WO2017092849A1 - Luminophores activés par mn - Google Patents

Luminophores activés par mn Download PDF

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Publication number
WO2017092849A1
WO2017092849A1 PCT/EP2016/001938 EP2016001938W WO2017092849A1 WO 2017092849 A1 WO2017092849 A1 WO 2017092849A1 EP 2016001938 W EP2016001938 W EP 2016001938W WO 2017092849 A1 WO2017092849 A1 WO 2017092849A1
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Prior art keywords
phosphors
light
compound according
light source
emission
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PCT/EP2016/001938
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German (de)
English (en)
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Holger Winkler
Thomas Juestel
Claudia SUESSEMILCH
Matthias Mueller
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Merck Patent Gmbh
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Publication of WO2017092849A1 publication Critical patent/WO2017092849A1/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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7706—Aluminates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

Definitions

  • the present invention relates to Mn + -activated garnet phosphors, a process for their preparation and their use as
  • Conversion phosphors or in light sources in particular in phosphorus-converted light-emitting devices, such as pc-LEDs (phosphor converted light emitting devices).
  • the present invention further relates to an emission-converting material comprising the conversion phosphor according to the invention, and to a light source which contains the conversion phosphor according to the invention or the emission-converting material.
  • Another object of the present invention is a
  • Lighting unit which is a light source with the conversion phosphor according to the invention or the invention
  • the Mn + -activated garnet phosphors according to the invention are particularly suitable for producing warm-white light in solid-state light sources.
  • inorganic phosphors have been developed to provide emitting screens, X-ray amplifiers, and radiation
  • RGB LEDs red + green + blue LEDs
  • white light is generated by mixing the light of three different emitting in the red, green and blue spectral light emitting diodes.
  • the systems UV LED + RGB phosphor in which a UV emitting semiconductor (primary light source) emits the light to the environment in which three different phosphors (conversion phosphors) are excited to emit in the red, green and blue spectral range.
  • a UV emitting semiconductor primary light source
  • three different phosphors conversion phosphors
  • two different phosphors can be used which emit yellow or orange and blue.
  • Primary light source emits, for example, blue light, which excites one or more phosphors (conversion phosphors) to emit light in the yellow area, for example. By mixing the blue and the yellow light, white light is created. Alternatively, two or more phosphors emitting, for example, green or yellow and orange or red light may be used.
  • Binary complementary systems have the advantage of being able to produce white light with only one primary light source and, in the simplest case, only one conversion phosphor.
  • the best known of these systems consists of an indium-aluminum-gallium-nitride chip as a primary light source emitting light in the blue spectral region, and a cerium-doped yttrium-aluminum garnet (YAG: Ce) as a conversion phosphor, which is excited in the blue region and emit light in the yellow spectral range.
  • YAG cerium-doped yttrium-aluminum garnet
  • improvements in the color rendering index as well as the stability of the color temperature are desirable.
  • other garnet phosphors of the general formula (Y, Gd, Lu, Tb) 3 (Al, Ga, Sc) 50i 2: Ce are known for this use.
  • Garnet phosphors are special because of their high stability to air and moisture
  • the binary-complementary systems therefore require a yellow converter when using a blue-emitting semiconductor as the primary light source.
  • fluorescent light to reflect white light.
  • green and red emitting conversion phosphors can be used.
  • a semiconductor emitting in the violet spectral region or in the near UV spectrum is used as the primary light source, then either an RGB phosphor mixture or a dichroic mixture must be used
  • Conversion luminescent material for light sources in particular for pc LEDs for producing warm white light.
  • a major disadvantage of using a primary light source with a broadband emitting Ce 3+ -doped garnet phosphor or an LED with a dichroic spectrum is their dependence of the color reproduction of the color temperature.
  • low color temperatures T c ⁇ 5000 K
  • sufficiently high color rendering CRI> 80
  • red-emitting phosphors with high absorption in the blue, violet or UV spectral range, with a high quantum efficiency and a high Lumen equivalent are provided.
  • red emitting phosphors Disadvantage of these previously used red emitting phosphors is their relatively low stability, which is partly due to the sensitivity to hydrolysis of the sulfidic or nitridic host lattice and partly due to the redoxability of the Eu 2+ activator.
  • the lumen equivalent of 200 to 270 lm / W is not as high as that of Eu 3+ phosphors with 280 to 360 Im W due to the broad emission band.
  • garnet phosphors have been proposed, which are characterized by a lower
  • JP 2009/079094 discloses garnet phosphors which are co-doped with Mn 2+ in addition to the Ce 3+ doping. Charge compensation takes place via the simultaneous incorporation of silicon instead of aluminum in the host lattice.
  • a disadvantage of the known garnet phosphors described above over the Mn 4+ -activated garnets of the present invention is that LEDs with high color rendering at low
  • Color temperatures (CCT ⁇ 4000 K) can not be realized because the red spectral component is missing.
  • Object of the present invention is therefore to phosphors
  • a further object of the present invention is to provide red phosphors which have a higher proportion of the emission in the red spectral region than the phosphors known from the prior art, or which have an emission spectrum with an emission maximum shifted to the longer wavelength range in comparison to conventional phosphors , This allows warm white pc LEDs with high color rendering at low
  • Color temperatures (CCT ⁇ 4000 K) can be realized.
  • Another object of the present invention is to provide red phosphors that are well known in the art
  • the present invention by providing a Mn 4+ -activated phosphor can be solved.
  • present invention are garnet phosphors doped with Mn + and an alkali metal selected from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals.
  • the present invention thus relates to a compound of the following general formula (1),
  • M 1 is selected from the group consisting of Y, Gd, Dy and Lu and mixtures of these metals;
  • M 2 is selected from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals;
  • M 1 is a triply charged one
  • M 2 is a singly charged metal atom (M 2 ) + .
  • Al and Ga are in each case present as triply charged metal atoms Al 3+ and Ga 3+ and Mn is present as a fourfold charged metal atom Mn 4+ , while oxygen in the form of O 2 " compensates for the positive charges in the compound.
  • the Mn 4+ -activated phosphors according to the invention are:
  • Garnet phosphors selected with Mn 4+ and an alkali metal (M 2 ) + from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals are doped.
  • Mn 4+ ions replace two Al 3+ ions and one (M 2 ) + ion (M 1 ) 3+ ion in the garnet crystal lattice.
  • the compounds according to the invention are obtained by the use of (M 2 ) 2CÜ 3 for co-doping, where M 2 is Li, Na, K or Rb and a mixture of two or more of these metals.
  • All of the Mn + and (M 2 ) + co-doped garnet phosphors described here have emission bands in the red spectral range between 600 and 750 nm and have a high photoluminescence quantum yield.
  • the compounds according to the invention are usually in the ultraviolet and / or blue spectral range from about 250 to about 550 nm,
  • the red spectral range preferably from about 300 to about 400 nm, excitable and usually emit with an emission maximum in the red spectral range of about 600 to about 750 nm, thereby covering the red spectral range.
  • UV light is defined as light whose emission maximum lies between 100 and 389 nm, when violet light denotes light whose emission maximum lies between 390 and 399 nm, and blue light denotes light of which
  • Emission maximum between 566 and 600 nm and is such as red light whose emission maximum is between 601 and 750 nm.
  • MY Lu or a mixture of Y and Lu.
  • M 1 is Y or Lu.
  • M 1 is Lu.
  • the compound of the invention preferably contains Al or a combination of Al with up to 20 atom% of Ga.
  • index x in the general formula (1) 0 ⁇ x 2.00, more preferably 0 ⁇ x -i 1, 00, more preferably 0 ⁇ x ⁇ 0.50, more preferably 0 ⁇ x ⁇ 0.10, and most preferably 0 ⁇ x 0.05.
  • index y in the general formula (1) preferably:
  • M 2 is selected from the group consisting of Li, Na and K and mixtures of two or more of these metals.
  • M 1 is selected from the group consisting of Y, Lu and mixtures of these metals;
  • M 2 is selected from the group consisting of Li, Na and K and mixtures of two or more of these metals;
  • the compound of the invention may preferably be coated on its surface with another compound, as below
  • Another object of the present invention is a process for preparing a compound according to the general formula (1), comprising the following steps: a) Preparation of a solution containing M 1 , M 2 , Al, Mn and
  • the solution in step a) is prepared by dissolving salts which contain M 1 , M 2 , Al, Mn and optionally Ga in an aqueous medium.
  • the salts in step a) can be added either successively in any order or simultaneously.
  • the salts can be added either as solids or as solutions.
  • the addition of the citric or tartaric acid in step b) takes place after the addition of all the salts in step a).
  • the use of citric acid in step b) is preferred.
  • the corresponding oxide (M 1 ) 2O3 is preferably used in step a) as salt for the ion (M 1 ) 3+ .
  • the oxide is preferably dissolved in an aqueous acid such as nitric acid.
  • the ion (M 2 ) + in step a) is preferably in the form of
  • M 2 halides selected from M 2 F, M Cl, M 2 Br and M 2 I.
  • Suitable for Al in step a) are various salts, such as, for example, nitrate (Al (NO 3) 3), acetate (Al (OAc) 3) or other water-soluble Al salts. Preference is given to the nitrate salts. If the compound according to the invention contains Ga, this becomes
  • Element in step a) is preferably used in the form of the nitrate (Ga (NO 3) 3), acetate (Ga (OAc) 3) or oxalate (Ga 2 (C 2 O-i) 3).
  • Mn is preferably used in step a) in the form of water-soluble manganese salts, for example Mn halides selected from MnF 2, MnCb, MBr 2 and Mn, manganese acetate ( ⁇ ( ⁇ ) or manganese oxalate (MnC 2 O-r 2 H 2 O)) of manganese oxalate
  • the solution in step a) is preferably an acidic solution.
  • first (M) 2O3 is dissolved in an acid, preferably in nitric acid, more preferably in dilute nitric acid.
  • the other salts are dissolved in demineralized water and then the previously dissolved (M) 2O3 is added. It follows the addition of
  • the dissolution of the starting compounds can be carried out at room temperature or elevated temperature.
  • the release of the starting compounds is carried out at room temperature or elevated temperature.
  • step c) The drying of the mixture in step c) is preferably carried out at elevated temperature, more preferably in a temperature range of 70 to 170 ° C, more preferably in a temperature range of 110 to 150 ° C. After drying in step c), a precursor compound is obtained which already contains all the phosphor present in the invention
  • the calcining of the solid in step d) of the process according to the invention is preferably carried out in two steps.
  • the first calcination step is carried out in air or under oxidizing conditions.
  • Preferred here is a reaction time of 0.5 to 10 h, more preferably from 1 to 5 h, most preferably from 2 to 4 h, and a temperature in the range of 800 to 1300 ° C, particularly preferably from 900 to 1 100 ° C, most preferably from 950 to 1050 ° C.
  • the precalcined product from the first calcination step is cooled and comminuted, for example, crushed, before being subjected to the second calcination step.
  • the second calcination step is preferably carried out in air or under oxidizing conditions. Preference is given here to a reaction time of from 1 to 1.5 h, particularly preferably from 2 to 10 h, very particularly preferably from 3 to 5 h, and a temperature in the range from 1400 to 1800 ° C., more preferably from 1500 to 1700 ° C., most preferably between 1550 and 1650 ° C.
  • the calcining can be carried out, for example, so that the resulting mixtures are introduced in a high-temperature furnace, for example in a chamber furnace.
  • a reaction vessel for example, a corundum crucible with lid is suitable.
  • the compounds according to the invention are comminuted after the second calcination step, for example by mortars.
  • the inventive compounds according to the invention are comminuted after the second calcination step, for example by mortars.
  • Suitable for this purpose are all the coating methods known to the person skilled in the art according to the prior art and used for phosphors.
  • Suitable materials for the coating are, in particular, metal oxides and nitrides, in particular earth metal oxides, such as Al 2 O 3, and earth metal nitrides, such as AlN, and also SiO 2.
  • the coating for example by fluidized bed process or be carried out wet-chemically.
  • Suitable coating methods are known, for example, from JP 04-304290, WO 91/10715, WO
  • the aim of the coating can be a higher stability of the phosphors, for example against air or moisture.
  • the goal can also be an improved coupling and decoupling of light by a suitable choice of the surface of the coating and the
  • Yet another object of the present invention is the use of the compound of the invention as a phosphor or conversion luminescent material, in particular for the partial or complete conversion of ultraviolet and / or blue light of a light emitting diode in light with a longer wavelength.
  • the compounds of the invention are therefore also referred to as phosphors.
  • a further subject of the present invention is therefore an emission-converting material comprising a compound according to the invention.
  • the emission-converting material may consist of the compound according to the invention and would in this case be equated with the term "conversion luminescent substance" as defined above It may also be preferred that the emission-converting material according to the invention contains, in addition to the compound according to the invention
  • Conversion phosphors contains.
  • the emission-converting material according to the invention preferably contains a mixture of at least two conversion phosphors, at least one of which is a compound according to the invention. It is particularly preferred that the at least two conversion phosphors are phosphors which emit light with mutually complementary wavelengths.
  • the compounds according to the invention are used in small amounts, they already give good LED qualities.
  • the LED quality is doing with usual parameters, such as the Color
  • CIE Correlated Color Temperature
  • Lumen equivalents or absolute lumens or the color point in CIE x and y coordinates described.
  • the Color Rendering Index is a familiar, non-standard photometric size, which the color fidelity of an artificial light source with that of sunlight or and
  • Correlated Color Temperature is a photometric quantity with unit Kelvin which is familiar to the person skilled in the art. The higher the numerical value, the higher the blue component of the light and the colder the white light of an artificial radiation source appears to the viewer.
  • the CCT follows the concept of the black light emitter, whose color temperature describes the so-called Planckian curve in the CIE diagram.
  • the lumen equivalent is a photometric quantity known to those skilled in the art with the unit Im / W, which describes how large the photometric luminous flux in lumens of a light source is at a certain radiometric radiation power with the unit Watt. The higher the lumen equivalent, the more efficient a light source is.
  • the lumen is a photometrical photometric quantity which is familiar to the person skilled in the art and describes the luminous flux of a light source, which is a measure of the total visible radiation emitted by a radiation source. The larger the luminous flux, the brighter the light source appears to the observer.
  • CIE x and CIE y represent the coordinates in the familiar CIE standard color diagram (in this case normal observer 1931), which describes the color of a light source.
  • the excitability of the phosphors according to the invention extends over a wide range, ranging from about 250 to about 550 nm, preferably from about 300 to about 400 nm. Usually, the maximum of the excitation curve is between 325 and 375 nm.
  • Another object of the present invention is a light source containing at least one primary light source and at least one compound of the invention.
  • the maximum emission of the primary light source is usually in the range of about 250 to about 550 nm, preferably in the range of about 300 to about 400 nm. Particularly preferred is a range between 325 and 375 nm, wherein the primary radiation partially or completely by the inventive
  • Phosphor is converted into longer-wave radiation.
  • the primary light source is a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC or else an arrangement based on an organic light-emitting layer (OLED).
  • OLED organic light-emitting layer
  • Light source is the primary light source is a source that shows electroluminescence and / or photoluminescence. Furthermore, the primary light source can also be a plasma or discharge source. Corresponding light sources according to the invention are also referred to as light-emitting diodes or LEDs.
  • the phosphors according to the invention can be used individually or as a mixture with suitable phosphors which are familiar to the person skilled in the art.
  • suitable phosphors which are familiar to the person skilled in the art.
  • Corresponding phosphors which are suitable in principle for mixtures are, for example:
  • Ba x Sri -x F 2 Eu 2+ (where 0 ⁇ x ⁇ 1), BaSrMgSi 2 0 7 : Eu 2+ , BaTiP 2 0 7 ,
  • CaAl 2 O 4 Tb 3+ , Ca 3 Al 2 Si 3 Oi 2 : Ce 3+ , Ca 3 Al 2 Si 3 Oi 2 : Ce 3+ ,
  • CaGa 2 S 4 Mn 2+ , CaGa 2 S: Pb 2+ , CaGeO 3 : Mn 2+ , Cal 2 : Eu 2+ in SiO 2 , Cal 2 : Eu 2+ , Mn 2+ in SiO 2l
  • CaLaB0 4 Eu 3+ , CaLaB 3 0 7 : Ce 3+ , Mn 2+ ,
  • Ca 5 (PO) 3 F Sb 3+
  • Ca 5 (PO 4 ) 3 F Sn + , ⁇ -Ca 3 (PO) 2 : Eu 2+ , ⁇ -Ca 3 (PO 4 ) 2 : Eu 2+
  • Ca 2 P 2 O Eu 2+
  • Ca 2 P 2 O 7 Eu +
  • CaP 2 0 6 Mn 2+
  • a-Ca 3 (P0) 2 Sn 2+
  • ⁇ -Ca 3 (PO 4 ) 2 Sn + , ⁇ -Ca 2 P 2 O 7 : Sn, Mn, ⁇ -Ca 3 (PO) 2 : Tr
  • CaS Bi 3+
  • CaSiO 3 Pb + , Mn 2+ , CaSiO 3 : Ti 4+ , CaSr 2 (PO 4 ) 2 : Bi 3+ ,
  • CeMgAlnOi 9 Ce: Tb, Cd 2 B 6 On: Mn 2+ , CdS: Ag + , Cr, CdS: In, CdS: In,
  • GdNb0 Bi 3+, Gd 2 02S: Eu 3+, Gd 2 0 2 Pr 3+, Gd202S: Pr, Ce, F, Gd 2 0 2 S: Tb 3+, Gd 2 Si0 5: Ce 3+, KAIiiOi 7 : TI + , KGanOi 7 : Mn 2+ , K 2 La 2 Ti 3 Oio: Eu, KMgF 3 : Eu 2+ , KMgF 3 : Mn 2+ , K 2 SiF 6 : Mn 4+ , LaAl 3 B40i 2 : Eu 3+ , LaAIB 2 O 6 : Eu 3+ , LaAIO 3 : Eu 3+ , LaAlO 3 : Sm 3+ , LaAsO 4 : Eu 3+ , LaBr 3 : Ce 3+ , LaB0 3 : Eu 3+ , LaCI 3 : Ce 3+ .
  • La 2 O 3 Bi 3+ , LaOBr: Tb 3+ , LaOBr: Tm 3+ , LaOCl: Bi 3+ , LaOCl: Eu 3+ , LaOF: Eu 3+ , La 2 0 3 : Eu 3+ , La 2 0 3 : Pr 3+ , La 2 O 2 S: Tb 3+ , LaP0 4 : Ce 3+ , LaP0 4 : Eu 3+ ,
  • LaSi0 3 Cl Ce 3+
  • LaSiO 3 Cl Ce 3+
  • Tb 3+ LaV0 4 : Eu 3+
  • La 2W 3 Oi 2 Eu 3+
  • LiAIF 4 Mn 2+ , LiAl 5 O 8 : Fe 3+ , LiAlO 2 : Fe 3+ , LiAlO 2 : Mn 2+ , LiAl 5 O 8 : Mn 2+ ,
  • Li2CaP207 Ce 3+, Mn 2+, LiCeBa Si4Oi4 4: Mn 2+, LiCeSrBa 3 Si40i 4: Mn 2+,
  • Mg 3 Si0 3 F 4 Ti 4+ , MgSO 4 : Eu 2+ , MgS0 4 : Pb + , MgSrBa 2 Si 2 O 7: Eu 2+ ,
  • MgSrP 2 0 7 Eu 2+
  • MgSr 5 (PO 4 ) 4 Sn 2+
  • MgSr 3 Si 2 O 8 Eu 2+ , Mn 2+ ,
  • SrGa 2 S 4 Eu 2+
  • SrGa 2 S 4 Pb +
  • Srln 2 0 4 Pr 3+ , Al 3+
  • (Sr, Mg) 3 (PO 4 ) 2 Sn
  • SrMgSi 2 O 6 Eu 2+
  • Sr2MgSi207 Eu +
  • Sr3MgSi208 Eu 2+
  • SrMoO 4 U
  • ⁇ 3 ⁇ 4 ⁇ 2 ⁇ 3+ , YAl 3 B 4 Oi 2: Ce 3+ , YAl 3 B 4 0i 2: Ce 3+ , Mn, YAl 3 B 4 Oi 2 : Ce 3+ , Tb 3+ , YAl 3 B Oi 2 Eu 3+ , YAl 3 B 4 O 2 : Eu 3+ , Cr 3+ , YAl 3 B40i 2: Th + , Ce 3+ I Mn 2+ ,
  • YAI0 3 Ce 3+, Y3AI 5 0i 2: Ce 3+, Y3AI 5 O 2: Cr 3+, YAlO 3: Eu 3+, Y3AI 5 O 2: Eu 3r, Y4AI 2 0 9: Eu 3+, Y3AI 5 Oi 2 : Mn 4+ , YAlO 3 : Sm 3+ , YAlO 3 : Tb 3+ , Y 3 Al 5 Oi 2: Tb 3+ , YAsO 4 : Eu 3+ , YBOs: Ce 3+ , YB0 3 : Eu 3 + , YF 3 : Er 3+ , Yb 3+ , YF 3 : Mn 2+ ,
  • YF 3 Mn 2+ , Th 4+ , YF 3 : Tm 3+ , Yb 3+ , (Y, Gd) B0 3 : Eu, (Y, Gd) B0 3 : Tb,
  • Zn 0 .4Cdo.6S Ag, Zn 0 .6Cd 0 .4S: Ag, (Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF 2 : Mn 2+ , ZnGa 2 0 4 , ZnGa 2 O 4 : Mn 2+ , ZnGa 2 S 4 : Mn 2+ , Zn 2 Ge0 4 : Mn 2+ , (Zn, Mg) F 2 : Mn 2+ , ZnMg 2 (P0 4 ) 2 : Mn 2 + , (Zn, Mg) 3 (PO 4 ) 2 : Mn 2+ , ZnO: Al 3+ , Ga 3+ , ZnO: Bi 3+ ,
  • Zn 2 Si0 Mn + , Zn 2 SiO: Mn + , As 5+ , Zn 2 SiO: Mn, Sb 2 O 2 , Zn 2 SiO: Mn 2+ , P, Zn 2 SiO 4 : Ti 4+ , ZnS: Sn 2+ , ZnS: Sn, Ag, ZnS: Sn 2+ , Li + , ZnS: Te, Mn, ZnS-ZnTe: Mn 2+ , ZnSe: Cu + , Cl and ZnWO 4 .
  • the compound according to the invention shows particular advantages in the mixture with other phosphors of other fluorescent colors or when used in LEDs together with such phosphors.
  • the compounds according to the invention are preferably used together with green-emitting phosphors. It has been shown that the optimization of illumination parameters for white LEDs succeeds particularly well when the inventive compounds are combined with green-emitting phosphors.
  • the compound according to the invention in a further preferred embodiment of the invention, it is preferred to use the compound according to the invention as the sole phosphor.
  • the compound of the invention shows by the broad emission spectrum with a high proportion of red even when used as a single phosphor very good results.
  • the phosphors are arranged on the primary light source, that the red emitting phosphor is substantially illuminated by the light of the primary light source, while the green emitting
  • Substance is substantially illuminated by the light that has already passed through the red emitting phosphor or was scattered by this. This can be realized by mounting the red emitting phosphor between the primary light source and the green emitting phosphor.
  • the phosphors or phosphor combinations according to the invention can be present as bulk material, powder material, thick or thin layer material or self-supporting material, preferably in the form of a film. Furthermore, it may be embedded in a potting material.
  • Phosphors or phosphor combinations according to the invention can be used either in a resin (eg epoxy or silicone resin) as
  • Potting material may be dispersed, or may be placed directly on the primary light source, or spaced therefrom, depending on the application (the latter arrangement also incorporates "remote phosphor technology”).
  • the advantages of "remote phosphor technology” are Known and expert eg in the following publication: Japanese J. of Appl. Phys. Vol. 44, no. 21 (2005), L649-L651.
  • the optical coupling between the phosphor and the primary light source is realized by a light-conducting arrangement.
  • the primary light source is installed at a central location and this is optically coupled to the phosphor by means of light-conducting devices, such as light-conducting fibers. In this way, the lighting requirements adapted lights can only be made of one or more different phosphors, the one to
  • a strong primary light source at a convenient location for the electrical installation and to install without further electrical wiring, but only by laying fiber optics at any location lights of phosphors, which are coupled to the light guide.
  • a lighting unit in particular for the backlight of display devices, characterized in that it contains at least one light source according to the invention, and a display device, in particular liquid crystal display device (LC display), with a backlight, characterized in that it contains at least one illumination unit according to the invention.
  • the particle size of the phosphors according to the invention is usually between 50 nm and 30 ⁇ m for use in LEDs, preferably between 1 and 20 ⁇ m.
  • the phosphors can also be converted into any external forms, such as spherical particles, platelets and structured materials and ceramics. According to the invention, these forms are combined under the term "shaped body.”
  • the shaped body is preferably a "phosphor body”.
  • Another object of the present invention is thus a molding containing the phosphors of the invention.
  • the compounds according to the invention can be prepared more simply and more efficiently than the garnet phosphors known from the prior art.
  • the compounds according to the invention have an emission spectrum with a high proportion of red and they have a high photoluminescence quantum yield.
  • the TQi / 2 values of the compounds according to the invention are usually in the range of more than 500 K.
  • the phase formation of the samples was checked by X-ray diffractometry.
  • the X-ray diffractometer Miniflex II of the company Rigaku with Bragg-Brentano geometry was used.
  • the emission spectra were recorded with a fluorescence spectrometer from Edinburgh Instruments Ltd., equipped with a mirror optics for powder samples, at an excitation wavelength of 450 nm.
  • the excitation source used was a 450 W Xe lamp.
  • the spectrometer was equipped with a cryostat from Oxford Instruments (MicrostatN2). Nitrogen was used as the coolant.
  • Reflectance spectra were measured with a fluorescence spectrometer from Edinburgh Instruments Ltd. certainly. The samples were placed in a BaS04 coated Ulbricht sphere and measured. Reflectance spectra were recorded in a range of 250 to 800 nm.
  • the white standard used was BaS0 4 (Alfa Aesar 99.998%).
  • Xe lamp served as an excitation source.
  • the excitation spectra were recorded with a fluorescence spectrometer from Edinburgh Instruments Ltd., equipped with a mirror optics for powder samples, at 550 nm. As a source of inspiration was a
  • Example 3 Production and measurement of LEDs using the phosphors
  • a mass of mLS (in g) of the phosphor listed in the respective LED example is weighed and mixed with nrtsiiikon (in g) of an optically transparent silicone and then homogeneously mixed in a planetary centrifugal mixer, so that the phosphor concentration in the total mass o_s (in % By weight).
  • the resulting silicone-phosphor mixture is applied by means of an automatic dispenser on the chip of a blue semiconductor LED and cured with heat.
  • the reference LED listed in the present examples for LED characterization was filled with pure silicone without phosphor.
  • the blue semiconductor LEDs used have a
  • the light-technical characterization of the LEDs is carried out with a spectrometer from the company Instrument Systems - spectrometer CAS 140 and an associated integrating sphere ISP 250.
  • the spectrum thus obtained of the light emitted by the LED is used to calculate the color point coordinates CIE x and y.
  • Table 1 Composition and properties of the manufactured reference LED, LED A and LED B.
  • Figure 1 powder X-ray diffractogram for Cu-K a radiation of
  • Figure 2 powder X-ray diffractogram for Cu-K a radiation of
  • FIG. 4 excitation spectrum of
  • FIG. 11 Spectrum of the LED A containing
  • FIG. 12 Spectrum of the LED B containing ⁇ 2.9875 ⁇ 0 . ⁇ 25 ⁇ 4 , 975 ⁇ , ⁇ 25 ⁇ 2.

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  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne des luminophores à base de grenat activés par Mn, un procédé pour les préparer, ainsi que leur utilisation en tant que luminophores de conversion. L'invention concerne en outre un matériau de conversion d'émission comprenant au moins le luminophore de conversion selon l'invention, ainsi que son utilisation dans des sources lumineuses, en particulier dans des dispositifs LED à conversion par phosphore (pc-LED : phosphor converted light emitting devices). L'invention concerne en outre des sources lumineuses, en particulier des pc-LED et des modules d'éclairage comprenant une source lumineuse primaire et le luminophore de conversion ou le matériau de conversion d'émission selon l'invention.
PCT/EP2016/001938 2015-12-01 2016-11-18 Luminophores activés par mn WO2017092849A1 (fr)

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DE102015015355.2A DE102015015355A1 (de) 2015-12-01 2015-12-01 Mn-aktivierte Leuchtstoffe

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CN111269717A (zh) * 2020-04-02 2020-06-12 常熟理工学院 一种白光led用复合钙钛矿红色荧光粉及其制备方法
CN112262198A (zh) * 2018-03-20 2021-01-22 礼泰克资产管理有限公司 作为基于LED的固态光源的转换发光体的Mn活化的卤氧化物

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TWI732041B (zh) * 2017-09-14 2021-07-01 美商現代照明解決方案公司 具有發射紅光磷光體之複合材料
CN108441218B (zh) * 2018-05-21 2021-04-23 沈阳化工大学 一种红色荧光粉及其制备方法
EP3831911B1 (fr) * 2019-12-05 2022-06-08 Friedrich-Alexander-Universität Erlangen-Nürnberg Convertisseur composite de longueur d'onde
CN115678556B (zh) * 2022-10-17 2023-10-03 闽都创新实验室 一种长余辉闪烁晶体及其制备方法和应用

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CN112262198A (zh) * 2018-03-20 2021-01-22 礼泰克资产管理有限公司 作为基于LED的固态光源的转换发光体的Mn活化的卤氧化物
CN112262198B (zh) * 2018-03-20 2023-04-04 礼泰克资产管理有限公司 作为基于LED的固态光源的转换发光体的Mn活化的卤氧化物
CN111269717A (zh) * 2020-04-02 2020-06-12 常熟理工学院 一种白光led用复合钙钛矿红色荧光粉及其制备方法
CN111269717B (zh) * 2020-04-02 2022-09-23 常熟理工学院 一种白光led用复合钙钛矿红色荧光粉及其制备方法

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