A red-emitting phosphor composed of an m-Al—Si—N system, comprising a cation m, wherein m is represented by at least one of the elements Ca or Ba or Sr and, if appropriate, can additionally be combined with at least one further element from the group Mg, Zn, Cd, wherein the phosphor is activated with eu, which partly replaces m, and wherein the phosphor additionally contains LiF.
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1. A red-emitting phosphor composed of an m-Al—Si—N—LiF system, comprising a cation m, an activator eu, and LiF, wherein m is selected from the group consisting of elements Ca, Ba, Sr, and combinations thereof; the proportion of LiF is at least 1 mol %, based on the total molar amount of m, eu, and LiF; and the LiF is included in the lattice of the phosphor.
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5. A light source comprising a phosphor as claimed in
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This is a U.S. national stage of application No. PCT/EP2008/054389, filed on Apr. 11, 2008.
This application claims the priority of German application no. 10 2007 018 099.5 filed Apr. 17, 2007, the entire content of which is hereby incorporated by reference.
The invention is related to a red-emitting phosphor and a light source comprising such a phosphor.
EP-A 1 568 753 and EP-A 1 614 738 disclose a phosphor which emits in the red and has the composition MSiAlN3:Z. In this case, M is principally Ca and the activator Z is principally Eu. They are referred to here as calsins. Said phosphor can be excited well in the UV and blue spectral range. It is suitable for light sources such as LEDs.
EP-A 1 153 101 discloses a red-emitting phosphor of the type nitride M2Si5N8:Eu, wherein M can be Ca inter alia, and the activator is Eu.
One object of the present invention is to provide a narrowband, thermally stable phosphor which emits in the red. In this case, the dominant wavelength is intended to be greater than 610 nm and the phosphor is intended to be suitable for use with UV and blue LEDs.
This and other objects are attained in accordance with one aspect of the present invention directed to a red-emitting phosphor composed of an M-Al—Si—N system, comprising a cation M, wherein M is represented by at least one of the elements Ca or Ba or Sr and, if appropriate, can additionally be combined with at least one further element from the group Mg, Zn, Cd, wherein the phosphor is activated with Eu, which partly replaces M, and wherein the phosphor additionally contains LiF
As in the case of the nitrides, the previously known systems are distinguished by very high efficiency and thermal stability, but have the disadvantage of the broadband emission. Although the known calsins exhibit narrower-band emission than the nitrides and a better absorption in the blue, the thermal stability of the luminescence is poorer than in the case of the nitrides. Moreover, a shorter-wave emission is desirable in specific applications, in particular in order to obtain a higher visual useful effect.
According an embodiment of the invention, fluorides are now added in the synthesis of calsins. This improves the phase formation, grain form and also the homogeneity of the phosphor. In order not to obtain any impurities as a result of foreign ions, in practice use is usually made of fluorides together with cations which are present in the target compound. In the case of CaSiAlN3:Eu this is therefore CaF2, AlF3 or else EuF3. LiF is likewise known, in principle, as a flux, that is to say in the typical small quantities suitable therefor. It has surprisingly been found, however, that LiF becomes incorporated into the target compound in significant quantities and at the same time significantly improves the properties of the calsins.
The novel phosphor is suitable for example for color on demand LEDs or for white LEDs or else other light sources such as lamps. It can be tailored to different color temperatures and applications having high efficiency and good color rendering.
As a result of the incorporation of Li ions into the lattice, the thermal stability of the phosphor, the so-called thermal quenching thereof, is significantly improved without other properties of the phosphor being adversely altered. The centroid and peak of the emission surprisingly shift in the direction of a shorter wavelength given a constant Eu content. This tends to increase the efficiency. From a theoretical point of view, by contrast, a long-wave shift would more likely be expected. The reasons for this reside theoretically in a coarser grain and in an increased self-absorption of the short-wave emission components with the use of LiF. However, these considerations have not been borne out.
Even the quantum efficiency and the radiation stability tend to improve.
The invention will be explained in more detail below on the basis of an exemplary embodiment. In the figures:
What is suitable as a basic phosphor, in principle, is a red-emitting phosphor composed of the M-Al—Si—N system, comprising a cation M, where M is represented by Ca or Ba or Sr alone or in a mixture or can additionally be combined with at least one further element from the group Mg, Zn, Cd, wherein the phosphor is activated with Eu.
The proportion of LiF should be at most 15 mol %, relative to M.
Preferably, the proportion of LiF should be at least 1 mol %, relative to M.
Advantageously, Ca alone or very predominantly, that is to say to the extent of more than 70 mol % of Ca, should be used for M.
The production of the novel phosphor can be carried out for example as follows, explained using the example of (Ca, Eu)AlSiN3—LiF(2 mol %):
The starting substances Ca3N2 (6.02 g), AlN (6.02 g), LiF (0.57 g), Si3N4 (6.87 g) and Eu2O3 (0.52 g) are mixed in the glove box and with the aid of a mixer.
The batch mixtures are cooled in a tubular furnace under an inert atmosphere, preferably N2 with addition of FG, for a number of hours at temperatures of around 1450 to 1680° C. In this case, the heating and cooling rate is approximately 150 to 300 K/h.
The scope of protection of the invention is not limited to the examples given hereinabove. The invention is embodied in each novel characteristic and each combination of characteristics, which includes every combination of any features which are stated in the claims, even if this feature or combination of features is not explicitly stated in the examples.
Fiedler, Tim, Zachau, Martin, Jermann, Frank, Becker, Daniel, Pohl, Bianca
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