EP1305833A1 - Illumination device with at least one led as the light source - Google Patents

Illumination device with at least one led as the light source

Info

Publication number
EP1305833A1
EP1305833A1 EP01956394A EP01956394A EP1305833A1 EP 1305833 A1 EP1305833 A1 EP 1305833A1 EP 01956394 A EP01956394 A EP 01956394A EP 01956394 A EP01956394 A EP 01956394A EP 1305833 A1 EP1305833 A1 EP 1305833A1
Authority
EP
European Patent Office
Prior art keywords
phosphor
lighting unit
unit according
white light
metals
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP01956394A
Other languages
German (de)
French (fr)
Inventor
Dieter Bokor
Andries Ellens
Günter Huber
Franz Zwaschka
Frank Jermann
Manfred Kobusch
Michael Ostertag
Wolfgang Rossner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osram GmbH
Ams Osram International GmbH
Original Assignee
Osram Opto Semiconductors GmbH
Patent Treuhand Gesellschaft fuer Elektrische Gluehlampen mbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Osram Opto Semiconductors GmbH, Patent Treuhand Gesellschaft fuer Elektrische Gluehlampen mbH filed Critical Osram Opto Semiconductors GmbH
Priority to EP08158704.0A priority Critical patent/EP1970970B1/en
Publication of EP1305833A1 publication Critical patent/EP1305833A1/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01L33/504—Elements with two or more wavelength conversion materials
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
    • C09K11/584—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/641—Chalcogenides
    • C09K11/642—Chalcogenides with zinc or cadmium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7732—Halogenides
    • C09K11/7733—Halogenides with alkali or alkaline earth metals
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates
    • C09K11/7796—Phosphates with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/886—Chalcogenides with rare earth metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention is based on a lighting unit with at least one LED as a light source according to the preamble of claim 1. It is in particular a luminescence conversion LED emitting in the visible or white, based on an LED emitting primarily in the near UV or short-wave blue.
  • LEDs that emit white light are currently mainly produced by the combination of a Ga (ln) N LED emitting in the blue at about 460 nm and a yellow emitting YAG: Ce 3+ phosphor (US Pat. No. 5,998,925 and EP 862 794).
  • these white light LEDs are of limited use for general lighting purposes because of their poor color rendering due to the lack of color components (especially the red component). Instead, attempts are also being made to combine primarily blue-emitting LEDs with several phosphors in order to improve the color rendering, see WO 00/33389 and WO 00/33390.
  • BaMgAl 10 O 17 : Eu 2+ or ZnS: Ag + are known as inorganic phosphors; as a blue-green component ZnS: Cu + , or (Zn, Cd) S: Cu + , or ZnS: (Al, Cu) + ; as red component Y 2 O 2 S: Eu 2+ .
  • a number of organic phosphors are also recommended. For white emitting sources of high light quality with small dimensions or as backlighting from e.g. B. LCDs, fluorescent lamps and incandescent lamps are not very suitable. OLEDs are more suitable for this, but the UV resistance of organic phosphors is poorer than that of inorganic phosphors. In addition, the manufacturing costs are higher.
  • Blue LEDs with the phosphor YAG: Ce 3+ (and garnets derived from them) are also suitable in principle, but there are disadvantages in the color locus setting: the color locus can only be selected to a limited extent in such a way that white light is produced which enables good color rendering, since the white color impression is primarily caused by the mixture of blue emission from the LED and yellow emission from the phosphor.
  • the disadvantage of fluorescent lamps and UN (O) LEDs is that UV energy is converted into visible light with poor energy efficiency: UV radiation (in fluorescent lamps 254 and 365 nm; in UV LEDs 300 - 370 nm) with a wavelength of z. B. 254 nm is converted into light with a wavelength of 450-650 nm. This means an energy loss of 40 to 60% with a theoretical quantum efficiency of 100%.
  • Organic phosphors are generally more difficult to produce than inorganic phosphors and, moreover, are generally too unstable to be used in light sources with a long service life (eg over 30,000 hours).
  • the invention is particularly advantageous in connection with the development of an LED emitting in the visible or white.
  • This LED can be produced by combining an LED emitting in near UV or very short-wave blue light (here collectively referred to as “short-wave”) with an emission wavelength between 370 and 430 nm and at least one of the phosphors listed below, which emits the radiation of the LED entirely or partially absorbed and even emitted in spectral ranges, the additive mixture of which with the light from the LED and / or other dyes gives white light with good color rendering or light with a desired color location, depending on the application, a single phosphor with the properties according to the invention may be sufficient it can also be combined with one or more other phosphors according to the invention or phosphors of other classes, for example of the YAG: Ce type.
  • the blue light of the LED cannot be used here (or can hardly be used), in contrast to the prior art, the longer-wave blue ( 430 to 480 nm) is used, but is suitable s
  • a primary radiation source whose emission is much closer to the wavelength at which the phosphors emit can significantly increase energy efficiency. For example, with a source that emits at 400 nm, the energy loss is reduced to only 12 to 39%.
  • the technical problem lies in the development and production of sufficiently efficient phosphors that can be excited in the spectral range between 370 nm and 430 nm and at the same time show suitable emission behavior.
  • a phosphor according to the invention is combined with a binder that is as transparent as possible (EP 862 794).
  • the phosphor completely or partially absorbs the light from the UV / blue light-emitting LED and emits it again broadband in other spectral ranges, so that an overall emission with the desired color location is produced. So far, there are hardly any phosphors that meet these requirements as well as the phosphors described here. she show a high quantum efficiency (typically 70%) and at the same time a spectral emission, which is perceived as bright due to the sensitivity of the eye.
  • the color locus can be set in a wide range.
  • the advantages of these phosphors also include their relatively easy, environmentally friendly producibility, their non-toxicity and their relatively high chemical stability.
  • the invention relates in particular to a lighting unit with at least one LED as a light source (light emitting diode), which generates special, specifically desired color tones (for example magenta) or which, for example, generates white light by using a primarily short-wave (i.e. UV to blue in the range from 370 to 430 nm) ) emitting radiation is converted into white by means of several phosphors: either by mixing the secondary radiation of a blue and yellow emitting phosphor or in particular by RGB mixture of three phosphors which emit red, green and blue. For particularly high demands on color rendering, more than three phosphors can also be combined.
  • a light source light emitting diode
  • special, specifically desired color tones for example magenta
  • white light by using a primarily short-wave (i.e. UV to blue in the range from 370 to 430 nm) ) emitting radiation is converted into white by means of several phosphors: either by mixing the secondary radiation of a blue and yellow emitting
  • one of the phosphors used according to the invention can also be combined with other phosphors already known for this use, such as, for example, SrS: Eu (WO 00/33390) or YAG: Ce (US Pat. No. 5,998,925).
  • a Ga (ln, Al) N LED is particularly suitable as the primary short-wave emitting LED, but also any other way of producing a short-wave LED with a primary emission in the range 370 to 430 nm.
  • the invention extends the spectral emission characteristics of LEDs by using other phosphors and their mixtures beyond the current state of knowledge (see Tables 1 to 3).
  • the selection of the phosphors and mixtures used can be made in such a way that, in addition to true-color white, other mixed colors with broadband emission are also generated.
  • the light emitted by the LED is absorbed by the mixture that contains phosphors. This mixture is either applied directly to the LED or dispersed in a resin or silicone or applied to a transparent disc over one LED or applied to a transparent disc over several LEDs.
  • the inventive step is that by using LEDs with emission wavelengths between 370 and 430 nm (invisible or barely visible deep blue) and the use of phosphors listed below, an improved spectral adjustment of the LED emission is made possible and any color locations can be set, with a higher energy efficiency than with conventional LEDs.
  • Inorganic phosphors that can be excited with a relatively long wavelength are hardly known at present. Surprisingly, however, it has been shown that there are a number of inorganic phosphors which are suitable for being efficiently excited with radiation having a peak emission wavelength of 370-430 nm. Typical half-value widths of the emission are 20 nm to 50 nm.
  • the absorption of the phosphors can be controlled by the selected structural parameters and chemical composition.
  • Such phosphors all have a relatively small band gap (typically around 3 eV) or they have a strong crystal field for the ion, which absorbs the UV / blue light emitted by the LED around 400 nm.
  • certain combinations of phosphors can be selected in the phosphor mixture.
  • the most suitable phosphor mixture therefore depends on the chosen target (color rendering, color location, color temperature) and the existing LED emission wavelength.
  • any phosphor that fulfills the conditions mentioned above is suitable for use.
  • Phosphors which emit efficiently and which can be excited or at least partially excited in the 370-430 nm region are listed in the following tables.
  • Tab. 1 describes suitable blue phosphors with a peak emission wavelength of 440 to 485 nm
  • Tab. 2 suitable green phosphors with a peak emission wavelength of 505 to 550 nm
  • Tab. 3 suitable red phosphors with a peak emission wavelength of 560 to 670 nm This makes it possible for the first time to manufacture LEDs with high efficiency, which are based on a short-wave emitting diode that excites several phosphors.
  • Table 1 Blue-emitting phosphors:
  • M s (PO 4 ) 3 (X): Eu 2+ with M at least one of the metals Ba, Ca alone or in
  • M * 3MgSi2O8: Eu2 + with M at least one of the metals Ba, Ca, Sr alone or in combination
  • M ** MgA110O17: Eu2 + with M ** at least one of the metals Eu, Sr alone or in combination with Ba (Ba fraction is preferably at most 75%);
  • Eu share in the activator Ak is preferably> 50%;
  • (Zn, Cd) S Ag + where Zn and Cd are only used in combination; Zn is preferably ⁇ Cd;
  • (Ml) 2 (M2) (BO3) 2: Eu2 + with Ml at least one of the metals Ba, Sr; and with M2 is at least one of the metals Mg, Ca; the proportion of Ba in the cation Ml is preferably at least 80%; the proportion of Mg in metal M2 is preferably at least 70%.
  • GalnN or GaN or GalnAlN is preferably used as the UV diode (primary radiation source). For example, it has a peak wavelength of 400 nm and a full width at half maximum of 20 nm.
  • the diode substrate is coated directly or indirectly with a suspension of three phosphors, each with an emission maximum in the red, green and blue spectral range. At least one of these phosphors is selected from Tables 1 to 3 and is combined either with known phosphors or with phosphors from the other tables.
  • the phosphor mixture is baked at about 200 ° C. A color rendering of typically 80 is thus achieved.
  • Figure 1 is a semiconductor device that serves as a light source (LED) for white light;
  • Figure 2 shows a lighting unit with phosphors according to the present
  • 3 to 17 show the emission spectrum of LEDs with different phosphor mixtures according to the present invention.
  • the light source is a semiconductor component (chip 1) of the InGaN type with a peak emission wavelength of 420 nm and a half-width of 25 nm with a first and second electrical connection 2, 3, which is embedded in an opaque basic housing 8 in the region of a recess 9 , One of the connections 3 is connected to the chip 1 via a bonding wire 14.
  • the recess has a wall 17 which serves as a reflector for the blue primary radiation of the chip 1.
  • the recess 9 is filled with a potting compound 5, the main components of which are an epoxy casting resin (80 to 90% by weight) and phosphor pigments 6 (less contains less than 15% by weight). Other small proportions include methyl ether and Aerosil.
  • the phosphor pigments are a mixture.
  • the first conversion phosphor is selected from Table 1.
  • the second phosphor is selected from Tab. 2 and the third from Tab. 3.
  • FIG. 2 shows a section of a surface light 20 as a lighting unit. It consists of a common carrier 21 onto which a cuboid outer housing 22 is glued. Its top is provided with a common cover 23.
  • the cuboid housing has cutouts in which individual semiconductor components 24 are accommodated. They are UV-emitting light-emitting diodes with a peak emission of 380 nm.
  • the conversion to white light takes place by means of conversion layers which are seated directly in the casting resin of the individual LEDs, as described in FIG. 1, or layers 25 which are attached to all surfaces accessible to UV radiation are. These include the inner surfaces of the side walls of the housing, the cover and the base part.
  • the conversion layers 25 consist of three phosphors which emit in the yellow, green and blue spectral range using at least one of the phosphors according to the invention from Tables 1 to 3.
  • Tab. 6 shows 15 exemplary embodiments of specific combinations of phosphors from Tab. 4 in connection with a primary light source (UV-LED) with an emission peak in the range 370 to 420 nm.
  • UV-LED primary light source
  • the individual UV diodes are summarized in Tab. 5, in which the emission peak and the color location (as far as defined, that is from 380 nm) of the individual diodes is given.
  • the UV diode does not provide any part in the secondary emission, also because of the strong absorption by the three phosphors.
  • the diode delivers a small proportion of the blue, which increases with increasing wavelength, in addition to the blue phosphor. This proportion appears in Table 5 as an additional fourth contribution.
  • the particularly suitable phosphors for use in three-color mixtures under primary irradiation at 370 to 420 nm are the blue-emitting phosphors No. 2, 4 and 6, and the green-emitting phosphors 8, 9, 10, 13, 15, 16, 17 and 18 as well as the red-emitting phosphors 26, 28 and 29.
  • Exemplary embodiment no. 15 uses a blue-emitting diode with 420 nm peak emission with such a high intensity that it can fully replace the blue phosphor and only requires two additional phosphors in the green and red.

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Abstract

The invention relates to a luminescence conversion LED based illumination device that emits primarily radiation in the range of from 370 and 430 nm of the optical spectrum (peak wavelength). Said radiation is converted to radiation having a longer wavelength using three luminescent substances that emit in the red, green and blue range.

Description

Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH., MünchenPatent trust company for electric light bulbs mbH., Munich
Beleuchtungseinheit mit mindestens einer LED als LichtquelleLighting unit with at least one LED as a light source
Technisches GebietTechnical field
Die Erfindung geht aus von einer Beleuchtungseinheit mit mindestens einer LED als Lichtquelle gemäß dem Oberbegriff des Anspruchs 1. Es handelt sich insbesondere um eine im Sichtbaren oder Weißen emittierenden Lumineszenz-Konversions-LED auf der Basis einer primär im nahen UV oder kurzwelligen Blau emittierenden LED.The invention is based on a lighting unit with at least one LED as a light source according to the preamble of claim 1. It is in particular a luminescence conversion LED emitting in the visible or white, based on an LED emitting primarily in the near UV or short-wave blue.
Stand der TechnikState of the art
LEDs, die weißes Licht abgeben, werden derzeit vorwiegend durch die Kombination einer im Blauen bei etwa 460 nm emittierenden Ga(ln)N-LED und eines gelb emittierenden YAG:Ce3+-Leuchtstoffs erzeugt (US 5 998 925 und EP 862 794). Allerdings sind diese Weißlicht-LEDs für Zwecke der Allgemeinbeleuchtung wegen ihrer schlechten Farbwiedergabe aufgrund fehlender Farbkomponenten (vor allem der Rot-Komponente) nur eingeschränkt zu gebrauchen. Statt dessen wird auch versucht, primär blau emittierende LEDs mit mehreren Leuchtstoffen zu kombinieren um die Farbwiedergabe zu verbessern, siehe WO 00/33389 und WO 00/33390.LEDs that emit white light are currently mainly produced by the combination of a Ga (ln) N LED emitting in the blue at about 460 nm and a yellow emitting YAG: Ce 3+ phosphor (US Pat. No. 5,998,925 and EP 862 794). , However, these white light LEDs are of limited use for general lighting purposes because of their poor color rendering due to the lack of color components (especially the red component). Instead, attempts are also being made to combine primarily blue-emitting LEDs with several phosphors in order to improve the color rendering, see WO 00/33389 and WO 00/33390.
Grundsätzlich ist außerdem bekannt, weiß emittierende LEDs auch mit sogenannten organischen LEDs zu realisieren oder durch Zusammenschalten monochromer LEDs mit entsprechender Farbmischung. Meist wird eine UV LED (Emissionsmaximum zwischen 300 und 370 nm) verwendet, die mittels mehrerer Leuchtstoffe, meist drei, die i roten, grünen und blauen Spektralbereich emittieren (RGB- Mischung) in weißes Licht umgewandelt werden (WO 98 39 805, WO 98 39 807 und WO 97 48 138). Als blaue Komponente sind als anorganische Leuchtstoffe BaMgAl10O17:Eu2+ oder ZnS:Ag+ bekannt; als blaugrüne Komponente ZnS:Cu+, oder (Zn,Cd)S:Cu+, oder ZnS:(Al,Cu)+; als rote Komponente Y2O2S:Eu2+. Außerdem wird eine Reihe organischer Leuchtstoffe empfohlen. Für weiß emittierende Quellen von hoher Lichtqualität mit kleinen Dimensionen oder als Hintergrundbeleuchtung von z. B. LCDs sind Leuchtstofflampen und Glühlampen wenig geeignet. OLEDs sind dazu zwar besser geeignet, allerdings ist die UV-Beständigkeit von organischen Leuchtstoffen im Vergleich zu anorganische Leuchtstoffen schlechter. Außerdem sind die Herstellkosten höher. Blaue LEDs mit dem Leuchtstoff YAG:Ce3+ (und davon abgeleiteten Granaten) sind prinzipiell ebenfalls geeignet, jedoch bestehen Nachteile in der Farborteinstellung: Nur in beschränkter Weise kann der Farbort derart gewählt werden, dass weißes Licht entsteht, das eine gute Farbwiedergabe ermöglicht, da der weiße Farbeindruck primär durch die Mischung blauer Emission der LED und gelber Emission des Leuchtstoffs entsteht. Der Nachteil von Leuchtstofflampen und UN-(O)LEDs besteht darin, dass UV-Energie in sichtbares Licht mit einer schlechten Energieeffizienz umgewandelt wird: UV-Strahlung (in Leuchtstofflampen 254 und 365 nm; in UV LEDs 300 - 370 nm) einer Wellenlänge von z. B. 254 nm wird umgewandelt in Licht mit einer Wel- lenlänge von 450-650 nm. Das bedeutet einen Energieverlust von 40 bis 60 % bei einer theoretischen Quanteneffizienz von 100%.Basically, it is also known to implement white-emitting LEDs with so-called organic LEDs or by interconnecting monochrome LEDs with a corresponding color mixture. Usually a UV LED (emission maximum between 300 and 370 nm) is used, which is converted into white light by means of several phosphors, usually three, which emit red, green and blue spectral range (RGB mixture) (WO 98 39 805, WO 98 39 807 and WO 97 48 138). As the blue component, BaMgAl 10 O 17 : Eu 2+ or ZnS: Ag + are known as inorganic phosphors; as a blue-green component ZnS: Cu + , or (Zn, Cd) S: Cu + , or ZnS: (Al, Cu) + ; as red component Y 2 O 2 S: Eu 2+ . A number of organic phosphors are also recommended. For white emitting sources of high light quality with small dimensions or as backlighting from e.g. B. LCDs, fluorescent lamps and incandescent lamps are not very suitable. OLEDs are more suitable for this, but the UV resistance of organic phosphors is poorer than that of inorganic phosphors. In addition, the manufacturing costs are higher. Blue LEDs with the phosphor YAG: Ce 3+ (and garnets derived from them) are also suitable in principle, but there are disadvantages in the color locus setting: the color locus can only be selected to a limited extent in such a way that white light is produced which enables good color rendering, since the white color impression is primarily caused by the mixture of blue emission from the LED and yellow emission from the phosphor. The disadvantage of fluorescent lamps and UN (O) LEDs is that UV energy is converted into visible light with poor energy efficiency: UV radiation (in fluorescent lamps 254 and 365 nm; in UV LEDs 300 - 370 nm) with a wavelength of z. B. 254 nm is converted into light with a wavelength of 450-650 nm. This means an energy loss of 40 to 60% with a theoretical quantum efficiency of 100%.
Organische Leuchtstoffe sind im allgemeinen schwieriger herzustellen als anorganische Leuchtstoffe, und sind darüber hinaus im allgemeinen zu instabil, um in Lichtquellen hoher Lebensdauer (z. B. über 30.000 Stunden) eingesetzt werden zu kön- nen.Organic phosphors are generally more difficult to produce than inorganic phosphors and, moreover, are generally too unstable to be used in light sources with a long service life (eg over 30,000 hours).
Dieser Stand der Technik hat einige bedeutende Nachteile hinsichtlich der Energieeffizienz der Kombination aus LED und Leuchtstoffen und /oder der Stabilität der Leuchtstoffe und /oder Beschränkungen hinsichtlich der geometrischen Dimensionen.This prior art has some significant disadvantages with regard to the energy efficiency of the combination of LEDs and phosphors and / or the stability of the phosphors and / or restrictions with regard to the geometric dimensions.
Darstellung der ErfindungPresentation of the invention
Es ist Aufgabe der vorliegenden Erfindung, eine Beleuchtungseinheit mit mindestens einer LED als Lichtquellegemäß dem Oberbegriff des Anspruchs 1 bereitzustellen, die sich durch hohe Effizienz auszeichnet. Diese Aufgaben werden durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst. Besonders vorteilhafte Ausgestaltungen finden sich in den abhängigen Ansprüchen.It is an object of the present invention to provide a lighting unit with at least one LED as a light source according to the preamble of claim 1, which is characterized by high efficiency. These objects are achieved by the characterizing features of claim 1. Particularly advantageous configurations can be found in the dependent claims.
Die Erfindung ist besonders vorteilhaft im Zusammenhang mit der Entwicklung einer im Sichtbaren bzw. Weißen emittierenden LED. Diese LED kann hergestellt werden durch Kombination einer im nahen UV oder sehr kurzwelligem blaues Licht (hier zusammenfassend als „kurzwellig" bezeichnet) emittierenden LED mit einer Emissionswellenlänge zwischen 370 und 430 nm und mindestens einem der unten angeführten Leuchtstoffe, der die Strahlung der LED ganz oder teilweise absorbiert und selbst in Spektralbereichen emittiert, deren additive Mischung mit dem Licht der LED und /oder anderen Farbstoffe weißes Licht mit guter Farbwiedergabe oder Licht mit einem gewünschten Farbort ergibt. Je nach Anwendung kann ein einziger Leuchtstoff mit den erfindungsgemäßen Eigenschaften ausreichen. Evtl. kann er auch mit einem oder mehreren anderen erfindungsgemäßen Leuchtstoffen oder Leuchtstoffen anderer Klassen, beispielsweise vom Typ YAG:Ce, kombiniert werden. Das blaue Licht der LED ist hier nicht (oder kaum) direkt nutzbar, im Gegensatz zum Stand der Technik, der längerwelliges Blau (430 bis 480 nm) verwendet, sondern eignet sich nur zur primären Anregung der Leuchtstoffe.The invention is particularly advantageous in connection with the development of an LED emitting in the visible or white. This LED can be produced by combining an LED emitting in near UV or very short-wave blue light (here collectively referred to as “short-wave”) with an emission wavelength between 370 and 430 nm and at least one of the phosphors listed below, which emits the radiation of the LED entirely or partially absorbed and even emitted in spectral ranges, the additive mixture of which with the light from the LED and / or other dyes gives white light with good color rendering or light with a desired color location, depending on the application, a single phosphor with the properties according to the invention may be sufficient it can also be combined with one or more other phosphors according to the invention or phosphors of other classes, for example of the YAG: Ce type. The blue light of the LED cannot be used here (or can hardly be used), in contrast to the prior art, the longer-wave blue ( 430 to 480 nm) is used, but is suitable s I only for the primary stimulation of the phosphors.
Eine primäre Strahlungsquelle, deren Emission viel näher an der Wellenlän- ge liegt, bei der die Leuchtstoffe emittieren, kann die Energieeffizienz erheblich steigern. Bei einer Quelle, die bei 400 nm emittiert, reduziert sich zum Beispiel der Energie- Verlust schon auf nur noch 12 bis 39%.A primary radiation source whose emission is much closer to the wavelength at which the phosphors emit can significantly increase energy efficiency. For example, with a source that emits at 400 nm, the energy loss is reduced to only 12 to 39%.
Das technische Problem liegt in der Entwicklung und Produktion ausreichend effizienter Leuchtstoffe, die im spektralen Bereich zwischen 370 nm und 430 nm an- regbar sind und gleichzeitig ein passendes Emissionsverhalten zeigen.The technical problem lies in the development and production of sufficiently efficient phosphors that can be excited in the spectral range between 370 nm and 430 nm and at the same time show suitable emission behavior.
Um eine farbige oder weiße LED zu realisieren, wird ein erfindungsgemäßer Leuchtstoff, evtl. in Verbindung mit einem oder mehreren anderen Leuchtstoffen mit einem möglichst transparenten Bindemittel kombiniert (EP 862 794). Der Leuchtstoff absorbiert das Licht der UV/Blau-Licht emittierenden LED ganz oder teilweise und emittiert es in anderen Spektralbereichen wieder breitbandig, so dass eine Gesamtemission mit gewünschtem Farbort entsteht. Bisher gibt es kaum Leuchtstoffe, die diese Anforderungen so gut erfüllen wie die hier beschriebenen Leuchtstoffe. Sie zeigen eine hohe Quanteneffizienz (typisch 70 %) und gleichzeitig eine spektrale Emission, die aufgrund der Empfindlichkeit des Auges als hell empfunden wird. Der Farbort lässt sich in einem weiten Bereich einstellen. Zu den Vorteilen dieser Leuchtstoffe zählen außerdem ihre relativ leichte, umweltschonende Herstellbarkeit, seine Ungiftigkeit und seine relativ hohe chemische Stabilität.In order to implement a colored or white LED, a phosphor according to the invention, possibly in combination with one or more other phosphors, is combined with a binder that is as transparent as possible (EP 862 794). The phosphor completely or partially absorbs the light from the UV / blue light-emitting LED and emits it again broadband in other spectral ranges, so that an overall emission with the desired color location is produced. So far, there are hardly any phosphors that meet these requirements as well as the phosphors described here. she show a high quantum efficiency (typically 70%) and at the same time a spectral emission, which is perceived as bright due to the sensitivity of the eye. The color locus can be set in a wide range. The advantages of these phosphors also include their relatively easy, environmentally friendly producibility, their non-toxicity and their relatively high chemical stability.
Die Erfindung betrifft insbesondere eine Beleuchtungseinheit mit mindestens einer LED als Lichtquelle (light emitting diode), die besondere spezifisch gewünschte Farbtöne erzeugt (beispielsweise Magenta) oder die beispielsweise weißes Licht erzeugt, indem eine primär kurzwellig (also UV bis blau im Bereich 370 bis 430 nm) emittierende Strahlung mittels mehrerer Leuchtstoffe in Weiß konvertiert wird: entweder durch Mischung der sekundären Strahlung eines blau und gelb emittierenden Leuchtstoffs oder insbesondere durch RGB-Mischung aus drei Leuchtstoffen die rot, grün und blau emittieren. Für besonders hohe Anforderungen an die Farbwiedergabe können auch mehr als drei Leuchtstoffe kombiniert werden. Zu diesem Zweck kann auch einer der erfindungsgemäß eingesetzten Leuchtstoffe mit anderen, bereits für diese Verwendung bekannten Leuchtstoffen wie beispielsweise SrS:Eu (WO 00/33390) oder YAG:Ce (US 5 998 925) kombiniert werden.The invention relates in particular to a lighting unit with at least one LED as a light source (light emitting diode), which generates special, specifically desired color tones (for example magenta) or which, for example, generates white light by using a primarily short-wave (i.e. UV to blue in the range from 370 to 430 nm) ) emitting radiation is converted into white by means of several phosphors: either by mixing the secondary radiation of a blue and yellow emitting phosphor or in particular by RGB mixture of three phosphors which emit red, green and blue. For particularly high demands on color rendering, more than three phosphors can also be combined. For this purpose, one of the phosphors used according to the invention can also be combined with other phosphors already known for this use, such as, for example, SrS: Eu (WO 00/33390) or YAG: Ce (US Pat. No. 5,998,925).
Als primär kurzwellig emittierende LED eignet sich insbesondere eine Ga(ln,AI)N- LED, aber auch jeder andere Weg zur Erzeugung einer kurzwelligen LED mit einer primären Emission im Bereich 370 bis 430 nm.A Ga (ln, Al) N LED is particularly suitable as the primary short-wave emitting LED, but also any other way of producing a short-wave LED with a primary emission in the range 370 to 430 nm.
Die Erfindung erweitert die spektrale Emissionscharakteristik von LEDs indem über den gegenwärtige Kenntnisstand hinaus weitere Leuchtstoffe und deren Mischungen Anwendung finden (siehe Tab. 1 bis 3). Dabei kann die Auswahl der angewendeten Leuchtstoffe und Mischungen hiervon so getroffen werden, das neben farbechten Weiß auch andere Mischfarben mit breitbandiger Emission erzeugt werden. Generell wird das emittierte Licht der LED von der Mischung, die Leuchtstoffe enthält, absorbiert. Diese Mischung ist entweder direkt auf der LED aufgebracht oder in einem Harz oder Silikon dispergiert oder aufgebracht auf einer transparenten Scheibe über einer LED oder aufgebracht auf einer transparenten Scheibe über mehreren LEDs.The invention extends the spectral emission characteristics of LEDs by using other phosphors and their mixtures beyond the current state of knowledge (see Tables 1 to 3). The selection of the phosphors and mixtures used can be made in such a way that, in addition to true-color white, other mixed colors with broadband emission are also generated. In general, the light emitted by the LED is absorbed by the mixture that contains phosphors. This mixture is either applied directly to the LED or dispersed in a resin or silicone or applied to a transparent disc over one LED or applied to a transparent disc over several LEDs.
Der erfinderische Schritt besteht darin, dass durch die Verwendung von LEDs mit Emissionswellenlängen zwischen 370 und 430 nm (unsichtbar oder kaum sichtbares tiefblau) und die Verwendung von Leuchtstoffen, die unten aufgelistet sind, eine verbesserte spektrale Anpassung der LED-Emission ermöglicht wird und beliebige Farborte einstellbar werden, und zwar mit einer höheren Energieeffizienz als mit den konventionellen LEDs.The inventive step is that by using LEDs with emission wavelengths between 370 and 430 nm (invisible or barely visible deep blue) and the use of phosphors listed below, an improved spectral adjustment of the LED emission is made possible and any color locations can be set, with a higher energy efficiency than with conventional LEDs.
Anorganische Leuchtstoffe, die relativ langwellig anregbar sind, sind derzeit kaum bekannt. Überraschenderweise hat sich jedoch gezeigt, dass es eine Anzahl von anorganischen Leuchtstoffen gibt, die geeignet sind, um mit Strahlung einer Peak- Emissions-Wellenlänge von 370-430 nm noch effizient angeregt zu werden. Typische Halbwertsbreiten der Emission liegen bei 20 nm bis 50 nm. Die Absorption der Leuchtstoffe kann durch die gewählten Strukturparameter und chemische Zusammensetzung gesteuert werden. Solche Leuchtstoffe haben alle eine relativ kleine Bandlücke (typisch etwa 3 eV) oder sie haben ein starkes Kristallfeld für das Ion, welches das von der LED emittierte UV/Blau -Licht um 400 nm absorbiert.Inorganic phosphors that can be excited with a relatively long wavelength are hardly known at present. Surprisingly, however, it has been shown that there are a number of inorganic phosphors which are suitable for being efficiently excited with radiation having a peak emission wavelength of 370-430 nm. Typical half-value widths of the emission are 20 nm to 50 nm. The absorption of the phosphors can be controlled by the selected structural parameters and chemical composition. Such phosphors all have a relatively small band gap (typically around 3 eV) or they have a strong crystal field for the ion, which absorbs the UV / blue light emitted by the LED around 400 nm.
Abhängig von der gewählten Lumineszenzwellenlänge der LED (370-430 nm) und abhängig von der gewünschten Farbwiedergabe und /oder dem gewünschten Farbort können bestimmte Kombinationen von Leuchtstoffen in der Leuchtstoffmischung gewählt werden. Die am besten geeignete Leuchtstoffmischung ist somit vom gewählten Ziel (Farbwiedergabe, Farbort, Farbtemperatur) und der vorhandenen LED-Emissionswellenlänge abhängig.Depending on the selected luminescence wavelength of the LED (370-430 nm) and depending on the desired color rendering and / or the desired color location, certain combinations of phosphors can be selected in the phosphor mixture. The most suitable phosphor mixture therefore depends on the chosen target (color rendering, color location, color temperature) and the existing LED emission wavelength.
Jeder Leuchtstoff, der die oben erwähnten Bedingungen erfüllt, ist im Prinzip geeignet für die Anwendung. Leuchtstoffe, die effizient emittieren und im Gebiet von 370-430 nm effizient anregbar oder zumindest teilweise anregbar sind, sind in den folgenden Tabellen aufgeführt. Tab. 1 beschreibt geeignete blaue Leuchtstoffe mit einer Wellenlänge der Peakemission von 440 bis 485 nm, Tab. 2 geeignete grüne Leuchtstoffe mit einer Wellenlänge der Peakemission von 505 bis 550 nm und Tab. 3 geeignete rote Leuchtstoffe mit Wellenlänge der Peakemission von 560 bis 670 nm. Damit ist es erstmals möglich, LEDs mit hoher Effizienz herzustellen, die auf einer kurzwellig emittierenden Diode basieren, die mehrere Leuchtstoffe anregt. Tabelle 1: Blau emittierende Leuchtstoffe:In principle, any phosphor that fulfills the conditions mentioned above is suitable for use. Phosphors which emit efficiently and which can be excited or at least partially excited in the 370-430 nm region are listed in the following tables. Tab. 1 describes suitable blue phosphors with a peak emission wavelength of 440 to 485 nm, Tab. 2 suitable green phosphors with a peak emission wavelength of 505 to 550 nm and Tab. 3 suitable red phosphors with a peak emission wavelength of 560 to 670 nm This makes it possible for the first time to manufacture LEDs with high efficiency, which are based on a short-wave emitting diode that excites several phosphors. Table 1: Blue-emitting phosphors:
Ms(PO4)3(X):Eu2+ mit M = zumindest eines der Metalle Ba, Ca allein oder inM s (PO 4 ) 3 (X): Eu 2+ with M = at least one of the metals Ba, Ca alone or in
Kombination mit Sr (bevorzugt ist Anteil Sr höchstens 85%), wobei X = zumindest eines der Halogene F oder Cl;Combination with Sr (Sr is preferably at most 85%), where X = at least one of the halogens F or Cl;
M*3MgSi2O8:Eu2+ mit M = zumindest eines der Metalle Ba, Ca, Sr allein oder in KombinationM * 3MgSi2O8: Eu2 + with M = at least one of the metals Ba, Ca, Sr alone or in combination
Ba5SiO4Br6:Eu2+ Ba 5 SiO 4 Br 6 : Eu 2+
Ba^A^O^Eu2* Ba ^ A ^ O ^ Eu 2 *
YSiO2N:Ce3+ YSiO 2 N: Ce 3+
(Sr,Ba)2Al6Oπ:Eu2+ (Sr, Ba) 2 Al 6 O π : Eu 2+
MF2:Eu2+ mit M = zumindest eines der Metalle Ba, Sr, Ca; bevorzugt ist der Anteil des Ba an M > 5 %, beispielsweise Ba = 10 %, also M = Ba010Sr045Ca045.MF 2 : Eu 2+ with M = at least one of the metals Ba, Sr, Ca; the proportion of Ba in M is preferably> 5%, for example Ba = 10%, that is to say M = Ba 010 Sr 045 Ca 045 .
Bao.57 Euo.oA34Alπ πO17:Eu2+ Ba o. 57 Eu o.oA 34 Al π π O 17 : Eu 2+
M**MgA110O17:Eu2+ mit M** = zumindest eines der Metalle Eu, Sr allein oder in Kombination mit Ba (bevorzugt ist Anteil Ba höchstens 75%);M ** MgA110O17: Eu2 + with M ** = at least one of the metals Eu, Sr alone or in combination with Ba (Ba fraction is preferably at most 75%);
MLn2S4:Ce3+ mit M = eine Kombination der Metalle Ca, Sr; und Ln = zumindest eines der Metalle La, Y, Gd. MLn2S4: Ce 3 + with M = a combination of the metals Ca, Sr; and Ln = at least one of the metals La, Y, Gd.
Tabelle 2: Grün (und Blaugrün) emittierende LeuchtstoffeTable 2: Green (and teal) emitting phosphors
SrAl2O4:Eu2+ SrAl 2 O 4 : Eu 2+
MBO3:(Ce3+,Tb3+) mit M = zumindest eines der Metalle Sc, Gd, Lu allein oder inMBO3: (Ce3 +, Rb3 +) with M = at least one of the metals Sc, Gd, Lu alone or in
Kombination mit Y (imsb. ist Y- Anteil < 40%); und als Aktivator fungie- ren die Metalle Ce und Tb gemeinsam; insbesondere liegt der Anteil desCombination with Y (in particular, Y content is <40%); and the metals Ce and Tb act together as an activator; in particular, the share of
Ce am Metall M im Bereich 5 % ≤ Ce ≤ 20 % und der Anteil des Tb amCe on metal M in the range 5% ≤ Ce ≤ 20% and the proportion of Tb on
Metall im Bereich 4 % ≤Tb < 20; bevorzugt ist Anteil Ce > Anteil Tb;Metal in the range 4% ≤Tb <20; Ce portion> Tb portion is preferred;
M2SiO5:(Ce3+,Tb3+) mit M = zumindest eines der Metalle Y, Gd, Lu; und als Aktivator fungieren die Metalle Ce und Tb gemeinsam (bevorzugt ist Anteil Ce > Anteil Tb);M2SiO5: (Ce3 +, Tb3 +) with M = at least one of the metals Y, Gd, Lu; and the metals Ce and Tb function together as activator (preference is given to proportion Ce> proportion Tb);
MN*2S4:Ak mit M = zumindest eines der Metalle Zn, Mg, Ca, Sr, Ba; mit NMN * 2S4: Ak with M = at least one of the metals Zn, Mg, Ca, Sr, Ba; with N
= zumindest eines der Metalle AI, Ga, In; und Ak = entweder eine Kombination von Eu2+, Mn2 zusammen (bevorzugt ist Anteil Eu > Anteil Mn) oder eine Kombination von Ce3+,Tb3+ zusammen (bevorzugt ist Anteil Ce > Anteil Tb);= at least one of the metals AI, Ga, In; and Ak = either a combination of Eu2 +, Mn2 together (Eu portion> Mn portion is preferred) or a combination of Ce3 +, Tb3 + together (Ce portion> Tb portion is preferred);
SrBaSiO4:Eu2+ SrBaSiO 4 : Eu 2+
Ba0.82AlEO1M.:EuIt Ba 0.82 Al E O 1M .: Eu It
Y5(SiO4)3N:Ce3+;Y 5 (SiO 4 ) 3 N: Ce 3+ ;
Ca8Mg(SiO4)4C12:Ak2+ mit Ak = Eu2+ allein oder mit Mn2 zusammen (bevorzugt ist Anteil Eu > 2xAnteil Mn);Ca8Mg (SiO4) 4C12: Ak2 + with Ak = Eu2 + alone or with Mn2 (Eu> 2xMn Mn is preferred);
Sr4A114O25:Eu2+Sr4A114O25: Eu 2+
(Ba,Sr)MgA110O17:Ak mit Ak = Eu2+ entweder in Kombination mit Ce3+ und(Ba, Sr) MgA110O17: Ak with Ak = Eu2 + either in combination with Ce3 + and
Tb3+, oder in Kombination mit Mn2+ ; bevorzugt ist Anteil Eu am Akti- vator Ak > 50 %;Rb3 +, or in combination with Mn2 +; Eu share in the activator Ak is preferably> 50%;
Sr6BP5O20:Eu2+Sr 6 BP 5 O 20 : Eu2 +
Sr2P2O7:(Eu2+,Tb3+) mit Eu und Tb gemeinsamSr 2 P 2 O 7 : (Eu 2+ , Tb 3+ ) together with Eu and Tb
BaSi2Os:Eu2+ Tabelle 3: Rot (Orangerot bis Tiefrot) emittierende LeuchtstoffeBaSi 2 O s : Eu 2+ Table 3: Phosphors emitting red (orange-red to deep red)
Ln2O2St: Ak3+ wobei Ln = zumindest eines der Metalle Gd, La, Lu allein oder in Kombination mit Y (bevorzugt ist Anteil Y höchstens 40%; insbeson- dere ist Anteil La mindestens 10 %); und mit St = zumindest eines derLn 2 O 2 St: Ak3 + where Ln = at least one of the metals Gd, La, Lu alone or in combination with Y (Y is preferably at most 40%; in particular, La is at least 10%); and with St = at least one of the
Elemente S, Se, Te; und wobei Ak = Eu allein oder in Kombination mitElements S, Se, Te; and where Ak = Eu alone or in combination with
Bi;Bi;
Ln2WmO6:Ak3+ wobei Ln = zumindest eines der Metalle Y, Gd, La, Lu; und mit Wm = zumindest eines der Elemente W, Mo, Te; und wobei Ak = Eu allein oder in Kombination mit Bi;Ln2WmO6: Ak3 + where Ln = at least one of the metals Y, Gd, La, Lu; and with Wm = at least one of the elements W, Mo, Te; and where Ak = Eu alone or in combination with Bi;
(Zn,Cd)S:Ag+ wobei Zn und Cd nur in Kombination verwendet werden; bevorzugt ist Anteil Zn < Anteil Cd;(Zn, Cd) S: Ag + where Zn and Cd are only used in combination; Zn is preferably <Cd;
Mg28Ge7,O38F10:Mn4+ Mg 28 Ge 7 , O 38 F 10 : Mn 4+
Sr:P:O.:Eu2*,Mn2+ Sr : P : O.:Eu 2 * , Mn 2+
M3MgSi2O8:Eu2+,Mn2 mit M = zumindest eines der Metalle Ca, Ba, Sr.M 3 MgSi 2 O 8 : Eu 2+ , Mn 2 with M = at least one of the metals Ca, Ba, Sr.
(Ml)2(M2)(BO3)2:Eu2+ mit Ml = zumindest eines der Metalle Ba, Sr; und mit M2 ist zumindest eines der Metalle Mg,Ca; bevorzugt ist der Anteil Ba am Kation Ml mindestens 80 %; bevorzugt ist der Anteil Mg am Metall M2 mindestens 70%.(Ml) 2 (M2) (BO3) 2: Eu2 + with Ml = at least one of the metals Ba, Sr; and with M2 is at least one of the metals Mg, Ca; the proportion of Ba in the cation Ml is preferably at least 80%; the proportion of Mg in metal M2 is preferably at least 70%.
Es wird angemerkt, dass der Aktivator im allgemeinen jeweils einen Anteil des führenden Kations (= Metall, insbesondere ein Lanthanid Ln) ersetzt, beispielsweise steht MS:Eu(5 %) für MM05Eu0D5S.It is noted that the activator generally replaces a portion of the leading cation (= metal, in particular a lanthanide Ln), for example MS: Eu (5%) stands for M M05 Eu 0D5 S.
Die Formulierung „M = zumindest eines der Metalle X, Y;" bedeutet entweder das Me- tall X oder das Metall Y allein oder aber eine Kombination beider Metalle, also M = X Y. mit a+b = 1. Bei einer weißen LED wird ein Aufbau ähnlich wie im eingangs erwähnten Stand der Technik beschrieben verwendet. Als UV-Diode (primäre Strahlungsquelle) wird bevorzugt GalnN oder GaN oder GalnAlN verwendet. Beispielsweise hat sie eine Peakwellenlange von 400 nm und eine Halb- wertsbreite von 20 nm. Das Diodensubstrat wird mit einer Suspension aus drei Leuchtstoffen, je einer mit einem Emissionsmaximum im Roten, Grünen und Blauen Spektralbereich direkt oder indirekt beschichtet. Von diesen Leuchtstoffen ist zumindest einer ausgewählt aus den Tabellen 1 bis 3, und kombiniert entweder mit bekannten Leuchtstoffen oder mit Leuchtstoffen aus den anderen Tabellen. Die Leuchtstoffmischung wird bei etwa 200 °C eingebrannt. Damit wird eine Farbwiedergabe von typisch 80 erzielt.The formulation “M = at least one of the metals X, Y;” means either the metal X or the metal Y alone or a combination of both metals, that is M = X Y. with a + b = 1. In the case of a white LED, a structure similar to that described in the prior art mentioned at the outset is used. GalnN or GaN or GalnAlN is preferably used as the UV diode (primary radiation source). For example, it has a peak wavelength of 400 nm and a full width at half maximum of 20 nm. The diode substrate is coated directly or indirectly with a suspension of three phosphors, each with an emission maximum in the red, green and blue spectral range. At least one of these phosphors is selected from Tables 1 to 3 and is combined either with known phosphors or with phosphors from the other tables. The phosphor mixture is baked at about 200 ° C. A color rendering of typically 80 is thus achieved.
Im folgenden soll die Erfindung anhand mehrerer Ausführungsbeispiele näher erläutert werden. Es zeigen:The invention will be explained in more detail below with the aid of several exemplary embodiments. Show it:
Figur 1 ein Halbleiterbauelement, das als Lichtquelle (LED) für weißes Licht dient;Figure 1 is a semiconductor device that serves as a light source (LED) for white light;
Figur 2 eine Beleuchtungseinheit mit Leuchtstoffen gemäß der vorliegendenFigure 2 shows a lighting unit with phosphors according to the present
Erfindung; Figur 3 bis 17 das Emissionsspektrum von LEDs mit verschiedenen Leuchtstoff mi- schungen gemäß der vorliegenden Erfindung.Invention; 3 to 17 show the emission spectrum of LEDs with different phosphor mixtures according to the present invention.
Beschreibung der ZeichnungenDescription of the drawings
Für den Einsatz in einer weißen LED zusammen mit einem GalnN-Chip wird beispielsweise ein Aufbau ähnlich wie in US 5 998 925 beschrieben verwendet. Der Aufbau einer derartigen Lichtquelle für weißes Licht ist in Figur 1 explizit gezeigt. Die Lichtquelle ist ein Halbleiterbauelement (Chip 1) des Typs InGaN mit einer Peak-Emissionswellenlänge von 420 nm und einer Halbwertsbreite von 25 nm mit einem ersten und zweiten elektrischen Anschluss 2,3, das in ein lichtundurchlässiges Grundgehäuse 8 im Bereich einer Ausnehmung 9 eingebettet ist. Einer der Anschlüsse 3 ist über einen Bonddraht 14 mit dem Chip 1 verbunden. Die Ausnehmung hat eine Wand 17, die als Reflektor für die blaue Primärstrahlung des Chips 1 dient. Die Ausnehmung 9 ist mit einer Vergussmasse 5 gefüllt, die als Hauptbe- standteile ein Epoxidgießharz (80 bis 90 Gew.-%) und Leuchtstoffpigmente 6 (weni- ger als 15 Gew.-%) enthält. Weitere geringe Anteile entfallen u.a. auf Methylether und Aerosil. Die Leuchtstoffpigmente sind eine Mischung. Der erste Konversions- Leuchtstoff ist aus Tab. 1 ausgewählt. Der zweite Leuchtstoff ist aus Tab. 2 und der dritte aus Tab. 3 ausgewählt.For use in a white LED together with a GalnN chip, for example, a structure similar to that described in US Pat. No. 5,998,925 is used. The structure of such a light source for white light is shown explicitly in FIG. 1. The light source is a semiconductor component (chip 1) of the InGaN type with a peak emission wavelength of 420 nm and a half-width of 25 nm with a first and second electrical connection 2, 3, which is embedded in an opaque basic housing 8 in the region of a recess 9 , One of the connections 3 is connected to the chip 1 via a bonding wire 14. The recess has a wall 17 which serves as a reflector for the blue primary radiation of the chip 1. The recess 9 is filled with a potting compound 5, the main components of which are an epoxy casting resin (80 to 90% by weight) and phosphor pigments 6 (less contains less than 15% by weight). Other small proportions include methyl ether and Aerosil. The phosphor pigments are a mixture. The first conversion phosphor is selected from Table 1. The second phosphor is selected from Tab. 2 and the third from Tab. 3.
In Figur 2 ist ein Ausschnitt aus einer Flächenleuchte 20 als Beleuchtungseinheit gezeigt. Sie besteht aus einem gemeinsamen Träger 21 , auf den ein quaderförmi- ges äußeres Gehäuse 22 aufgeklebt ist. Seine Oberseite ist mit einer gemeinsamen Abdeckung 23 versehen. Das quaderförmige Gehäuse besitzt Aussparungen, in denen einzelne Halbleiter-Bauelemente 24 untergebracht sind. Sie sind UV- emittierende Leuchtdioden mit einer Peakemission von 380 nm. Die Umwandlung in weißes Licht erfolgt mittels Konversionsschichten, die direkt im Gießharz der einzelnen LED sitzen ähnlich wie in Figur 1 beschrieben oder Schichten 25, die auf allen der UV-Strahlung zugänglichen Flächen angebracht sind. Dazu zählen die innen liegenden Oberflächen der Seitenwände des Gehäuses, der Abdeckung und des Bodenteils. Die Konversionsschichten 25 bestehen aus drei Leuchtstoffen, die im gelben, grünen und blauen Spektralbereich emittieren unter Benutzung zumindest einen der erfindungsgemäßen Leuchtstoffe aus Tab. 1 bis 3.FIG. 2 shows a section of a surface light 20 as a lighting unit. It consists of a common carrier 21 onto which a cuboid outer housing 22 is glued. Its top is provided with a common cover 23. The cuboid housing has cutouts in which individual semiconductor components 24 are accommodated. They are UV-emitting light-emitting diodes with a peak emission of 380 nm. The conversion to white light takes place by means of conversion layers which are seated directly in the casting resin of the individual LEDs, as described in FIG. 1, or layers 25 which are attached to all surfaces accessible to UV radiation are. These include the inner surfaces of the side walls of the housing, the cover and the base part. The conversion layers 25 consist of three phosphors which emit in the yellow, green and blue spectral range using at least one of the phosphors according to the invention from Tables 1 to 3.
Einige konkrete Ausführungsbeispiele von in Kombination untersuchten Leuchtstoffen sind in Tab. 4 zusammengefasst. Es handelt sich um eine Zusammenfassung geeigneter erfindungsgemäßer und an sich bekannter Leuchtstoffe in allen drei Spektralbereichen. In Sp. 1 ist die Versuchsnummer angegeben, in Sp. 2 die chemische Formel des Leuchtstoffs, in Sp. 3 das Emissionsmaximum des Leuchtstoffs, in Sp. 4 und 5 die x- und y- Farbortkoordinaten. In Sp. 6 und 7 sind die Reflektivität und die Quanteneffizienz (jeweils in Prozent) angegeben. Besonders bevorzugt ist auch die Anwendung der ZnS-Leuchtstoffe für LEDs. Sie zeigen ein gutes Verarbeitungsverhalten in der LED-Umgebung. Es handelt sich dabei vor allem um den blau emittierenden Leuchtstoff ZnS:Ag, den grün emittierenden Leuchtstoff ZnS:Cu,AI und- den rot emittierenden Leuchtstoff ZnS:Cu,Mn aus Tab. 4. Besonders hervorzuheben ist, dass sich mit diesen drei Leuchtstoffen eine weiß emittierende Leuchtstoff-Mischung realisieren lässt, unter Anregung durch eine LED mit Primärstrahlung im Bereich 370 bis 410 nm, siehe Ausführungsbeispiel 6 in Fig. 6. Da diese drei Leuchtstoffe chemisch nahezu identische Materialien sind, lassen sie sich sehr gut als Leuchtstoffmischung in einem Gießharz oder anderem Harz oder bei einer Beschlämmung verarbeiten. Tab. 4Some specific exemplary embodiments of phosphors examined in combination are summarized in Tab. 4. It is a summary of suitable phosphors according to the invention and known per se in all three spectral ranges. The experimental number is given in column 1, the chemical formula of the phosphor in column 2, the maximum emission of the phosphor in column 3, and the x and y coordinate coordinates in columns 4 and 5. Columns 6 and 7 show the reflectivity and the quantum efficiency (both in percent). The use of ZnS phosphors for LEDs is also particularly preferred. They show good processing behavior in the LED environment. These are primarily the blue-emitting phosphor ZnS: Ag, the green-emitting phosphor ZnS: Cu, Al and the red-emitting phosphor ZnS: Cu, Mn from Table 4. It should be emphasized that these three phosphors are particularly noteworthy a white-emitting phosphor mixture can be realized, with excitation by an LED with primary radiation in the range 370 to 410 nm, see exemplary embodiment 6 in FIG. 6. Since these three phosphors are chemically almost identical materials, they can be used very well as a phosphor mixture in one Use cast resin or other resin or with a slurry. Tab. 4
Nr. Formel Em X y R (%) Q.E (%)Formula Em X y R (%) Q.E (%)
1 Ba3MgSi208: Eu (5%) 440 0,16 0,07 42 501 Ba 3 MgSi 2 0 8 : Eu (5%) 440 0.16 0.07 42 50
2 (Ba0,i5Sro,85)5(P04)3CI:Eu2+ 448 0,15 0,05 46 762 (Ba 0, i 5 Sro, 85 ) 5 (P0 4 ) 3 CI: Eu2 + 448 0.15 0.05 46 76
3 ZnS :Ag 452 0,14 0,07 76 633 ZnS: Ag 452 0.14 0.07 76 63
4 (Ba,Sr)MgAI10O17:Eu2+ 454 0,15 0,08 49 834 (Ba, Sr) MgAI 10 O 17 : Eu2 + 454 0.15 0.08 49 83
5 SrMgAI10O17:Eu2+ 467 0,15 0,19 63 925 SrMgAI 10 O 17 : Eu2 + 467 0.15 0.19 63 92
6 EuMgAI10O17 481 0,17 0,31 35 636 EuMgAI 10 O 17 481 0.17 0.31 35 63
7 ZnS :Cu 506 0,19 0,43 22 487 ZnS: Cu 506 0.19 0.43 22 48
8 Ba0.-74EU0.08AI12Oi8.e2 507 0,22 0,43 52 878 Ba0.-74EU0.08AI12Oi8.e2 507 0.22 0.43 52 87
9 Ca8Mg(Siθ4)4CI2:Eu2+ 508 0,17 0,6 34 679 Ca 8 Mg (SiO 4 ) 4 CI 2 : Eu2 + 508 0.17 0.6 34 67
10 ZnS :Cu 510 0,2 0,46 16 5510 ZnS: Cu 510 0.2 0.46 16 55
11 BaMgAlι0Oι7:Eu2+,Mn2+ 513 0,14 0,21 64 9511 BaMgAlι 0 Oι 7 : Eu2 +, Mn2 + 513 0.14 0.21 64 95
12 Bao.72Euo.o5Mno.o5Ali2θ18.82 514 0,21 0,48 71 9712 Bao.72Euo.o5Mno.o5Ali2θ 18 .82 514 0.21 0.48 71 97
13 BaMgAlι0O17:Eu2+,Mn2+ 515 0,14 0,65 39 8813 BaMgAlι 0 O 17 : Eu2 +, Mn2 + 515 0.14 0.65 39 88
14 (Sr,Ba)Si04:Eu2+ 517 0,23 0,61 5414 (Sr, Ba) Si0 4 : Eu2 + 517 0.23 0.61 54
15 SrAI204:Eu2+ 523 0,29 0,58 28 7715 SrAI 2 0 4 : Eu2 + 523 0.29 0.58 28 77
16 ZnS :Cu,AI 534 0,31 0,61 29 8316 ZnS: Cu, Al 534 0.31 0.61 29 83
17 YBO3 :(Ce3+,Tb3+) (9.5%/5%) 545 0,34 0,59 80 6917 YBO 3 : (Ce3 +, Rb3 +) (9.5% / 5%) 545 0.34 0.59 80 69
18 Ca8Mg(Si04)4CI2:Eu2+, Mn2+ 550 0,38 0,57 30 6118 Ca 8 Mg (Si0 4 ) 4 CI 2 : Eu2 +, Mn2 + 550 0.38 0.57 30 61
19 Srι.gsBao.o3Euo.o2Siθ4 563 0,44 0,53 2119 Srι.gsBao.o 3 Euo.o 2 Siθ 4 563 0.44 0.53 21
20 Sr2P207:Eu2+ , Mn2+ 570 0,32 0,27 63 4620 Sr 2 P 2 0 7 : Eu2 +, Mn2 + 570 0.32 0.27 63 46
21 ZnS :Cu,Mn 585 0,49 0,45 19 4421 ZnS: Cu, Mn 585 0.49 0.45 19 44
22 Gd2Mo06:Eu3+ (20%) 610 0,66 0,34 5022 Gd 2 Mo0 6 : Eu3 + (20%) 610 0.66 0.34 50
23 Y2Wo.98Mo0.o206:Eu3+ 612 0,61 0,38 68 7323 Y 2 wk 98 Mo 0 .o 2 0 6 : Eu 3+ 612 0.61 0.38 68 73
24 Y2W06:Eu3+, Bi3+ (7.5%, 0.5%) 612 0,64 0,36 5224 Y 2 W0 6 : Eu3 +, Bi3 + (7.5%, 0.5%) 612 0.64 0.36 52
25 Lu2W06:Eu3+, Bi3+ (7.5%, 1%) 612 0,64 0,36 6525 Lu 2 W0 6 : Eu3 +, Bi3 + (7.5%, 1%) 612 0.64 0.36 65
26 SrS:Eu2+ (2%) 616 0,63 0,37 52 9126 SrS: Eu2 + (2%) 616 0.63 0.37 52 91
27 La2Te06:Eu3+ ( %) 617 0,66 0,34 7627 La 2 Te0 6 : Eu3 + (%) 617 0.66 0.34 76
28 (La,Y)202S:Eu3+ (..) 626 0,67 0,33 84 7328 (La, Y) 2 0 2 S: Eu3 + (..) 626 0.67 0.33 84 73
29 Sr2Si5N8:Eu2+ (10%) 636 0,64 0,36 12 7029 Sr 2 Si 5 N 8 : Eu2 + (10%) 636 0.64 0.36 12 70
30 (Ba,Ca,Sr)MgSi208: Eu.Mn 657 0,39 0,16 47 5230 (Ba, Ca, Sr) MgSi 2 0 8 : Eu.Mn 657 0.39 0.16 47 52
Der Leuchtstoff Nr. 14 (Sr,Ba)Si04:Eu2+ ist im Grünen so breitbandig, dass hier auf eine separate Rotkomponente verzichtet werden. In Tab. 6 sind schließlich 15 Ausführungsbeispiele konkreter Kombinationen von Leuchtstoffen aus Tab. 4 in Verbindung mit einer primären Lichtquelle (UV-LED) mit einem Emissionspeak im Bereich 370 bis 420 nm gezeigt. Die einzelnen UV-Dioden sind in Tab. 5 zusammengefasst, in der der Emissionspeak und der Farbort (soweit definiert, also ab 380 nm) der einzelnen Dioden angegeben ist.The phosphor no. 14 (Sr, Ba) Si0 4 : Eu2 + is so broad-banded in the green that a separate red component is dispensed with here. Finally, Tab. 6 shows 15 exemplary embodiments of specific combinations of phosphors from Tab. 4 in connection with a primary light source (UV-LED) with an emission peak in the range 370 to 420 nm. The individual UV diodes are summarized in Tab. 5, in which the emission peak and the color location (as far as defined, that is from 380 nm) of the individual diodes is given.
In Sp. 1 bis 4 der Tab. 6 sind die Angaben aus Tab. 4 nochmals eingefügt zum besseren Abgleich. In Sp. 5 bis 10 ist die Brauchbarkeit der einzelnen Leuchtstoffe für Anregung bei verschiedenen Wellenlängen festgehalten und zwar systematisch für die kurzwelligen Dioden mit Emissionspeak bei 370 bis 420 nm in Schritten von 10 nm. Die anschließenden 15 Spalten zeigen konkrete Beispiele (als Ex 1 bis Ex 15 bezeichnet) einer RGB-Mischung, also die Kombination der kurzwelligen LED (die zweite Zeile gibt die gewählte Peakemission an) mit drei Leuchtstoffen aus dem roten, grünen und blauen Spektralbereich. Die in der jeweiligen Spalte angegebene Zahl bezeichnet den relativen Anteil an der spektralen Emission.In Columns 1 to 4 of Tab. 6 the information from Tab. 4 is inserted again for better comparison. The usefulness of the individual phosphors for excitation at different wavelengths is recorded in columns 5 to 10, specifically for the short-wave diodes with emission peak at 370 to 420 nm in steps of 10 nm. The following 15 columns show concrete examples (as Ex 1 to Ex 15) of an RGB mixture, i.e. the combination of the short-wave LED (the second line indicates the selected peak emission) with three phosphors from the red, green and blue spectral range. The number given in the respective column denotes the relative proportion of the spectral emission.
Bei einer stark kurzwelligen UV-Diode, unter 380 nm, liefert die UV-Diode keinerlei Anteil an der sekundären Emission, auch wegen der starken Absorption durch die drei Leuchtstoffe.In the case of a strongly short-wave UV diode, below 380 nm, the UV diode does not provide any part in the secondary emission, also because of the strong absorption by the three phosphors.
Ab einer primären Emission von 380 nm liefert die Diode jedoch einen kleinen, mit steigender Wellenlänge steigenden Anteil im Blauen zusätzlich zum blauen Leucht- stoff. Dieser Anteil erscheint in der Tab. 5 als zusätzlicher vierter Beitrag.From a primary emission of 380 nm, however, the diode delivers a small proportion of the blue, which increases with increasing wavelength, in addition to the blue phosphor. This proportion appears in Table 5 as an additional fourth contribution.
Schließlich sind in den letzten beiden Zeilen der Tab. 6 die gemessenen Farbortkoordinaten des Gesamtsystems eingetragen, die einen weiten Bereich von Weißtönen in der Farbtafel abdecken. Die spektrale Verteilung dieser System ist in den Figuren 3 (entsprechend Ex 1) bis 17 (entsprechend Ex 15) dargestellt.Finally, the measured color location coordinates of the overall system are entered in the last two lines of Table 6, which cover a wide range of white tones in the color table. The spectral distribution of this system is shown in Figures 3 (corresponding to Ex 1) to 17 (corresponding to Ex 15).
Als besonders geeignete Leuchtstoffe für die Anwendung in Dreifarbenmischungen unter Primärbestrahlung bei 370 bis 420 nm haben sich dabei die blau emittierenden Leuchtstoffe Nr. 2, 4 und 6, die grün emittierenden Leuchtstoffe 8, 9, 10, 13, 15, 16, 17 und 18 sowie die rot emittierenden Leuchtstoffe 26, 28 und 29 erwiesen.The particularly suitable phosphors for use in three-color mixtures under primary irradiation at 370 to 420 nm are the blue-emitting phosphors No. 2, 4 and 6, and the green-emitting phosphors 8, 9, 10, 13, 15, 16, 17 and 18 as well as the red-emitting phosphors 26, 28 and 29.
Das Ausführungsbeispiel Nr. 15 verwendet eine blau emittierende Diode mit 420 nm Peakemission mit so hoher Intensität, dass sie den blauen Leuchtstoff voll ersetzen kann und nur zwei zusätzliche Leuchtstoffe im Grünen und Roten benötigt. Exemplary embodiment no. 15 uses a blue-emitting diode with 420 nm peak emission with such a high intensity that it can fully replace the blue phosphor and only requires two additional phosphors in the green and red.
m cö m co

Claims

Ansprüche Expectations
1. Beleuchtungseinheit mit mindestens einer LED als Lichtquelle, wobei die LED primär Strahlung im Bereich von 370 bis 430 nm des optischen Spektralbereichs emittiert (Peakwellenlange), wobei diese Strahlung teilweise oder vollständig in längerwellige Strahlung konvertiert wird durch drei Leuchtstoffe, die der primären Strah- lung der LED ausgesetzt sind, und die im blauen, grünen und roten Spektralbereich emittieren, so dass weißes Licht entsteht, dadurch gekennzeichnet, dass die Konversion zumindest unter Zuhilfenahme eines Leuchtstoffs, der blau mit einem Maximum der Wellenlänge bei 440 bis 485 nm emittiert, und unter Zuhilfenahme eines Leuchtstoffs, der grün mit einem Maximum der Wellenlänge bei 505 bis 550 nm e- mittiert und unter Zuhilfenahme eines Leuchtstoffs, der rot mit einem Maximum der1. Illumination unit with at least one LED as a light source, the LED primarily emitting radiation in the range from 370 to 430 nm of the optical spectral range (peak wavelength), this radiation being partially or completely converted into longer-wave radiation by three phosphors which correspond to the primary radiation tion of the LED, and which emit in the blue, green and red spectral range, so that white light is produced, characterized in that the conversion, at least with the aid of a phosphor which emits blue with a maximum wavelength at 440 to 485 nm, and with the help of a phosphor that emits green with a maximum of the wavelength at 505 to 550 nm and with the help of a phosphor that red with a maximum of
Wellenlänge bei 560 bis 670 nm emittiert, erreicht wird, wobei zumindest einer dieser drei Leuchtstoffe aus einer der Tabellen 1 , 2 oder 3 stammt.Wavelength emitted at 560 to 670 nm is achieved, at least one of these three phosphors originating from one of Tables 1, 2 or 3.
2. Beleuchtungseinheit nach Anspruch 1 , dadurch gekennzeichnet, dass die LED weiße Strahlung emittiert unter Verwendung von drei Leuchtstoffen, je einer aus den drei Tabellen.2. Lighting unit according to claim 1, characterized in that the LED emits white radiation using three phosphors, one from each of the three tables.
3. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass als primäre Strahlungsquelle eine LED auf Basis von Ga(ln,AI)N verwendet wird.3. Lighting unit according to claim 1, characterized in that an LED based on Ga (ln, AI) N is used as the primary radiation source.
4. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass weißes Licht erzeugt wird unter Verwendung eines blauen Leuchtstoffs: M5(PO4)3(X):Eu2+ mit M = zumindest eines der Metalle Ba, Ca allein oder in Kombination mit Sr, wobei X = zumindest eines der Halogene F oder Cl; oder eines blauen Leuchtstoffs:4. Lighting unit according to claim 1, characterized in that white light is generated using a blue phosphor: M 5 (PO 4 ) 3 (X): Eu 2+ with M = at least one of the metals Ba, Ca alone or in combination with Sr, where X = at least one of the halogens F or Cl; or a blue fluorescent:
M*3MgSi2O8:Eu2+ mit M = zumindest eines der Metalle Ba, Ca, Sr allein oder in Kombination; oder eines blauen Leuchtstoffs : ZnS:Ag oderM * 3 MgSi 2 O 8 : Eu 2+ with M = at least one of the metals Ba, Ca, Sr alone or in combination; or a blue phosphor: ZnS: Ag or
M**MgAl10O17:Eu2+ it M** = zumindest eines der Metalle Eu, Sr allein oder in Kombination mit Ba.M ** MgAl 10 O 17 : Eu 2+ it M ** = at least one of the metals Eu, Sr alone or in combination with Ba.
5. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass weißes Licht erzeugt wird unter Verwendung eines grünen Leuchtstoffs: SrAl2O4:Eu2+ oder eines grünen Leuchtstoffs Ba0.82AlßO1882:Eu2+,Mn2+ oder eines grünen Leuchtstoffs Ca8Mg(SiO4)4Cl2:Eu2+, Mn2+ oder eines grünen Leuchtstoffs5. Lighting unit according to claim 1, characterized in that white light is generated using a green phosphor: SrAl 2 O 4 : Eu 2+ or a green phosphor Ba 0 . 82 Al ß O 1882 : Eu 2+ , Mn 2+ or a green phosphor Ca 8 Mg (SiO 4 ) 4 Cl 2 : Eu 2+ , Mn 2+ or a green phosphor
Sr4A114025:Eu oder eines grünen Leuchtstoffs ZnS:Cu,Al oderSr4A114025: Eu or a green phosphor ZnS: Cu, Al or
BaMgAl10O]7:(Eu2+ kombiniert mit Ce3+,Tb3+, oder mit Mn2+).BaMgAl 10 O ] 7 : (Eu2 + combined with Ce 3+ , Tb 3+ , or with Mn 2+ ).
6. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass weißes Licht erzeugt wird unter Verwendung eines roten Leuchtstoffs Ln2O2SSt:Ak3+ wobei Ln = zumindest eines der Metalle Gd, La, Lu allein oder in Kombination mit Y; und mit St = zumindest eines der Elemente Se, Te; und wobei Ak = Eu allein oder in Kombination mit Bi; oder eines roten Leuchtstoffs ZnS:Cu,Mn oder6. Lighting unit according to claim 1, characterized in that white light is generated using a red phosphor Ln 2 O 2 SSt: Ak 3+ where Ln = at least one of the metals Gd, La, Lu alone or in combination with Y; and with St = at least one of the elements Se, Te; and where Ak = Eu alone or in combination with Bi; or a red phosphor ZnS: Cu, Mn or
Sr2P2O7: Ak2+ mit Ak = zumindest eines der Metalle Eu, Mn .Sr 2 P 2 O 7 : Ak 2+ with Ak = at least one of the metals Eu, Mn.
7. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlängenbereich 370 bis 420 nm liegt, unter Verwendung eines blauen Leuchtstoffs M5(PO4)3(X):Eu2t mit M = zumindest eines der Metalle Ba, Ca allein oder in Kombination mit Sr, wobei X = zumindest eines der Halogene F oder Cl; oder eines Leuchtstoffs7. Lighting unit according to claim 1, characterized in that for the generation of white light the primary emitted radiation is in the wavelength range 370 to 420 nm, using a blue phosphor M 5 (PO 4 ) 3 (X): Eu 2t with M = at least one of the metals Ba, Ca alone or in combination with Sr, where X = at least one of the halogens F or Cl; or a phosphor
M**MgAl10O]7:Eu2+ mit M** = zumindest eines der Metalle Eu, Sr allein oder in Kombination mit Ba.M ** MgAl 10 O ] 7 : Eu 2+ with M ** = at least one of the metals Eu, Sr alone or in combination with Ba.
8. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlängenbereich unterhalb 380 nm liegt, unter Verwendung eines blauen Leuchtstoffs M*3MgSi2O8:Eu2+ mit M = zumindest eines der Metalle Ba, Ca, Sr allein oder in Kombination.8. Lighting unit according to claim 1, characterized in that for the generation of white light, the primarily emitted radiation in the wavelength range is below 380 nm, using a blue phosphor M * 3 MgSi 2 O 8 : Eu 2+ with M = at least one of the metals Ba, Ca, Sr alone or in Combination.
9. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlän- genbereich 370 bis 420 nm liegt, unter Verwendung eines grünen Leuchtstoffs9. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation is in the wavelength range 370 to 420 nm, using a green phosphor
SrAl2O4:Eu2+ oder eines grünen LeuchtstoffsSrAl 2 O 4 : Eu 2+ or a green phosphor
Ca8Mg(SiO4)4Cl2:Eu2+, Mn2+ oder eines grünen Leuchtstoffs Sr4A114O25:Eu oder eines grünen LeuchtstoffsCa 8 Mg (SiO 4 ) 4 Cl 2 : Eu 2+ , Mn 2+ or a green phosphor Sr4A114O25: Eu or a green phosphor
BaMgAl10O17:(Eu2+ kombiniert mit Ce3+,Tb3+, oder mit Mn2+).BaMgAl 10 O 17 : (Eu2 + combined with Ce 3+ , Tb 3+ , or with Mn 2+ ).
10. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlän- genbereich unterhalb 390 nm liegt, unter Verwendung eines grünen Leuchtstoffs Ba^Al^^Eu^Mn2*).10. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation in the wavelength range is below 390 nm, using a green phosphor Ba ^ Al ^^ Eu ^ Mn 2 * ).
11. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlän- genbereich unterhalb von 380 nm liegt, unter Verwendung eines roten11. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation in the wavelength range is below 380 nm, using a red
Leuchtstoffsphosphor
Ln2O2St:Ak3+ wobei Ln = zumindest eines der Metalle Gd, La, Lu allein oder inLn 2 O 2 St: Ak 3+ where Ln = at least one of the metals Gd, La, Lu alone or in
Kombination mit Y; und mit St = zumindest eines der Elemente S, Se, Te; und wobei AkCombination with Y; and with St = at least one of the elements S, Se, Te; and where Ak
= Eu allein oder in Kombination mit Bi; oder eines roten Leuchtstoffs= Eu alone or in combination with Bi; or a red phosphor
SrJP )_:Ak2 mit Ak = zumindest eines der Metalle Eu, Mn .SrJP) _: Ak 2 with Ak = at least one of the metals Eu, Mn.
12. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlän- genbereich 370 bis 400 nm liegt, unter Verwendung eines roten Leuchtstoffs MMgSLO8:Eu,Mn wobei M = zumindest eines der Metalle Ba, Ca, Sr.12. Lighting unit according to claim 1, characterized in that for the generation of white light, the primarily emitted radiation in the wavelength gene range 370 to 400 nm, using a red phosphor MMgSLO 8 : Eu, Mn where M = at least one of the metals Ba, Ca, Sr.
13. Beleuchtungseinheit nach Anspruch 1 , dadurch gekennzeichnet, dass die Beleuchtungseinheit eine Lumineszenzkonversions-LED ist, bei der die Leuchtstoffe direkt oder mittelbar in Kontakt mit dem Chip stehen.13. Lighting unit according to claim 1, characterized in that the lighting unit is a luminescence conversion LED, in which the phosphors are in direct or indirect contact with the chip.
14. Beleuchtungseinheit nach Anspruch 1 , dadurch gekennzeichnet, dass die Beleuchtungseinheit ein Feld (Array) von LEDs ist.14. Lighting unit according to claim 1, characterized in that the lighting unit is a field (array) of LEDs.
15. Beleuchtungseinheit nach Anspruch 9, dadurch gekennzeichnet, dass zumindest einer der Leuchtstoffe auf einer vor dem LED-Feld angebrachten optischen Vorrich- tung angebracht ist.15. Lighting unit according to claim 9, characterized in that at least one of the phosphors is attached to an optical device attached in front of the LED field.
16. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlängenbereich 370 bis 410 nm liegt, unter Verwendung eines blauen Leuchtstoffs ZnS:Ag.16. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation is in the wavelength range 370 to 410 nm, using a blue phosphor ZnS: Ag.
17. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlängenbereich 370 bis 410 nm liegt, unter Verwendung eines grünen Leuchtstoffs ZnS:Cu,Al wobei Cu und AI gemeinsam verwendet werden.17. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation is in the wavelength range 370 to 410 nm, using a green phosphor ZnS: Cu, Al wherein Cu and Al are used together.
18. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlängenbereich 370 bis 410 nm liegt, unter Verwendung eines roten Leuchtstoffs ZnS:Cu,Mn, wobei Cu und Mn gemeinsam verwendet werden..18. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation is in the wavelength range 370 to 410 nm, using a red phosphor ZnS: Cu, Mn, wherein Cu and Mn are used together.
19. Beleuchtungseinheit nach Anspruch 1, dadurch gekennzeichnet, dass zur Erzeugung von weißem Licht die primär emittierte Strahlung im Wellenlän- genbereich 370 bis 410 nm liegt, unter gemeinsamer Verwendung eines blauen, grünen und roten Leuchtstoffs gemäß den Ansprüchen 16, 17, und 18. 19. Lighting unit according to claim 1, characterized in that for the generation of white light, the primary emitted radiation is in the wavelength range 370 to 410 nm, using a blue, green and red phosphor according to claims 16, 17 and 18.
EP01956394A 2000-07-28 2001-07-27 Illumination device with at least one led as the light source Ceased EP1305833A1 (en)

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DE10036940A DE10036940A1 (en) 2000-07-28 2000-07-28 Luminescence conversion LED
DE10036940 2000-07-28
PCT/DE2001/002849 WO2002011214A1 (en) 2000-07-28 2001-07-27 Illumination device with at least one led as the light source

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