WO2007102094A1 - Luminescent material using (y, gd)-containing nanoparticle and surface bound organic ligands - Google Patents

Luminescent material using (y, gd)-containing nanoparticle and surface bound organic ligands Download PDF

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WO2007102094A1
WO2007102094A1 PCT/IB2007/050565 IB2007050565W WO2007102094A1 WO 2007102094 A1 WO2007102094 A1 WO 2007102094A1 IB 2007050565 W IB2007050565 W IB 2007050565W WO 2007102094 A1 WO2007102094 A1 WO 2007102094A1
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systems
alkyl
ylene
luminescent material
group
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French (fr)
Inventor
Thomas JÜSTEL
Joachim Opitz
Petra Huppertz
Detlef Uwe Wiechert
Helga Bettentrup
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Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
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Philips Intellectual Property and Standards GmbH
Koninklijke Philips Electronics NV
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Priority to JP2008557859A priority Critical patent/JP2009529085A/en
Priority to EP07705931A priority patent/EP1994120A1/en
Priority to US12/281,159 priority patent/US20090014685A1/en
Publication of WO2007102094A1 publication Critical patent/WO2007102094A1/en
Anticipated expiration legal-status Critical
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778—Borates
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C09K11/7771—Oxysulfides
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention is directed to luminescent materials, especially to the field of converter materials for fluorescent light sources, especially LEDs
  • a luminescent material for pcLEDs which can be adapted to various emission wavelength of the semiconductor and application areas of the pcLED.
  • This object is solved by a luminescent material according to claim 1 of the present invention. Accordingly, a luminescent material is provided comprising an (Y,Gd)-containing nanoparticle material, which surface is linked to at least one organic ligand molecule.
  • the term ,,linked means, describes and/or includes that the nanoparticle material and the at least one organic molecule are bonded to each other via covalent bonds, electrostatic bonds, hydrogen bonds, complex bonds (e.g. coordinative metal complex bonds) and/or any other suitable bonds and/or forces.
  • the dso size of the nanoparticle material and the at least one organic molecule are bonded to each other via covalent bonds, electrostatic bonds, hydrogen bonds, complex bonds (e.g. coordinative metal complex bonds) and/or any other suitable bonds and/or forces.
  • the dso size of the nanoparticle material and the at least one organic molecule are bonded to each other via covalent bonds, electrostatic bonds, hydrogen bonds, complex bonds (e.g. coordinative metal complex bonds) and/or any other suitable bonds and/or forces.
  • the dso size of the nanoparticle material and the at least one organic molecule are bonded to each other via covalent bonds, electrostatic bonds, hydrogen bonds, complex bonds (e.g. co
  • (Y,Gd)-containing nanoparticle material is >2 nm to ⁇ 100 nm.
  • the dso size of the (Y,Gd)-containing nanoparticle material is >4 nm to ⁇ 50 nm.
  • the dso size of the (Y,Gd)-containing nanoparticle material is >5 nm to ⁇ 20 nm.
  • the (Y,Gd)- containing nanoparticle material is a (Y,Gd)-oxide material.
  • the (Y,Gd)- containing nanoparticle material is selected out of the group comprising (Yi_ x Gd x )B ⁇ 3, (Yi- ⁇ Gd x )VO 4 , (Yi- x Gd x )NbO 4 , (Yi_ x Gd x ) 2 O 2 S, (Y 1-x Gd x ) 3 Al 5 Oi 2 , (Yi- x Gd x ) 2 Si ⁇ 5, (Yi_ x Gd x )P ⁇ 4 and mixtures thereof.
  • the (Y,Gd)- containing nanoparticle material is doped with at least one trivalent dopant material.
  • the (Y,Gd)- containing nanoparticle material is doped with at least one dopant material selected out of the group La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
  • At least one of the dopant material(s) serves as an activator material which is capable of emitting light.
  • the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 0.5 mol-% to ⁇ 50 %.
  • the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 1% to ⁇ 25 %.
  • the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 2% to ⁇ 10 %.
  • the at least one organic ligand molecule is a multidentate and / or chelate material.
  • the at least one organic ligand molecule is a N and/or O-donor molecule.
  • the at least one organic ligand molecule absorbs in the region of > 300 nm to ⁇ 500 nm.
  • the at least one organic ligand molecule absorbs in the region of > 320 nm to ⁇ 480 nm.
  • the at least one organic ligand molecule absorbs in the region of > 350 nm to ⁇ 450 nm. According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >3000 cm “1 to ⁇ 13000 cm “1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
  • the at least one organic ligand molecule has a triplet state which is >4000 cm “1 to ⁇ 10000 cm “1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
  • the at least one organic ligand molecule has a triplet state which is >20000 cm “1 to ⁇ 50000 cm “1 above the ground state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
  • the at least one organic ligand molecule has a triplet state which is >25000 cm “1 to ⁇ 45000 cm “1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
  • the at least one organic ligand molecule has a triplet state which is >30000 cm “1 to ⁇ 40000 cm “1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
  • the ratio of organic ligand molecule(s) to the light emitting material(s) in the (Y,Gd)-containing nanoparticle material is > 0.01 :1 to ⁇ 0.9:1. According to an embodiment of the present invention, the ratio of organic ligand molecule(s) to the light emitting material(s) in the (Y,Gd)-containing nanoparticle material is > 0.1 :1 to ⁇ 0.5:1
  • At least one of the organic ligand molecule(s) has the following structure I
  • Ri, R2 and/or R 3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, al
  • alkyl linear and branched Cl-C8-alkyl
  • long-chain alkyl linear and branched C5-C20 alkyl
  • alkenyl C2-C6-alkenyl
  • cycloalkyl C3-C8-cycloalkyl
  • alkoxy Cl-C6-alkoxy
  • long-chain alkoxy linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of: methylene; 1,1 -ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3- propylene; 2,2-propylidene; butan-2-ol-l,4-diyl; propan-2-ol-l,3-diyl; 1, 4-butylene; cycl
  • R is independently selected from: hydrogen, alkyl, aryl, halogen and n is from 1 to 250
  • alkyl linear and branched Cl-C6-alkyl
  • long-chain alkyl linear and branched C5-C10 alkyl, preferably linear C6-
  • C8 alkyl alkenyl C3-C6-alkenyl
  • cycloalkyl C6-C8-cycloalkyl
  • alkoxy Cl-C4-alkoxy
  • long-chain alkoxy linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy alkylene: selected from the group consisting of: methylene; 1,2-ethylene; 1,3 -propylene; butan-2-ol-l,4-diyl; 1,4-butylene; cyclohexane-l,l-diyl; cyclohexan-1,2- diyl; cyclohexan-l,4-diyl; cyclopentane-l,l-diyl; and cyclopentan-l,2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl
  • polyether chosen from the group comprising-(O-CH 2 -CH(R)) n -OH and - (O-CH 2 -CH(R)) n -H whereby R is independently selected from: hydrogen, methyl, halogen and n is from 5 to 50, preferably 10 to 25.
  • M, M n (n being an integer) : Metals (either charged or uncharged), whereby two Metals M n and M m are independently selected from each other unless otherwise indicated.
  • At least one of the organic ligand molecule(s) has the following structure II
  • Ri, and/or R 2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
  • Ri is selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl,
  • At least one of the organic ligand molecule(s) has the following structure IV
  • Ri, and/or R 2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
  • At least one of the organic ligand molecule(s) has the following structure V
  • Ri, and/or R 2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
  • At least one of the organic ligand molecule(s) has the following structure VI
  • R 2 is selected out of a group comprising single bond, methyl, alkyl, methylaryl, aryl, heteroaryl, methylheteroaryl, alkenyl, vinyl, alkinyl, methylalkinyl, ketoaryl, methylketoaryl, keto, ketoheteroaryl, methylketoheteroaryl, ketoalkenyl, methylketoalkenyl, ketoalkinyl, methylketoalkenyl, halogenmethyl, halogenmethyl aryl, arylene, halogenaryl, halogenalkyl, halogenheteroaryl, halogenmethylheteroaryl, halogenalkenyl, halogenvinyl, halogenalkinyl, halogenmethylalkinyl, halogenketoaryl, halogenmethylketoaryl, halogenmethylketoaryl, halogenmethylketoaryl, halogenmethylketoheteroaryl, halogenketo
  • Ri and R 3 does not mean or intend that there is only one substituted residue in each of the aromatic rings; rather the formula is to be read as if all possible substitutions (from mono- di- to quinquies substitution) were meant by this notation. This also goes for all further structures mentioned in this application.
  • At least one of the organic ligand molecule(s) has the following structure VII
  • Ri, R 2 and/or R 3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, al
  • At least one of the organic ligand molecule(s) has the following structure VIII:
  • Ri and/or R 2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halo genketo aryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, al
  • At least one of the organic ligand molecule(s) has the following structure IX:
  • Ri and/or R 2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
  • X and Y are independently selected out of a group comprising C, N, O, S.
  • at least one of the organic ligand molecule(s) has the following structure X: wherein Ri is selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl,
  • At least one of the organic ligand molecule(s) has the following structure XI:
  • Ri, R 2 and/or R 3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halo genketo aryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl,
  • At least one of the organic ligand molecule(s) has the following structure XII
  • Ri, R 2 , R 3 and/or R 4 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl
  • At least one of the organic ligand molecule(s) has the following structure XIII
  • Ri, R 2 , R 3 and/or R 4 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl,
  • the present invention furthermore relates to light emitting device, especially a LED comprising a luminescent material as described above.
  • the present invention furthermore relates to a use of a luminescent material as described above in biological applications, preferably bio- and/or immunoassays.
  • a luminescent material as described within the present invention may be used as "labelling" substance in biochemical applications, e.g. in bio- and/or immunoassays.
  • the luminescent material can according to one application of the present invention be used as a marker to label certain biochemical molecules or according to another application of the present invention be used as a marker to label cell moieties.
  • the labelling may according to one application of the present invention occur via a linker molecule or according to one application of the present invention by physical adhesion.
  • a luminescent material and/or a light emitting device may be of use in a broad variety of systems and/or applications, amongst them one or more of the following: Office lighting systems household application systems - shop lighting systems, home lighting systems, accent lighting systems, spot lighting systems, theater lighting systems, - fiber-optics application systems, projection systems, self-lit display systems, pixelated display systems, segmented display systems, - warning sign systems, medical lighting application systems, indicator sign systems, and decorative lighting systems portable systems - automotive applications green house lighting systems
  • the aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.
  • Fig. 1 shows an XRD spectrum of a (Y,Gd)-containing nanoparticle material according to a first example of the present invention
  • Fig. 2 shows an excitation and an emission spectrum of the material of
  • Fig. 3 shows an excitation and an emission spectrum of a luminescent material according to a first embodiment of the present invention employing the (Y,Gd)- containing nanoparticle material of Fig. 1 and 2
  • Figs. 1 to 3 refer to a (Y,Gd)-containing nanoparticle material and a luminescent material using this (Y,Gd)-containing nanoparticle material.
  • the (Y,Gd)- containing nanoparticle material used within this example is GdVO 4 IEu (5%) which was made as follows
  • Fig. 1 shows an XRD spectra of the GdVO 4 IEu material. It can be seen that the dso size of the particles is 10 nm.
  • Fig. 2 shows an excitation (dotted line) and an emission spectrum of the material of Fig. 1.
  • the excitation spectrum (dotted line) shows a maximum somewhat around 290-300 nm, the emission spectrum has several sharp bands, the most prominent band is at 625 nm.
  • the GdVO 4 IEu material was then suspended in Ethanol and a solution of 2-Thenoyltrifluoracetylacetone (see structure) and NaOMe in Ethanol was added. The suspension was heated at reflux for one hour. After cooling, the resulting precitipate was collected and washed twice with ethanol. The yield was 0,1075 g light-yellow powder.
  • TTFA Thenoyltrifluoracetylacetone
  • the luminescent material shows a further excitation band in the area around 380 nm.
  • This additional excitation band is due to the presence of the organic ligand, which absorbs in the near UV and transfers the absorbed energy to the Eu 3+ centre.

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

Abstract

The invention relates to a luminescent material for an light emitting device comprising an (Y,Gd)-containing nanoparticle material linked to at least one organic ligand molecule

Description

Luminescent material using (Y,Gd)-containing nanoparticle and surface bound organic ligands
The present invention is directed to luminescent materials, especially to the field of converter materials for fluorescent light sources, especially LEDs
For phosphor converted LEDs (pcLEDs) there is a need that the excitation and emission spectrum of the applied phosphors are adapted to the emission spectrum of the semiconductor and to the aimed applications wherein the LEDs are intended to be used. However, especially in the field of red emitting phosphors based on the activator Eu3+, such an adaption can only be achieved with great difficulty since there are only few measures to shift the absorption edge of an Eu3+ phosphor into the visible range.
It is an object of the present invention to provide a luminescent material for pcLEDs, which can be adapted to various emission wavelength of the semiconductor and application areas of the pcLED. This object is solved by a luminescent material according to claim 1 of the present invention. Accordingly, a luminescent material is provided comprising an (Y,Gd)-containing nanoparticle material, which surface is linked to at least one organic ligand molecule.
By doing so, for most applications at least one of the following advantages can be achieved:
Higher photoluminescence efficiency Stronger absorption
Absorption in the near UV and blue spectral range (for selected organic ligands) The term ,,linked" means, describes and/or includes that the nanoparticle material and the at least one organic molecule are bonded to each other via covalent bonds, electrostatic bonds, hydrogen bonds, complex bonds (e.g. coordinative metal complex bonds) and/or any other suitable bonds and/or forces. According to an embodiment of the present invention, the dso size of the
(Y,Gd)-containing nanoparticle material is >2 nm to < 100 nm.
According to an embodiment of the present invention, the dso size of the (Y,Gd)-containing nanoparticle material is >4 nm to <50 nm.
According to an embodiment of the present invention, the dso size of the (Y,Gd)-containing nanoparticle material is >5 nm to <20 nm.
According to an embodiment of the present invention, the (Y,Gd)- containing nanoparticle material is a (Y,Gd)-oxide material.
According to an embodiment of the present invention, the (Y,Gd)- containing nanoparticle material is selected out of the group comprising (Yi_xGdx)Bθ3,
Figure imgf000003_0001
(Yi-χGdx)VO4, (Yi-xGdx)NbO4, (Yi_xGdx)2O2S, (Y1-xGdx)3 Al5Oi2, (Yi- xGdx)2Siθ5, (Yi_xGdx)Pθ4 and mixtures thereof.
According to an embodiment of the present invention, the (Y,Gd)- containing nanoparticle material is doped with at least one trivalent dopant material.
According to an embodiment of the present invention, the (Y,Gd)- containing nanoparticle material is doped with at least one dopant material selected out of the group La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
According to an embodiment of the present invention, at least one of the dopant material(s) serves as an activator material which is capable of emitting light.
According to an embodiment of the present invention, the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 0.5 mol-% to < 50 %.
According to an embodiment of the present invention, the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 1% to < 25 %.
According to an embodiment of the present invention, the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 2% to < 10 %.
According to an embodiment of the present invention, the at least one organic ligand molecule is a multidentate and / or chelate material.
According to an embodiment of the present invention, the at least one organic ligand molecule is a N and/or O-donor molecule.
According to an embodiment of the present invention, the at least one organic ligand molecule absorbs in the region of > 300 nm to < 500 nm.
According to an embodiment of the present invention, the at least one organic ligand molecule absorbs in the region of > 320 nm to < 480 nm.
According to an embodiment of the present invention, the at least one organic ligand molecule absorbs in the region of > 350 nm to < 450 nm. According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >3000 cm"1 to <13000 cm"1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >4000 cm"1 to < 10000 cm"1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >20000 cm"1 to <50000 cm"1 above the ground state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >25000 cm"1 to <45000 cm"1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material. According to an embodiment of the present invention, the at least one organic ligand molecule has a triplet state which is >30000 cm"1 to <40000 cm"1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
According to an embodiment of the present invention, the ratio of organic ligand molecule(s) to the light emitting material(s) in the (Y,Gd)-containing nanoparticle material is > 0.01 :1 to < 0.9:1. According to an embodiment of the present invention, the ratio of organic ligand molecule(s) to the light emitting material(s) in the (Y,Gd)-containing nanoparticle material is > 0.1 :1 to < 0.5:1
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure I
Figure imgf000005_0001
I whereby Ri, R2 and/or R3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
Generic group definition: Throughout the description and claims generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred groups that may be applied to generic groups found within compounds disclosed herein: alkyl: linear and branched Cl-C8-alkyl, long-chain alkyl: linear and branched C5-C20 alkyl alkenyl: C2-C6-alkenyl, cycloalkyl: C3-C8-cycloalkyl, alkoxy: Cl-C6-alkoxy, long-chain alkoxy: linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of: methylene; 1,1 -ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3- propylene; 2,2-propylidene; butan-2-ol-l,4-diyl; propan-2-ol-l,3-diyl; 1, 4-butylene; cyclohexane-l,l-diyl; cyclohexan-l,2-diyl; cyclohexan-1,3- diyl; cyclohexan-l,4-diyl; cyclopentane-l,l-diyl; cyclopentan-l,2-diyl; and cyclopentan-l,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300, arylene: selected from the group consisting of: 1 ,2-phenylene; 1,3- phenylene; 1,4-phenylene; 1,2-naphtalenylene; 1,3-naphtalenylene; 1,4- naphtalenylene; 2,3-naphtalenylene; l-hydroxy-2,3-phenylene; l-hydroxy-2,4- phenylene; l-hydroxy-2,5- phenylene; and l-hydroxy-2,6-phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; thenoyl, oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2, 3-diyl; pyridin-2,4-diyl; pyridin-2, 5-diyl; pyridin-2, 6-diyl; pyridin-3,4- diyl; pyridin-3,5-diyl; quinolin-2, 3-diyl; quinolin-2,4-diyl; quinolin-2, 8-diyl; isoquinolin-1, 3-diyl; isoquinolin-l,4-diyl; pyrazol- 1, 3-diyl; pyrazol-3,5- diyl; triazole-3, 5-diyl; triazole-1, 3-diyl; pyrazin-2, 5-diyl; and imidazole-2,4-diyl, a -Cl-C6-heterocycloalkyl, wherein the heterocycloalkyl of the -Cl - Cβ-heterocycloalkyl is, selected from the group consisting of: piperidinyl; piperidine; 1 ,4-piperazine, tetrahydrothiophene; tetrahydrofuran; 1,4,7-triazacyclononane; 1,4,8,11- tetraazacyclotetradecane; 1,4,7,10,13-pentaazacyclopentadecane; 1,4-diaza- 7-thia- cyclononane; 1,4- diaza-7-oxa-cyclononane; 1,4,7,10-tetraazacyclododecane; 1,4- dioxane; 1,4, 7-trithia-cyclononane; pyrrolidine; and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-1,2- ylene; piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; 1,4-piperazin- 2,3-ylene; l,4-piperazin-2,5-ylene; l,4-piperazin-2,6-ylene; 1,4-piperazin- 1,2-ylene; 1,4- piperazin- 1 ,3-ylene; 1 ,4-piperazin- 1 ,4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran- 3,4-ylene; tetrahydrofuran-2,3-ylene; pyrrolidin-2,5-ylene; pyrrolidin- 3,4-ylene; pyrrolidin-2,3-ylene; pyrrolidin- 1,2-ylene; pyrrolidin-l,3-ylene; pyrrolidin-2,2- ylidene; l,4,7-triazacyclonon-l,4-ylene; 1,4,7- triazacyclonon-2,3-ylene; 1,4,7- triazacyclonon-2,9-ylene; 1 ,4,7-triazacyclonon-3,8-ylene; 1 ,4,7-triazacyclonon-2,2- ylidene; 1 ,4,8,11 -tetraazacyclotetradec- 1 ,4-ylene; 1 ,4,8, 11 - tetraazacyclotetradec- 1,8- ylene; 1,4,8,1 l-tetraazacyclotetradec-2,3-ylene; 1,4,8,1 l-tetraazacyclotetradec-2, 5- ylene; 1,4,8,11- tetraazacyclotetradec- 1,2-ylene; 1,4,8,11- tetraazacyclotetradec-2,2- ylidene; 1 ,4,7, 10-tetraazacyclododec- 1 ,4-ylene; 1 ,4,7, 10-tetraazacyclododec- 1 ,7-ylene; l,4,7,10-tetraazacyclododec-l,2- ylene; l,4,7,10-tetraazacyclododec-2,3- ylene; l,4,7,10-tetraazacyclododec-2,2-ylidene; 1,4,7,10,13 pentaazacyclopentadec-l,4-ylene; 1 ,4,7, 10,13- pentaazacyclopentadec- 1 ,7-ylene; 1 ,4,7, 10, 13-pentaazacyclopentadec-2,3- ylene; 1,4,7,10, 13 -pentaazacyclopentadec- 1,2-ylene; 1,4,7,10, 13- pentaazacyclopentadec-2,2-ylidene; l,4-diaza-7-thia-cyclonon- 1,4-ylene; l,4-diaza-7- thia-cyclonon- 1,2-ylene; l,4-diaza-7thia-cyclonon- 2,3-ylene; l,4-diaza-7-thia-cyclonon- 6,8-ylene; l,4-diaza-7-thia-cyclonon- 2,2-ylidene; l,4-diaza-7-oxacyclonon- 1,4-ylene; 1 ,4-diaza-7-oxa-cyclonon- 1,2-ylene; l,4diaza-7-oxa-cyclonon-2,3-ylene; l,4-diaza-7- oxa-cyclonon-6, 8-ylene; l,4-diaza-7-oxa-cyclonon-2,2-ylidene; l,4-dioxan-2,3-ylene; 1,4- dioxan-2,6-ylene; l,4-dioxan-2,2-ylidene; tetrahydropyran-2,3-ylene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5-ylene; tetrahydropyran-2,2- ylidene; l,4,7-trithia-cyclonon-2,3-ylene; l,4,7-trithia-cyclonon-2,9- ylene; and 1 ,4,7-trithia- cyclonon-2,2-ylidene, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11- tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; l,4-diaza-7- thiacyclononanyl; l,4-diaza-7-oxa- cyclononanyl; 1,4,7,10-tetraazacyclododecanyl; 1,4- dioxanyl; 1 ,4,7- trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, amine: the group -N(R)2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl- C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, halogen: selected from the group consisting of: F; Cl; Br and I, halogenalkyl: selected from the group consisting of mono, di, tri-, poly and perhalogenated linear and branched Cl-C8-alkyl pseudohalogen: selected from the group consisting of -CN, -SCN, -OCN, N3, -CNO, -SeCN sulphonate: the group -S(O)2OR, wherein R is selected from: hydrogen; Cl- C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, sulphate: the group -OS(O)2OR, wherein R is selected from: hydrogen;
Cl- C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, sulphone: the group -S(O)2R, wherein R is selected from: hydrogen; Cl- C6- alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulphonamide) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6- alkyl; ClC6-alkyl-C6H5 ; and phenyl, wherein when both R are C 1 -C6-alkyl both R' together may form an -NC3 to an -NCS heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, carboxylate derivative: the group -C(O)OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, carbonyl derivative: the group -C(O)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give amide) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl- C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R' are C1-C6- alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, phosphonate: the group -P(O) (OR) 2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphate: the group -OP(O)(O R)2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5, phosphine oxide: the group -P (O) R2, wherein R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. polyether: chosen from the group comprising-(O-CH2-CH(R))n-OH and -
(0-CH2-CH(R))n-H whereby R is independently selected from: hydrogen, alkyl, aryl, halogen and n is from 1 to 250
Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched Cl-C6-alkyl, long-chain alkyl: linear and branched C5-C10 alkyl, preferably linear C6-
C8 alkyl alkenyl: C3-C6-alkenyl, cycloalkyl: C6-C8-cycloalkyl, alkoxy: Cl-C4-alkoxy, long-chain alkoxy: linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy alkylene: selected from the group consisting of: methylene; 1,2-ethylene; 1,3 -propylene; butan-2-ol-l,4-diyl; 1,4-butylene; cyclohexane-l,l-diyl; cyclohexan-1,2- diyl; cyclohexan-l,4-diyl; cyclopentane-l,l-diyl; and cyclopentan-l,2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: 1 ,2-phenylene; 1,3- phenylene; 1,4-phenylene; 1,2-naphtalenylene; 1,4-naphtalenylene; 2,3- naphtalenylene and l-hydroxy-2,6-phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridin 2,3-diyl; pyridin-2,4-diyl; pyridin-2,6-diyl; pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; isoquinolin-l,3-diyl; isoquinolin-l,4-diyl; pyrazol- 3,5-diyl; and imidazole-2,4-diyl, heterocycloalkyl: selected from the group consisting of: pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1,4 piperazinyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; 1,4- piperazin-2,3-ylene; 1 ,4-piperazin-2,6-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2-ylidene; l,4,7-triazacyclonon-l,4- ylene; 1,4,7- triazacyclonon-2,3-ylene; l,4,7-triazacyclonon-2,2-ylidene; 1,4,8,11- tetraazacyclotetradec- 1 ,4-ylene; 1 ,4,8, 11 - tetraazacyclotetradec- 1 ,8-ylene; 1 ,4,8, 11 - tetraazacyclotetradec-2,3-ylene; 1,4,8,11- tetraazacyclotetradec-2,2-ylidene; 1,4,7,10- tetraazacyclododec- 1 ,4-ylene; 1 ,4,7, 10- tetraazacyclododec- 1 ,7-ylene; 1 ,4,7, 10- tetraazacyclododec-2,3-ylene; 1,4,7,10- tetraazacyclododec-2,2-ylidene; 1,4,7,10,13- pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; 1,4- diaza-7-thia-cyclonon-l,4 ylene; l,4-diaza-7-thia-cyclonon-2,3-ylene; l,4-diaza-7-thia cyclonon-2,2-ylidene; l,4-diaza-7-oxa-cyclonon-l,4-ylene; 1,4 diaza-7-oxa-cyclonon- 2,3-ylene;l,4-diaza-7-oxa-cyclonon-2,2- ylidene; l,4-dioxan-2,6-ylene; l,4-dioxan-2,2- ylidene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5-ylene; and tetrahydropyran- 2,2- ylidene, a -Cl-Cβ-alkyl-heterocycloalky, wherein the heterocycloalkyl of the -Cl- C6- heterocycloalkyl is selected from the group consisting of: piperidinyl; 1,4-piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10-tetraazacyclododecanyl; and pyrrolidinyl, wherein the heterocycloalkyl may be connected to the -C1-C6- alkyl via any atom in the ring of the selected heterocycloalkyl, amine: the group -N (R) 2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, halogen: selected from the group consisting of: F and Cl, sulphonate: the group -S(O)2OR, wherein R is selected from: hydrogen;
Cl- C6-alkyl; Na; K; Mg; and Ca, sulphate: the group -OS(O)2OR, wherein R is selected from: hydrogen; Cl- C6-alkyl; Na; K; Mg; and Ca, sulphone: the group -S(O)2R, wherein R is selected from: hydrogen; Cl- C6- alkyl; benzyl and amine selected from the group: -NR'2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, carboxylate derivative: the group -C(O)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl, carbonyl derivative: the group: -C(O)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphonate: the group -P(O) (OR)2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphate: the group -OP(O) (OR)2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphine oxide: the group -P(O)R2, wherein R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl. polyether: chosen from the group comprising-(O-CH2-CH(R))n-OH and - (O-CH2-CH(R))n-H whereby R is independently selected from: hydrogen, methyl, halogen and n is from 5 to 50, preferably 10 to 25.
M, Mn (n being an integer) : Metals (either charged or uncharged), whereby two Metals Mn and Mm are independently selected from each other unless otherwise indicated.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure II
Figure imgf000012_0001
II whereby Ri, and/or R2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether. According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure III
Figure imgf000012_0002
III whereby Ri is selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure IV
Figure imgf000013_0001
IV whereby Ri, and/or R2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure V
Figure imgf000013_0002
V whereby Ri, and/or R2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure VI
Figure imgf000014_0001
VI wherein R2 is selected out of a group comprising single bond, methyl, alkyl, methylaryl, aryl, heteroaryl, methylheteroaryl, alkenyl, vinyl, alkinyl, methylalkinyl, ketoaryl, methylketoaryl, keto, ketoheteroaryl, methylketoheteroaryl, ketoalkenyl, methylketoalkenyl, ketoalkinyl, methylketoalkenyl, halogenmethyl, halogenmethyl aryl, arylene, halogenaryl, halogenalkyl, halogenheteroaryl, halogenmethylheteroaryl, halogenalkenyl, halogenvinyl, halogenalkinyl, halogenmethylalkinyl, halogenketoaryl, halogenmethylketoaryl, halogenketo, halogenketoheteroaryl, halogenmethylketoheteroaryl, halogenketoalkenyl, halogenmethylketoalkenyl, halogenketoalkinyl, halogenmethylketoalkenyl, and wherein Ri and/or R3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
It should be noted that the way of indication and/or notation for Ri and R3 does not mean or intend that there is only one substituted residue in each of the aromatic rings; rather the formula is to be read as if all possible substitutions (from mono- di- to quinquies substitution) were meant by this notation. This also goes for all further structures mentioned in this application.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure VII
Figure imgf000015_0001
VII wherein Ri, R2 and/or R3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure VIII:
Figure imgf000015_0002
VIII wherein Ri and/or R2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halo genketo aryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether and X, Y and Z are independently selected out of a group comprising C, N, O, S.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure IX:
Figure imgf000016_0001
IX wherein Ri and/or R2 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether; and
X and Y are independently selected out of a group comprising C, N, O, S. According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure X:
Figure imgf000017_0001
wherein Ri is selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether. and W, X, Y and Z are independently selected out of a group comprising C, N, O, S.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure XI:
Figure imgf000017_0002
XI wherein Ri, R2 and/or R3 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halo genketo aryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether. and X, Y and Z are independently selected out of a group comprising C,
N, O, S.
It should be noted that the bonds
Figure imgf000018_0001
are supposed to indicate that all possible cis/trans isomers are covered by the structure XI.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure XII
Figure imgf000018_0002
XII wherein Ri, R2, R3 and/or R4 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
According to an embodiment of the present invention, at least one of the organic ligand molecule(s) has the following structure XIII
Figure imgf000019_0001
XIII wherein Ri, R2, R3 and/or R4 are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene,heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether.
The present invention furthermore relates to light emitting device, especially a LED comprising a luminescent material as described above.
The present invention furthermore relates to a use of a luminescent material as described above in biological applications, preferably bio- and/or immunoassays. Surprisingly it has been found that a luminescent material as described within the present invention may be used as "labelling" substance in biochemical applications, e.g. in bio- and/or immunoassays.
The luminescent material can according to one application of the present invention be used as a marker to label certain biochemical molecules or according to another application of the present invention be used as a marker to label cell moieties. The labelling may according to one application of the present invention occur via a linker molecule or according to one application of the present invention by physical adhesion. A luminescent material and/or a light emitting device according to the present invention may be of use in a broad variety of systems and/or applications, amongst them one or more of the following: Office lighting systems household application systems - shop lighting systems, home lighting systems, accent lighting systems, spot lighting systems, theater lighting systems, - fiber-optics application systems, projection systems, self-lit display systems, pixelated display systems, segmented display systems, - warning sign systems, medical lighting application systems, indicator sign systems, and decorative lighting systems portable systems - automotive applications green house lighting systems The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations. BRIEF DESCRIPTION OF THE DRAWINGS
Additional details, characteristics and advantages of the object of the invention are disclosed in the subclaims, the figures and the following description of the respective figures and examples, which —in an exemplary fashion— show several embodiments of an Eu-comprising material use in a light emitting device according to the invention as well as an LED according to embodiments of the present invention.
Fig. 1 shows an XRD spectrum of a (Y,Gd)-containing nanoparticle material according to a first example of the present invention
Fig. 2 shows an excitation and an emission spectrum of the material of
Fig. 1
Fig. 3 shows an excitation and an emission spectrum of a luminescent material according to a first embodiment of the present invention employing the (Y,Gd)- containing nanoparticle material of Fig. 1 and 2
EXAMPLE I
Figs. 1 to 3 refer to a (Y,Gd)-containing nanoparticle material and a luminescent material using this (Y,Gd)-containing nanoparticle material. The (Y,Gd)- containing nanoparticle material used within this example is GdVO4IEu (5%) which was made as follows
GdCl3 (9.5 mmol) and EuCl3 (0.5 mmol) were dissolved in 375 ml H2O. NaVO4 was subsequently added in 50 ml at ambient temperature, resulting in a "milky" solution which was heated to 1000C for about 30 minutes. The resulting precipitate was collected, washed with water and with acetone and dried at 6O0C. The yield was 2,5162 g-
Fig. 1 shows an XRD spectra of the GdVO4IEu material. It can be seen that the dso size of the particles is 10 nm.
Fig. 2 shows an excitation (dotted line) and an emission spectrum of the material of Fig. 1. The excitation spectrum (dotted line) shows a maximum somewhat around 290-300 nm, the emission spectrum has several sharp bands, the most prominent band is at 625 nm.
The GdVO4IEu material was then suspended in Ethanol and a solution of 2-Thenoyltrifluoracetylacetone (see structure) and NaOMe in Ethanol was added. The suspension was heated at reflux for one hour. After cooling, the resulting precitipate was collected and washed twice with ethanol. The yield was 0,1075 g light-yellow powder.
Figure imgf000022_0001
Thenoyltrifluoracetylacetone (TTFA) Fig. 3 shows an excitation spectrum (dotted line) and an emission spectrum of the GdVO4 :Eu / TTFA material.
From the spectra it can be clearly seen that the luminescent material shows a further excitation band in the area around 380 nm. This additional excitation band is due to the presence of the organic ligand, which absorbs in the near UV and transfers the absorbed energy to the Eu3+ centre. The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.

Claims

CLAIMS:
1. Luminescent material for a light emitting device comprising an (Y,Gd)- containing nanoparticle material linked to at least one organic ligand molecule.
2. Luminescent material of claim 1, whereby the size of the (Y5Gd)- containing nanoparticle material is >2 nm to < 100 nm.
3. The luminescent material of claim 1 or 2, whereby (Y,Gd)-containing nanoparticle material is doped with at least one dopant material selected out of the group La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
4. The luminescent material of any of the claims 1 to 3 whereby the dotation level of the dopant material in the (Y,Gd)-containing nanoparticle material is > 0,5% to < 50 %.
5. The luminescent material of any of the claims 1 to 4 whereby the at least one organic ligand molecule is a multidentate and /or chelate material.
6. The luminescent material of any of the claims 1 to 5 whereby the at least one organic ligand molecule is a N and/or O-donor material.
7. The luminescent material of any of the claims 1 to 6 whereby the at least one organic ligand molecule absorbs in the region of > 300 nm to < 500 nm and/or has a triplet state which is >3000 cm"1 to <13000 cm"1 above the light emitting state of the light emitting material(s) in the (Y,Gd)-containing nanoparticle material.
8. The luminescent material of any of the claims 1 to 7 whereby ratio of organic ligand molecule(s) to the light emitting material(s) in the (Y,Gd)-containing nanoparticle material is > 0.01 :1 to ≤ 0.9:l.
9. A light emitting device, especially a LED comprising a luminescent material according to any of the claims 1 to 8.
10. A system comprising a luminescent material according to any of the claims 1 to 8 and/or a light emitting device according to Claim 9, the system being used in one or more of the following applications:
Office lighting systems household application systems shop lighting systems, - home lighting systems, accent lighting systems, spot lighting systems, theater lighting systems, fiber-optics application systems, - projection systems, self-lit display systems, pixelated display systems, segmented display systems, warning sign systems, - medical lighting application systems, indicator sign systems, and decorative lighting systems portable systems automotive applications - green house lighting systems
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