Patent Application
20100224896
The present invention is directed to light emitting devices, especially to the field of LEDs.
In today's white emitting LEDs, usually red and green emitting luminescence conversion materials are present. These components are used in most applications as separate components.
At present there are many attempts being made to substitute these two components by a single component which is able to emit light in the desired wavelength range.
However, there is a continuing need for new components which are able to emit light over a broad wavelength range in order to make the manufacture of LEDs easier.
It is an object of the present invention to provide a light emitting device with a converter material which is able to emit light over a broad wavelength range.
This object is achieved by means of a light emitting device according to claim 1 of the present invention. Said light emitting device especially is a LED comprising a ceramic composite material essentially of the composition M1−yA2−xBxO2−2xN2+x:Euy, where M is selected out of the group comprising Sr, Ca, Ba, Mg or mixtures thereof, A is selected out of the group comprising Si, Ge or mixtures thereof, B is selected out of the group comprising Al, B, Ga or mixtures thereof and x and y are independently selected from >0 to ≦1.
The term “composite” especially means and/or includes that the material is comprised of at least two different phases with different compositions (as will be described in more detail later on) which jointly form an overall composition as described. The ceramic composite material may be either directly attached to the light emitting device like a LED or the ceramic composite material may be placed at a certain distance from the light emitting device like a LED. The latter means there is no direct contact between the surface of the light emitting device and the ceramic composite material.
The term “essentially” means especially that ≧95%, preferably ≧97% and most preferred ≧99% of the material has the desired composition.
The term “ceramic material” in the sense of the present invention means and/or includes especially a crystalline or polycrystalline compact material or composite material with a controlled amount of pores or without any pores.
The term “polycrystalline material” in the sense of the present invention means and/or includes especially a material with a volume density larger than 90 percent of the main constituent, consisting for more than 80 percent of single crystal domains, with each domain being larger than 0.5 μm in diameter and possibly having different crystallographic orientations. The single crystal domains may be interconnected by amorphous or glassy material or by additional crystalline constituents.
Such a material has shown to have, for a wide range of applications within the present invention, at least one of the following advantages:
According to a preferred embodiment of the present invention, the composite material comprises at least one amber to red emitting phase and at least one cyan to green emitting phase. By virtue thereof, it has been found that the wavelength range of the material in the visible spectrum can be greatly enhanced for many applications.
According to a preferred embodiment of the present invention x is ≦0.6. This has been found to be advantageous for many applications, since the ratio of the amber to red emitting phase(s) and the cyan to green emitting phase(s) is usually such that the material will show a broad emission band in the visible spectral area.
Preferably, x is ≧0.01 and ≦0.5, more preferably ≦0.01 and ≦0.4.
According to a preferred embodiment of the present invention, the composite material comprises a phase of composition M(A,B)2(O,N)3:Eu and a phase of composition MA2O2N2:Eu.
Surprisingly, it has been found for many applications that many inventive composite materials can be made comprising these two phases and that these two phases can even be found when high-temperature steps (e.g. high temperature sintering) are used. Without being bound to any theory, the inventors believe that trivalent B cations from the M(A,B)2(O,N)3 phase are not (or only to a very small extent) built in the MA2O2N2 lattice, therefore these two phases can coexist separately in the composite material.
According to a preferred embodiment of the present invention, at least one amber to red emitting phase and/or at least one cyan to green emitting phase are essentially present in the composite material in form of ceramic grains.
According to a preferred embodiment of the present invention, the d50 of the grains of
at least one amber to red emitting phase and/or least one cyan to green emitting phase is ≧3 μm to ≦50 μm. By virtue thereof, for many applications, the lighting features as well as the stability of the inventive composite ceramic can be improved.
According to a preferred embodiment of the present invention, the average grain size of the grains of the amber to red emitting phase is larger than the average grain size of the grains of the at least one cyan to green emitting phase. By virtue thereof, the amber to red emitting material will in many applications be dispersed within the composite ceramic.
Preferably, the d50 of the grain size of the grains of at least one amber to red emitting phase is ≧2 μm larger, preferably ≧10 μm larger than the d50 of the grain size of the grains of the at least one cyan to green emitting phase.
According to a preferred embodiment of the present invention, the emission maximum of the ceramic composite material is in the range of ≧520 nm to ≦650 nm
According to a preferred embodiment of the present invention, the half-width of the emission band of the material in the visible wavelength range is in the range of ≧90 nm to ≦160 nm.
It should be noted that within a wide range it is possible to “tune” the emission maximum as well as the half-width of the emission band of the material in the visible wavelength range by selecting the amount of amber to red emitting material in the composite ceramic.
Furthermore, it has surprisingly been shown that the emission spectrum of the cyan to green emitting MA2O2N2:Eu (M=Sr, Ca, Ba, Mg; A=Si, Ge) ceramic grains may for a wide range of applications be tuned by varying the M content of the material. The larger the average ionic radius of the M cations, the more blue-shifted the emission may be. The emission maximum thus can in practice be tuned from 490 nm to 570 nm for a wide range of applications.
The emission spectrum of the amber to red emitting M(A,B)2(O,N)3:Eu ceramic grains may be tuned, also for a wide range of applications, by varying the M content of the material. The larger the average ionic radius of the M cations, the more blue-shifted the emission may be. The emission maximum thus can in practice be tuned from 600 nm to 670 nm for a wide range of applications.
In addition, it has been found for many applications that the spectra of the constituent phases of the composite ceramic may be tuned by changing the Eu concentration. A higher Eu concentration leads to an overall red shift of the composite material emission bands.
Preferably, y [which is the Eu content] is ≧0.001 and ≦0.05, preferably ≧0.002 and ≦0.01
According to a preferred embodiment of the present invention, the photothermal stability of the ceramic composite material is in the range of ≦80% to ≦100% after exposure of the ceramic material for 1000 hrs at 200° C. with a light power density of 10 W/cm2 and an average photon energy of 2.75 eV.
The term “photothermal stability” in the sense of the present invention especially means and/or includes the conservation of the luminescence intensity under simultaneous application of heat and high intensity excitation, i.e. a photothermal stability of 100% indicates that the material is virtually unaffected by the simultaneous irradiation and heat up.
According to a preferred embodiment of the present invention, the photothermal stability of the ceramic composite material is in the range of ≧82.5% to ≦95%, preferably ≧85% to ≦97%, after exposure of the ceramic material for 1000 hrs at 200° C. with a light power density of 10 W/cm2 and an average photon energy of 2.75 eV.
According to a preferred embodiment of the present invention, the thermal conductivity of the ceramic composite material is in the range of ≧0.02 W cm−1 K−1 to ≦0.30 W cm−1 K−1.
According to one embodiment of the present invention, the ceramic composite material shows a transparency at normal incidence in air in the range of ≧10% to ≦85% for light in the wavelength range from ≧550 nm to ≦1000 nm.
Preferably, the transparency for normal incidence in air is in the range of ≧20% to ≦80% for light in the wavelength range from ≧550 nm to ≦1000 nm, more preferably in the range of ≧30% to ≦75% and most preferably in the range of >40% to <70% for light in the wavelength range from ≧550 nm to ≦1000 nm.
The term “transparency” in the sense of the present invention means especially that
≧10% preferably ≧20%, more preferably ≧30%, most preferably ≧40% and ≦85% of the incident light of a wavelength, which cannot be absorbed by the material, is transmitted through the sample for normal incidence in air (at an arbitrary angle). This wavelength is preferably in the range of ≧550 nm and ≦1000 nm.
According to a preferred embodiment of the present invention, the ceramic composite material has a density in the range of ≧95% and ≦101% of the theoretical density.
According to a preferred embodiment of the present invention, the ceramic composite material has a density of ≧97% and ≦100% of the theoretical density.
The present invention furthermore relates to a method of producing a ceramic composite material for a light emitting device according to the present invention comprising a sintering step.
The term “sintering step” in the sense of the present invention means especially densification of a precursor powder under the influence of heat, which may be combined with the application of uniaxial or isostatic pressure, without reaching the liquid state of the main constituents of the sintered material.
According to a preferred embodiment of the present invention, the sintering step is pressureless, preferably in a reducing or inert atmosphere.
According to a preferred embodiment of the present invention, the method furthermore comprises the step of pressing the ceramic composite precursor material to ≧50% and ≦70%, preferably ≧55% and ≦65%, of its theoretical density before sintering. It has been shown in practice that this improves the sintering steps for most ceramic composite materials as described with respect to the present invention.
According to a preferred embodiment of the present invention, the method of producing a ceramic composite material for a light emitting device according to the present invention comprises the following steps:
According to this method, for most desired material compositions, this production method has produced the best ceramic composite materials, as used in the present invention.
A light emitting device according to the present invention as well as a ceramic composite material as produced with the present method may be of use in a broad variety of systems and/or applications, amongst them one or more of the following:
The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept, so that the selection criteria known in the pertinent field can be applied without limitations.
Additional details, features, characteristics and advantages of the object of the invention are disclosed in the subclaims, the figures and the following description of the respective figures and examples, which—in an exemplary fashion—show several embodiments and examples of a ceramic composite material for use in a light emitting device according to the invention.
The invention will be better understood by referring to Examples Ito IV which—in a merely illustrative fashion—are four Examples of inventive ceramic composite materials.
Example I refers to Sr4CaSi9AlO8N11:Eu (2%), which was made in the following way:
Powders (a) and (b) are wet-mixed by planetary ball milling with cyclohexane, and dried. The powder mixture is then pressed in a boron nitride-coated graphite die at 1500° C. in a vacuum for 4 hrs. After annealing at 1400° C. in a H2/N2 atmosphere, the composite ceramic is then sliced and polished to a thickness of 100 μm.
Example II was made in analogous fashion, except that for Example II only 44.4 wt % of Powder (b) was used.
The change of the emission spectrum with excitation wavelength is highly advantageous for a LED application, because color consistency is greatly improved compared to single-phase phosphor-converted LEDs. For example, if the blue emitting pump LED changes its spectral position, e.g. to longer wavelengths, the ceramic composite material also changes its spectrum in such a way that less green but more red emission is obtained. This spectral shift leads to a stabilization of the overall LED color point, which is highly advantageous for the systems and applications mentioned above.
The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and other patents/applications (incorporated herein by reference) are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and different implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07115592.3 | Sep 2007 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/IB2008/053507 | 8/29/2008 | WO | 00 | 5/18/2010 |
