, composant à semi-conducteur électroluminescent comprenant un mélange de substances luminescentes et réverbère comprenant un mélange de substances luminescentes
US10190046B2 (en) 2013-12-03 2019-01-29 Osram Opto Semiconductors Gmbh Luminescent-substance mixture, light-emitting semiconductor component having a luminescent-substance mixture, and streetlamp having a luminescent-substance mixture
JP2017017059A (ja) * 2015-06-26 2017-01-19 パナソニックＩｐマネジメント株式会社 照明用光源及び照明装置
DE102020127450A1 (de) 2020-10-19 2022-04-21 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Optoelektronisches bauelement und verfahren zur herstellung eines optoelektronischen bauelements
DE112021004536B4 (de) * 2020-10-19 2024-11-28 Ams-Osram International Gmbh Optoelektronisches bauelement und verfahren zur herstellung eines optoelektronischen bauelements

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