Patent Grant
10644206
Various embodiments relate to a lighting device, in particular a conversion light-emitting diode (conversion LED).
Phosphors which can be efficiently excited by ultraviolet, blue or green primary radiation and have an efficient emission in the blue, green, yellow, red or deep-red spectral range are of very great interest for the production of white and colored conversion LEDs. Conversion LEDs are used for many applications, for example for general lighting, display backlighting, signage, display panels, in automobiles and in numerous further consumer products. Conversion LEDs for the backlighting of display elements, such as displays, for example, differ greatly from conversion LEDs for general lighting. The requirements made of conversion LEDs for general lighting consist, in particular, in a high luminous efficiency combined with a high efficiency, a high color rendering index and a color temperature of less than 3500 K. Conversion LEDs for the backlighting of display elements require, in particular, phosphors having narrowband emission in the blue, green and red spectral range in order to cover the widest possible color space. Moreover, there is great demand for colored conversion LEDs which render colors adapted to consumer desires (so-called “color on demand” applications).
Previous white-emitting conversion LEDs for general lighting and backlighting use a semiconductor chip which emits a blue primary radiation, and a red and green phosphor. What is disadvantageous about this solution is that the epitaxially grown semiconductor chips, based for example on GaN or InGaN, can have fluctuations in the peak wavelength of the emitted primary radiation. This leads to fluctuations in the white overall radiation, such as a change in the color locus and the color rendering, since the primary radiation contributes the blue portion to the overall radiation. This is problematic particularly when a plurality of semiconductor chips are used in a device.
In order to avoid fluctuations, the semiconductor chips are sorted in accordance with their color loci (“binning”). The narrower the tolerances set with regard to the wavelength of the emitted primary radiation, the higher the quality of conversion LEDs which consist of more than one semiconductor chip. However, even after sorting with narrow tolerances, the peak wavelength of the semiconductor chips can change significantly in the case of variable operating temperatures and forward currents. In general lighting and other applications, this can lead to a change in the optical properties, such as the color locus and the color temperature.
In the backlighting of display elements, such as displays in televisions, computer monitors, tablets and smartphones, manufacturers endeavor to render the colors in a vivid and lifelike way, since this is very attractive to consumers. The backlighting of display elements therefore requires light sources having very narrowband emissions, that is to say a small full width at half maximum, in the green, blue and red spectral range in order to cover the widest possible color space. As light sources for backlighting applications, predominantly a blue-emitting semiconductor chip is combined with a phosphor having a peak wavelength in the green spectral range and a phosphor having a peak wavelength in the red spectral range.
Conversion LEDs for backlighting applications conventionally use as green phosphor, for example, an yttrium aluminum garnet, a lutetium aluminum garnet or a β-SiAlON (Si6−zAlzOzN8−z:RE or Si6−xAlzOyN8−y:REz where RE=rare earth metal). However, yttrium aluminum garnet has an emission peak having a large full width at half maximum, such that, as a result of considerable filter losses, the achievable color space is restricted and the efficiency is also reduced. β-SiAlON with a full width at half maximum of less than 60 nm has a narrowband emission in the green spectral range which leads to a more saturated green rendering than with a garnet phosphor. However, β-SiAlONs lack a good internal and external quantum efficiency, which makes the entire backlighting not very efficient. Furthermore, the production of these phosphors requires very high temperatures and expensive equipment. The production of the phosphor is thus very expensive and thus so is the production of conversion LEDs comprising said phosphor.
Quantum dots, on account of their very narrowband emission, are also used for converting primary radiation for backlighting applications. However, quantum dots are very unstable. Moreover, most commercially available quantum dots comprise harmful elements such as Hg or Cd, the concentration of which is limited in commercial electrical and electronic devices under the RoHS regulations (“reduction of hazardous substances”, EU Directive 2011/65/EU).
Known blue-green to green phosphors for conversion LEDs are for example the phosphors Ca8Mg(SiO4)4Cl2:Eu, (Sr,Ba)2SiO4:Eu and Lu3(Al,Ga)5O12:Ce. However, conversion LEDs comprising these phosphors have inadequate color purity and cannot achieve specific color loci, for which reason they are not appropriate for many “color on demand” applications.
The object of the present disclosure is to specify a lighting device, in particular a conversion LED, which is improved by comparison with the prior art and which can be used in particular for general lighting, backlighting and “color on demand” applications.
The object is achieved by means of a lighting device as claimed in independent claim 1. Advantageous embodiments and developments of the present disclosure are respectively specified in the dependent claims.
A phosphor is specified. The phosphor has the general molecular formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n.
In this case, MA is selected from a group of monovalent metals, MB is selected from a group of divalent metals, MC is selected from a group of trivalent metals, MD is selected from a group of tetravalent metals, TA is selected from a group of monovalent metals, TB is selected from a group of divalent metals, TC is selected from a group of trivalent metals, TD is selected from a group of tetravalent metals, TE is selected from a group of pentavalent elements, TF is selected from a group of hexavalent elements, XA is selected from a group of elements which comprises halogens, XB is selected from a group of elements which comprises O, S and combinations thereof, XC=N and XD=C. The following furthermore hold true:
In accordance with at least one embodiment, the phosphor comprises within its molecular formula at least Eu, Ce, Yb and/or Mn. Eu, Ce, Yb and/or Mn serve as activators of the phosphor which is responsible for the emission of radiation. The phosphor can thus have in particular the following formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n:E, wherein E=Eu,Ce,Yb and/or Mn.
Here and hereinafter phosphors are described on the basis of molecular formulae. In the case of the specified molecular formulae it is possible for the phosphor to comprise further elements for instance in the form of impurities, wherein these impurities taken together should advantageously have at most a proportion by weight in the phosphor of at most 1 per mille or 100 ppm (parts per million) or 10 ppm.
In accordance with at least one embodiment, the following holds true for the phosphor having the general molecular formula
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(A)k(XB)l(C)m(XD)n or
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n:E:0≤m<0.875v and/or v≥1>0.125v.
A lighting device comprising a phosphor is specified. The phosphor has the following general molecular formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n,
wherein
The assignment of the elements to MA, MB, MC, MD, TA, TB, TC, TD, TE, TF is based in particular on the arrangement thereof within the crystal structures of the phosphors. In particular, in this case, within the crystal structures TA, TB, TC, TD, TE and/or TF are surrounded by XA, XB, XC and/or XD and the resultant structural units are linked via common corners and edges. The corner and edge linkage of the structural units results in particular in the formation of cavities or channels in which MA, MB, MC and/or MD are arranged. On account of this assignment, it is possible for the possible elements in MA, MB, MC, MD, TA, TB, TC, TD, TE and TF to overlap.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
(MA)a(MB)b(TA)e(TB)f(TC)g(TD)h(XC)m(XB)l,
wherein
In one embodiment, the lighting device is a conversion light-emitting diode.
A conversion light-emitting diode (conversion LED) is specified. The conversion light-emitting diode (conversion LED) comprises a phosphor of the molecular formula (MA)a(MB)b (MC)c(MD)d(TA)e (TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n.
In this case, MA is selected from a group of monovalent metals, MB is selected from a group of divalent metals, MC is selected from a group of trivalent metals, MD is selected from a group of tetravalent metals, TA is selected from a group of monovalent metals, TB is selected from a group of divalent metals, TC is selected from a group of trivalent metals, TD is selected from a group of tetravalent metals, TE is selected from a group of pentavalent elements, TF is selected from a group of hexavalent elements, XA is selected from a group of elements which comprises halogens, XB is selected from a group of elements which comprises O, S and combinations thereof, XC=N and XD=C. The following furthermore hold true:
In accordance with one embodiment, the lighting device, in particular the conversion LED, comprises a primary radiation source configured to emit an electromagnetic primary radiation during operation of the lighting device, in particular of the conversion LED. Furthermore, the lighting device, in particular the conversion LED, comprises a conversion element arranged in the beam path of the electromagnetic primary radiation. The conversion element comprises a phosphor configured at least partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation during operation of the lighting device, in particular of the conversion LED. The phosphor has in particular the following molecular formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n,
wherein
The fact that the phosphor at least partly converts the electromagnetic primary radiation into an electromagnetic secondary radiation can mean, firstly, that the electromagnetic primary radiation is partly absorbed by the phosphor and emitted as secondary radiation having a wavelength range that is at least partly different, in particular longer, than the primary radiation. In the case of this so-called partial conversion, the lighting device, in particular the conversion LED, emits in particular an overall radiation composed of the primary radiation and the secondary radiation. It is thus possible for the lighting device, in particular the conversion LED, to emit a mixed radiation composed of primary radiation and secondary radiation.
The fact that the phosphor at least partly converts the electromagnetic primary radiation into an electromagnetic secondary radiation can also mean that the electromagnetic primary radiation is almost completely absorbed by the phosphor and is emitted in the form of an electromagnetic secondary radiation. This can also be referred to as full conversion. The emitted radiation or overall radiation of the lighting device, in particular of the conversion LED, in accordance with this embodiment thus almost completely corresponds to the electromagnetic secondary radiation. Almost complete conversion should be understood to mean a conversion of more than 90%, in particular more than 95%. It is thus possible for the lighting device, in particular the conversion LED, to emit predominantly secondary radiation.
In accordance with at least one embodiment, the primary radiation source is a layer sequence comprising an active layer configured to emit an electromagnetic primary radiation during operation of the lighting device.
In this context, “layer sequence” should be understood to mean a layer sequence comprising more than one layer, for example a sequence of a p-doped and an n-doped semiconductor layer, wherein the layers are arranged one above another and wherein at least one active layer which emits electromagnetic primary radiation is contained.
The layer sequence can be embodied as an epitaxial layer sequence or as a radiation-emitting semiconductor chip having an epitaxial layer sequence, that is to say as an epitaxially grown semiconductor layer sequence. In this case, the layer sequence can be embodied for example on the basis of InGaAlN. InGaAlN-based semiconductor chips and semiconductor layer sequences are, in particular, those in which the epitaxially produced semiconductor layer sequence comprises a layer sequence composed of different individual layers which contains at least one individual layer comprising a material from the III-V compound semiconductor material system InxAlyGa1-x-yN where 0≤x≤1, 0≤y≤1 and x+y≤1. Semiconductor layer sequences comprising at least one active layer on the basis of InGaAlN can emit for example electromagnetic radiation in an ultraviolet to blue wavelength range.
Besides the active layer, the active semiconductor layer sequence can comprise further functional layers and functional regions, for instance p- or n-doped charge carrier transport layers, that is to say electron or hole transport layers, undoped or p- or n-doped confinement, cladding or waveguide layers, barrier layers, planarization layers, buffer layers, protective layers and/or electrodes and combinations thereof. Furthermore, one or more mirror layers can be applied for example on a side of the semiconductor layer sequence facing away from the growth substrate. The structures described here, concerning the active layer or the further functional layers and regions, are known to the person skilled in the art in particular with regard to construction, function and structure and are therefore not explained in greater detail at this juncture.
In one embodiment, the emitted primary radiation of the primary radiation source or of the active layer of the layer sequence is in the near UV range to blue range of the electromagnetic spectrum. In this case, in the near UV range can mean that the emitted primary radiation has a wavelength of between 300 nm and 420 nm inclusive. In this case, in the blue range of the electromagnetic spectrum can mean that the emitted primary radiation has a wavelength of between 420 nm and 500 nm inclusive, advantageously up to and including 460 nm.
In one embodiment, during operation of the lighting device the active layer of the layer sequence emits an electromagnetic primary radiation having a wavelength of between 300 nm and 500 nm inclusive or between 300 nm and 460 nm inclusive, advantageously between 300 nm or 330 nm and 450 nm or 440 nm or 430 nm inclusive.
In accordance with at least one embodiment, the primary radiation source or the layer sequence has a radiation exit surface, above which the conversion element is arranged.
Here and hereinafter the fact that one layer or one element is arranged or applied “on” or “above” another layer or another element can mean in this case that said one layer or said one element is arranged directly in direct mechanical and/or electrical contact on the other layer or the other element. Furthermore, it can also mean that said one layer or said one element is arranged indirectly on or above the other layer or the other element. In this case, further layers and/or elements can then be arranged between said one or the other layer or between said one or the other element.
In this case, the radiation exit surface is a main surface of the primary radiation source or of the layer sequence. The radiation exit surface extends in particular parallel to a main extension plane of the semiconductor layers of the layer sequence. By way of example, at least 75% or 90% of the primary radiation leaving the layer sequence emerges from the layer sequence via the radiation exit surface.
In one embodiment, the conversion element has direct mechanical contact with the primary radiation source or the layer sequence, in particular with the radiation exit surface of the primary radiation source or of the layer sequence.
In one embodiment, the conversion element is arranged over the whole area above the primary radiation source or the layer sequence, in particular the radiation exit surface of the primary radiation source or of the layer sequence.
In one embodiment, the conversion element comprises a matrix material. The phosphor can be distributed in the matrix material; by way of example, the phosphor is distributed homogeneously in the matrix material.
The matrix material is transparent both to the primary radiation and to the secondary radiation and is selected for example from a group of materials consisting of: glasses, silicones, epoxy resins, polysilazanes, polymethacrylates and polycarbonates and combinations thereof. Transparent is understood to mean that the matrix material is at least partly transmissive to the primary radiation and also to the secondary radiation.
In accordance with at least one embodiment, MA, MB, MC, MD, TA, TB, TC, TD, TE and TF are the corresponding monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent cations. In other words, MA and TA have the oxidation number +1, MB and TB have the oxidation number +2, MC and TC have the oxidation number +3, MD and TD have the oxidation number +4, TE has the oxidation number +5 and TF has the oxidation number +6. XA, XB, XC and XD are, in particular, the anions of the corresponding elements. In this case, XA advantageously has the oxidation number −1, XB the oxidation number −2, XC, that is to say N, the oxidation number −3 and XD, that is to say C, the oxidation number −4.
WO 2013/175336 A1 describes a new family of red-emitting phosphors which have an emission having small values of the full width at half maximum. The phosphors disclosed therein have a proportion of at least 87.5% nitrogen and at most 12.5% oxygen relative to the total amount of anionic elements of the phosphor. In accordance with WO 2013/175336 A1, a higher oxygen content in the phosphors leads to unstable compounds. Consequently, phosphors having an oxygen content of more than 12.5% could not be isolated.
Here and hereinafter the full width at half maximum is understood to mean the spectral width at the level of half the maximum of the emission peak, FWHM for short. The emission peak is understood to mean the peak having the maximum intensity.
The inventors of the present disclosure have surprisingly established that a higher oxygen and/or sulfur proportion, that is to say an oxygen and/or sulfur proportion in the phosphor of more than 12.5 mol % relative to the total substance amount of anionic elements, or a lower nitrogen proportion, that is to say a nitrogen proportion in the phosphor of less than 87.5 mol % relative to the total substance amount of anionic elements, leads to very stable and efficient phosphors having a high quantum efficiency. The phosphors have a high absorptivity in the UV range to green range, in particular between 300 nm and 500 nm or between 300 nm and 460 nm, advantageously between 300 nm and 430 nm or 300 nm and 450 nm, and can thus be efficiently excited by a primary radiation in this wavelength range. The primary radiation can be converted completely (full conversion) or partly (partial conversion) into a radiation of longer wavelength, also called secondary radiation, by the phosphors.
In accordance with at least one embodiment, it advantageously holds true that: 0≤m<0.75 v or v≥l>0.25 v, 0≤m<0.625 v or v≥l>0.375 v. Particularly advantageously: 0≤m<0.5 v or v≥l>0.5 v, 0≤m<0.375 v or v≥l>0.625 v, 0≤m<0.25 v or v≥l>0.7 v, 0≤m<0.125 v or v≥l>0.875 v or m=0 or 1=v.
The inventors have discovered that, surprisingly, with increasing oxygen and/or sulfur content or with decreasing nitrogen content, the peak wavelength of the phosphors shifts toward shorter wavelengths and moreover very stable phosphors result. As a result it is advantageously possible to correspondingly set the desired peak wavelength of the phosphor by varying the oxygen or nitrogen content. Moreover, the peak wavelength and/or the full width at half maximum of the phosphor can be varied by combinations or substitutions of the metals or elements MA, MB, MC, MD, TA, TB, TC, TD, TE, TF, XA, XC, XD and/or XB. A possibility has thus been found of providing phosphors which, in terms of their properties, in particular the peak wavelength and the full width at half maximum, can be adapted in a targeted manner for a corresponding application and in this case are surprisingly also still very stable. In particular, the phosphors can have very narrow values of the full width at half maximum, for example below 50 nm, below 30 nm or below 20 nm, which makes the phosphors interesting for many applications, for example for backlighting applications.
In the present case, “peak wavelength” denotes the wavelength in the emission spectrum at which the maximum intensity is present in the emission spectrum.
In accordance with at least one embodiment, the following hold true for the phosphor having the molecular formula (MA)a(MB)b (MC)c(MD)d(TA)e (TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n:E:
a+b+c+d=1;
e+f+g+h+i+j=4;
k+l+m+n=4;
a+2b+3c+4d+e+2f+3g+4h+5i+6j−k−2l−3m−4n=0 and m<3.5 or l>0.5. This is therefore an electroneutral phosphor.
In accordance with at least one embodiment, it holds true that n=0, k=0, v=4 and m<3.5 and l>0.5. Then the phosphor thus has the following molecular formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XB)l(XC)m:E.
In this case, MA, MB, MC, MD, TA, TB, TC, TD, TE, TF, XC and XB are defined as above. In accordance with this embodiment, the phosphor comprises only nitrogen and oxygen, nitrogen and sulfur or nitrogen, sulfur and oxygen, advantageously only nitrogen and oxygen, as anions. However, this does not exclude the presence of further, including anionic, elements in the form of impurities. It advantageously holds true that m<3.0 and l>1.0; m<2.5 and l>1.5; m<2.0 and l<2.0; m<1.5 and l>2.5; m<1.5 and l>2.5; m<1.0 and l>3.0; m<0.5 and l>3.5 or m=0 and 1=4.
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)a(MB)b(TA)e(TD)h(XB)l(XC)m:E.
In this case, the following advantageously hold true:
In accordance with at least one embodiment, the phosphor has the general molecular formula
(MA)a(MB)b(TA)e(TD)h(XB)l(XC)m:E.
In this case, the following hold true:
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)a(MB)b(TA)e(TC)g(TD)h(XB)l(XC)m:E auf, wherein
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)a(MB)b(TA)e(TC)g(TD)h(XB)l(XC)m:E auf, wherein
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)a(MB) b (TA) e (TC)g (TD) h (XB)l(XC)m:E, wherein
In accordance with at least one embodiment, the phosphor is an oxide, that is to say that only oxygen is present as anionic element in the phosphor. The phosphor then has one of the following general molecular formulae:
(MA)1(TA)3(TD)1(XB)4:E,
(MA)1(TA)3-x(TD)1-x(TB)x(TC)x(XB)4:E,
(MA)1-x′(MB)x′(TA)3(TD)1−x′(TC)x′(XB)4:E,
(MA)1−x″(MB)x(TA)3−x″(TD)1−x″(TB)2x″(XB)4:E,
(MA)1(TA)3−2z(TB)3z(TD)1−z(XB)4:E or
(MA)1(TA)3(TD)1−2z′(TC)z′(TE)z′(XB)4:E, wherein
XB=O,
0≤x≤1, for example x=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<x<1, for example x=0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8 or 0.9,
0≤x′≤1, for example x′=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<x′<1, for example x′=0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8 or 0.9,
0≤x″≤1, for example x″=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<x<1, for example x″=0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8 or 0.9,
0≤z≤1, advantageously z=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<z<1, for example z=0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8 or 0.9,
0≤z′≤0.5, advantageously 0<z′<0.5, for example z′=0, 0.1; 0.2; 0.3 or 0.4,
and E is selected from a group comprising Eu, Ce, Yb, Mn and combinations thereof.
Here and hereinafter E can also be referred to as activator. The activator and in particular its surroundings in the host lattice are responsible for the luminescence, in particular the peak wavelength of the emission of the phosphor.
The metals or elements MA, MB, TA, TB, TC, TD, TE and/or XB form in the phosphors in particular the host lattice; in this case, E can partly replace lattice sites of the cationic elements MA, MB, TA, TB, TC, TD and/or TE, or occupy interstitial sites. In particular, in this case E occupies the lattice sites of MA. For charge balancing, the proportion of the further elements, for example that of TA and/or TD, may change.
In accordance with at least one embodiment, the phosphor is an oxide or oxonitride, advantageously an oxonitride, and therefore has in its molecular formula only oxygen or oxygen and nitrogen as anionic elements. In this case, the phosphor can have one of the following general molecular formulae:
(MA)1−y(TB)y(TA)3−2y(TC)3y(TD)1−y(XB)4−4y(XC)4y:E,
(MA)1−y*(MB)y*(TA)3−2y*(TC)3y*(TD)1−y*(XB)4−4y*(XC)4y*:E,
(MA)1(TA)3−y′(TC)y′(TD)1(XB)4−2y′(XC)2y′:E,
(MA)1(TA)3−y″(TB)y″(TD)1(XB)4−y″(XC)y″:E,
(MA)1−w′″(MB)w′″(TA)3(TD)1(XB)4−w′″(XC)w′″:E,
(MA)1(TA)3−w′(TC)2w′(TD)1−w′(XB)4−w′(XC)w′:E or
(MA)1−w″(MB)w″(TA)3−w″(TD)1−w″(TC)2w″(XB)4−2w″(XC)2w″:E,
wherein
XB=O,
0≤y≤1, for example y=0; 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<y<0.875, for example y=0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7 or 0.8, very particularly advantageously 0≤y≤0.4,
0<y*<0.875 or advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1,
0≤y′≤2, for example y′=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9; 1.0; 1.1; 1.2; 1.3; 1.4; 1.5; 1.6; 1.7; 1.8; 1.9 or 2.0, advantageously 0<y′≤1.75, particularly advantageously 0≤y′≤0.9,
0≤y″≤3, for example y″=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9; 1.0; 1.1; 1.2; 1.3; 1.4; 1.5; 1.6; 1.7; 1.8; 1.9; 2.0; 2.1; 2.2; 2.3; 2.4; 2.5; 2.6; 2.7; 2.8; 2.9 or 3.0, advantageously 0<y″<3, particularly advantageously 0<y″≤1.9,
0≤w′″≤1, for example w′″=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<w′″<1,
0≤w′≤1, for example w′=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<w′<1,
0≤w″≤1, for example w″=0, 0.1; 0.2; 0.3; 0.4; 0.5; 0.6; 0.7; 0.8; 0.9 or 1, advantageously 0<w″<1, and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof.
In accordance with at least one embodiment, E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof. In particular, E is Eu3+, Eu2+, Ce3+, Yb3+, Yb2+ and/or Mn4+.
The metals or elements MA, MB, TA, TB, TC, TD, XC and/or XB form the host lattice in the phosphors; in this case, E can partly replace lattice sites of MA, MB, TA, TB, TC and/or TD, advantageously of MA, or occupy interstitial sites.
By using the activators Eu, Ce, Yb and/or Mn, in particular Eu or Eu in combination with Ce, Yb and/or Mn, it is possible for the color locus of the phosphor in the CIE color space, the peak wavelength λpeak thereof or the dominant wavelength λdom thereof, and the full width at half maximum to be set particularly well.
The dominant wavelength is a possibility for describing non-spectral (polychromatic) light mixtures by spectral (monochromatic) light that produces a similar hue perception. In the CIE color space, the line connecting a point for a specific color and the point CIE-x=0.333, CIE-y=0.333 can be extrapolated such that it meets the contour of the space at two points. The intersection point that is nearer to said color represents the dominant wavelength of the color as wavelength of the pure spectral color at this intersection point. The dominant wavelength is thus the wavelength that is perceived by the human eye.
In accordance with a further embodiment, the activator E can be present in mol % amounts of between 0.1 mol % and 20 mol %, 1 mol % and 10 mol %, 0.5 mol % and 5 mol %, 2 mol % and 5 mol %. Excessively high concentrations of E may lead to a loss of efficiency as a result of concentration quenching. Here and hereinafter, mol % indications for the activator E, in particular Eu, are understood in particular as mol % indications relative to the molar proportions of MA, MB, MC and MD in the respective phosphor.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(MA)Li3−xSi1−xZnxAlxO4:E;
(MA)Li3−xSi1−xMgxAlxO4:E;
(MA)1−x′Cax′Li3Si1−x′Alx′O4:E;
(MA)1−x″Cax″Li3−x″Si1−x″Mg2x″O4:E;
(MA)Li3−2zMg3zSi1−zO4:E;
(MA)Li3Si1−2z′Alz′Pz′O4:E.
In particular, MA, E, x, x′, x″, z and z′ are accorded the definitions disclosed above.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E, in accordance with at least one embodiment, LiSi can be at least partly replaced by ZnAl or MgAl and a phosphor of the formula (MA)Li3−xSi1−xZnxAlxO4:E or (MA)Li3−xSi1−xMgxAlxO4:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)Si can be at least partly replaced by CaAl and a phosphor of the formula (MA)1−x′Cax′Li3Si1−x′Alx′O4:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)LiSi can be at least partly replaced by CaMg2 and a phosphor of the formula (MA)1−x″Cax″Li3−x″Si1−x″Mg2x″O4:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, Li2Si can be at least partly replaced by Mg3 and a phosphor of the formula (MA)Li3−2zMg3zSi1−zO4:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, Si2 can be at least partly replaced by AlP and a phosphor of the formula (MA)Li3Si1−2z′Alz′Pz′O4:E is obtained.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(MA)1−yZnyLi3−2yAl3ySi1−yO4−4yN4y:E
(MA)1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E,
(MA)1−y***Sry***Li3−2y***Al3y***Si1−y***O4−4y***N4y***:E
(MA)1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E
(MA)Li3−y′Aly′SiO4−2y′N2y′:E,
(MA)Li3−y″Mgy″SiO4−y″Ny″:E,
(MA)1−w′″Caw′″Li3SiO4−w′″Nw′″:E,
(MA)Li3−w′Al2w′Si1−w′O4−w′Nw′:E,
(MA)1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E.
In particular, MA, E, y, y*, y′, y″, w′″, w′ and w″ are accorded the definitions disclosed above. It furthermore holds true that 0<y**≤1, advantageously 0<y**<0.875 or 0<y**<0.5, particularly advantageously 0.05≤y**≤0.45, very particularly advantageously 0.1≤y**≤0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3 and 0≤y***≤1, advantageously 0<y***<0.875 or 0<y***≤0.5, particularly advantageously 0<y***≤0.3.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)Li3SiO4 can be at least partly replaced by CaLiAl3N4 and a phosphor of the formula (MA)1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E is obtained. In this case, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs, Cu, Ag and combinations thereof, and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof. Advantageously, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb and combinations thereof and E=Eu. Very advantageously, MA=Na. The phosphor is an oxonitridolithoalumosilicate phosphor. It holds true that 0<y*<0.875, advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1. By way of example, it holds true that y*=0.01; 0.02; 0.03; 0.04 or 0.05.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)Li3SiO4 can be at least partly replaced by SrLiAl3N4 and a phosphor of the formula (MA)1−y***Sry***Li3−2y***Al3y***Si1−y***O4−4y***N4y***:E is obtained. In this case, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs, Cu, Ag and combinations thereof and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof, advantageously, E=Eu. Advantageously, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb and combinations thereof. Very advantageously, MA=Na. The phosphor is an oxonitridolithoalumosilicate phosphor. It holds true that 0<y***<0.875, advantageously 0<y***≤0.5, particularly advantageously 0<y***≤0.3. For example y***=0.25.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)Li3SiO4 can be at least partly replaced by EuLiAl3N4 and a phosphor of the formula (MA)1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E is obtained. In this case, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs, Cu, Ag and combinations thereof, and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof; advantageously, E=Eu. Advantageously, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb and combinations thereof. Very advantageously, MA=Na. The phosphor is an oxonitridolithoalumosilicate phosphor. It advantageously holds true that 0<y**<0.875 or 0<y**<0.5, particularly advantageously 0.05≤y**≤0.45, very particularly advantageously 0.1≤y**≤0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3. Surprisingly, despite the in some instances very high proportions of Eu, the phosphor does not exhibit any concentration-governed quenching behavior and the associated loss of efficiency. Despite the high proportion of Eu, the phosphor is thus surprisingly very efficient.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, LiO2 can be at least partly replaced by AlN2 and a phosphor of the formula (MA)Li3−y′Aly′SiO4−2y′N2y′:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, LiO can be at least partly replaced by MgN and a phosphor of the formula (MA)Li3−y″Mgy″SiO4−y″Ny″:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)O can be at least partly replaced by CaN and a phosphor of the formula (MA)1−w′″Caw′″Li3SiO4−w′″Nw′″:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, LiSiO can be at least partly replaced by Al2N and a phosphor of the formula (MA)Li3w′Al2w′Si1−w′O4−w′Nw′:E is obtained.
Proceeding from the phosphor of the molecular formula (MA)Li3SiO4:E in accordance with at least one embodiment, (MA)Li3SiO2 can be at least partly replaced by CaAl2N2 and a phosphor of the formula (MA)1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E is obtained.
In accordance with at least one embodiment, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs and combinations thereof. By way of example, MA can be chosen as follows: MA=Na, K, (Na,K), (Rb,Li). (Na,K), (Rb,Li) in this case means that a combination of Na and K or a combination of Rb and Li is present. This choice of MA yields particularly efficient phosphors that are applicable in diverse ways.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
NaLi3−xSi1−xZnxAlxO4:E,
NaLi3−xSi1−xMgxAlxO4:E,
Na1−x′Cax′Li3Si1−x′Alx′O4:E,
Na1−x″Cax″Li3−x″Si1−x″Mg2x″O4:E,
NaLi3−2zMg3zSi1−zO4:E,
NaLi3Si1−2z′Alz′Pz′O4:E.
In particular, x, x′, x″, z and z′ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(NarK1−r)1Li3−xSi1−xZnxAlxO4:E,
(NarK1−r)1Li3−xSi1−xMgxAlxO4:E,
(NarK1−r)1−x′Cax′Li3Si1−x′Alx′O4:E,
(NarK1−r)1−x″Cax″Li3−x″Si1−x″Mg2x″O4:E,
(NarK1−r)1Li3−2zMg3zSi1−zO4:E,
(NarK1−r)1Li3Si1−2z′Alz′Pz′O4:E, wherein
0≤r≤1, for example r=0; 0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0. Advantageously, 0≤r≤0.1 or 0.1<r≤0.4 or 0.4<r≤1.0; particularly advantageously r=0, 0.125, 0.25, 0.5 or 1.0. In particular, x, x′, x″, z and z′ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(Rbr′Li1−r′)1Li3−xSi1−xZnxAlxO4:E,
(Rbr′Li1−r′)1Li3−xSi1−xMgxAlxO4:E,
(Rbr′Li1−r′)1−x′Cax′Li3Si1−x′Alx′O4:E,
(Rbr′Li1−r′)1−x″Cax″Li3−x″Si1−x″Mg2x″O4:E,
(Rbr′Li1−r′)1Li3−2zMg3zSi1−zO4:E,
(Rbr′Li1−r′)1Li3Si1−2z′Alz′Pz′O4:E, wherein
0≤r′≤1, for example r′=0; 0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, very particularly advantageously r′=0.5. In particular, x, x′, x″, z and z′ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(NarK1−r)1−y*Cay*Li3−2y*Al3y*Si1−yO4−4y*N4y*:E,
(NarK1−r)Li3−y′Aly′SiO4−2y′N2y′:E,
(NarK1−r)Li3−y″Mgy″SiO4−y″Ny″:E,
(NarK1−r)1−w′″Caw′″Li3SiO4−w′″Nw:E,
(NarK1−r)Li3−w′Al2w′Si1−w′O4−w′Nw′:E,
(NarK1−r)1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E, wherein
0≤r≤1, for example r=0; 0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0. Advantageously, 0≤r≤0.1 or 0.1<r≤0.4 or 0.4<r≤1.0; particularly advantageously r=0, 0.25, 0.5 or 1.0. In particular, y*, y′, y″, w′″, w′ and w″ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
(Rbr′Li1−r′)1−y*Cay*Li3−2y*Al3y*Si1−y*N4y*:E,
(Rbr′Li1−r′)Li3−y′Aly′SiO4−2y′N2y′:E,
(Rbr′Li1−r′)Li3−y″Mgy″SiO4−y″Ny″:E,
(Rbr′Li1−r′)1−w′″Caw′″Li3SiO4−w′″Nw:E,
(Rbr′Li1−r′)Li3−w′Al2w′Si1−w′O4−w′Nw′:E,
(Rbr′Li1−r′)1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E, wherein
0≤r′≤1, for example r′=0; 0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, very particularly advantageously r′=0.5. In particular, y*, y′, y″, w′″, w′ and w″ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has one of the following general molecular formulae:
Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E,
NaLi3−y′Aly′SiO4−2y′N2y′:E,
NaLi3−y″Mgy″SiO4−y″Ny″:E,
Na1−w′″Caw′″Li3SiO4−w′″Nw:E,
NaLi3−w′Al2w′Si1−w′O4−w′Nw′:E,
Na1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E.
In particular, y*, y′, y″, w′″, w′ and w″ are accorded the meanings mentioned above.
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)1(TA)3(TD)1(XB)4:E. In this case, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs, Cu, Ag and combinations thereof. Advantageously, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs and combinations thereof. TA is selected from a group of monovalent metals which comprises Li, Na, Cu, Ag and combinations thereof. TD is selected from a group of tetravalent metals which comprises Si, Ge, Sm, Mn, Ti, Zr, Hf, Ce and combinations thereof. XB is selected from a group of elements which comprises O, S and combinations thereof. E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof; advantageously, E=Eu. In particular, E occupies the lattice sites of MA or interstitial sites. For charge balancing, in this case the proportion of the further elements, for example that of TA and/or TD, may change. By way of example, E=Eu2+ and replaces MA+ in the molecular formula; the charge balancing is effected by changing the proportion of TA and/or TD.
In accordance with at least one embodiment, the phosphor has the general molecular formula (MA)1(TA)3(TD)1(XB)4:E. In this case, MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs and combinations thereof. TA=Li, TD=Si, XB=O and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof. It advantageously holds true that: E=Eu or a combination of Eu with Ce, Yb and/or Mn.
Surprisingly, it has been found that the properties of the phosphor, in particular with regard to the peak wavelength and the full width at half maximum, can be changed considerably by varying the composition of MA. Moreover, the phosphors have a high absorptivity of primary radiation in the range of 300 nm to 460 nm or 300 nm to 500 nm, in particular between 300 nm and 450 nm or 300 nm and 430 nm.
By way of example, the phosphor of the formula NaLi3SiO4:Eu, upon excitation with a primary radiation having a wavelength of 400 nm, emits in the blue spectral range of the electromagnetic spectrum and exhibits a narrowband emission, that is to say an emission having a small full width at half maximum. By contrast, upon excitation with a primary radiation having a wavelength of 400 nm, the phosphor of the formula KLi3SiO4:Eu exhibits very broadband emission from the blue to red spectral range, thus giving rise to a white-colored luminous impression. The phosphors of the formula (Na0.5K0.5) Li3SiO4:Eu, (Rb0.25Na0.75) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu, (Rb0.25Na0.5K0.25) Li3SiO4:Eu and (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu exhibit narrowband emission in the blue-green spectral range of the electromagnetic spectrum and the phosphors of the formula (Rb0.5Li0.5) Li3SiO4:Eu, (Rb0.5Na0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu, (Na0.25K0.50Li0.25) Li3SiO4:Eu and (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu exhibit narrowband emission in the green spectral range of the electromagnetic spectrum. Upon excitation with a primary radiation having a wavelength of 460 nm, the phosphor of the formula Na0.125K0.875Li3SiO4:Eu has a band in the yellow-orange range. Besides the latter, Na0.125K0.875Li3SiO4:Eu exhibits a further emission peak having high intensity in the blue-green range.
The properties of the phosphors are presented in the table below:
By virtue of the different emission properties, the phosphors are suitable for a wide variety of applications.
The blue or blue-green spectral range is understood to mean the range of the electromagnetic spectrum between 420 nm and 520 nm.
The green spectral range is understood to mean the range of the electromagnetic spectrum between 520 nm and 580 nm inclusive.
The red spectral range is understood to mean the range of the electromagnetic spectrum between 630 nm and 780 nm.
The yellow or yellow-orange spectral range is understood to mean the range of the electromagnetic spectrum between 580 nm and 630 nm.
In accordance with at least one embodiment, the phosphor has the general molecular formula (NarK1−r)1(TA)3(TD)1(XB)4:E, where 0≤r≤1, for example r=0; 0.05; 0.1; 0.125; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0. Advantageously, 0≤r≤0.1 or 0.1<r≤0.4 or 0.4<r≤1.0; particularly advantageously r=0, 0.125, 0.25, 0.5 or 1.0. Advantageously, TA=Li, TD=Si, XB=O and E=Eu, Ce, Yb and/or Mn, advantageously E=Eu. Surprisingly, the properties of the phosphor, in particular the peak wavelength and the full width at half maximum, change upon variation of the proportions of Na and K in the phosphor. As a result, a wide variety of applications are usable by virtue of these phosphors.
In accordance with at least one embodiment, the phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r) Li3SiO4:E crystallizes in a tetragonal, monoclinic or triclinic crystal system, in particular in a tetragonal or triclinic crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I41/a, I4/m or P-1. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I41/a or I4/m or in a triclinic crystal system with the space group P-1.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, advantageously 0.45<r≤1, very particularly advantageously r=0.5 or 1. Advantageously, TA=Li, TD=Si, XB=O and E=Eu, Ce, Yb and/or Mn, and the phosphor has the formula (NarK1-r)Li3SiO4:E. Advantageously, it holds true that E=Eu. By way of example, the phosphor has the formula NaLi3SiO4:Eu or (Na0.5K0.5)Li3SiO4:Eu. The peak wavelength of the phosphor is in the blue spectral range, in particular in the range between 450 nm and 500 nm.
The phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r) Li3SiO4:E where 0.4<r≤1, for example NaLi3SiO4:Eu or (Na0.5K0.5)Li3SiO4:Eu, is suitable in particular for use in conversion LEDs which emit white radiation. To that end, the phosphor can be combined with a red and green phosphor.
Moreover, the phosphor (NarK1-)1(TA)3(TD)1(XB)4:E or (NarK1-r) Li3SiO4:E where 0.4<r≤1, in particular (Na0.5K0.5)Li3SiO4:Eu, is suitable for use in lighting devices such as conversion LEDs which emit a blue radiation.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, very particularly advantageously r=0.25. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (NarK1−r)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. By way of example, the phosphor has the formula (Na0.25K0.75) Li3SiO4:Eu. The peak wavelength of the phosphor is in the green spectral range, in particular.
The phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r)Li3SiO4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.4, particularly advantageously 0.2<r≤0.3, very particularly advantageously r=0.25, is suitable in particular for use in conversion LEDs for the backlighting of displays.
Moreover, the phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1-r)Li3SiO4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.4, in particular (Na0.25K0.75)Li3SiO4:Eu, is suitable for use in lighting devices such as conversion LEDs which emit a green radiation.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.05<r≤0.2, advantageously 0.1<r≤0.2. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (NarK1−r)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. By way of example, the phosphor is Na0.125K0.875Li3SiO4:Eu.
Surprisingly, the phosphor of the formula (NarK1-r)1(TA)3(TD)1(XB)4:E or (NarK1−r)Li3SiO4:E where 0.05<r≤0.2 has a wide emission band. In particular, besides the band having the highest intensity (=peak wavelength), the phosphor has a further emission peak, which has an intensity of similar magnitude to that of the emission peak at the peak wavelength.
The phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r) Li3SiO4:E where 0.05<r≤0.2, advantageously 0.1<r≤0.2, in particular Na0.125K0.875Li3SiO4:Eu, is suitable for example for use in lighting devices such as conversion LEDs which emit white radiation. By virtue of the wide emission, in particular the two emission peaks in the blue or blue-green range and in the yellow-orange range, the phosphor can advantageously be used as sole phosphor in a lighting device such as a conversion LED. In particular, with such a conversion LED it is possible to generate a white overall radiation having color temperatures above 8000 K and a high color rendering index and great color space coverage, which can be used in particular for general lighting and backlighting of displays.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0≤r≤0.05, advantageously r=0. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (NarK1−r)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof, advantageously, E=Eu. By way of example, the phosphor is KLi3SiO4:Eu. The phosphor exhibits very broadband emission from the blue to red spectral range, thus giving rise to a white luminous impression.
The phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r)Li3SiO4:E where 0≤r≤0.05, in particular KLi3SiO4:Eu, is suitable for example for use in lighting devices such as conversion LEDs which emit white radiation. As a result of the wide emission of the phosphor, the latter can advantageously be used as sole phosphor in a lighting device such as a conversion LED.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E, wherein 0≤r′≤1, for example r′=0; 0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95; 1.0, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, very particularly advantageously r′=0.5. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rbr′Li1−r′)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. It has been found that these phosphors have a small full width at half maximum and are applicable in diverse ways.
In accordance with at least one embodiment, the phosphor has the general molecular formula (K,Na,Li,Cs)1(TA)3(TD)1(XB)4:E, wherein K, Na, Li and Cs are contained in the phosphor. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (K,Na,Li,Cs)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. Particularly advantageously, the phosphor has the formula (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Cs0.25Na0.25K0.25Li0.25)Li3SiO4:E. The peak wavelength of the phosphor is in the green spectral range, in particular, and has a full width at half maximum of less than 50 nm.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rb,Na,Li,Cs)1(TA)3(TD)1(XB)4:E, wherein Rb, Na, Li and Cs are contained in the phosphor.
Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rb,Na,Li,Cs) Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. Particularly advantageously, the phosphor has the formula (Cs0.25Na0.25Rb0.25Li0.25) (TA)3(TD)1(XB)4:E or (Cs0.25Na0.25Rb0.25Li0.25)Li3SiO4:E. The peak wavelength of the phosphor is in the blue spectral range, in particular, and has a full width at half maximum of less than 30 nm.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Cs,Na,K)1(TA)3(TD)1(XB)4:E, wherein Na, K and Cs are contained in the phosphor. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Cs,Na,K)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. Particularly advantageously, the phosphor has the formula (Cs0.25Na0.50K0.25) (TA)3(TD)1(XB)4:E or (Cs0.25Na0.50K0.25)Li3SiO4:E. The peak wavelength of the phosphor is in the blue spectral range, in particular, and has a full width at half maximum of less than 30 nm.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rb,Na,K)1(TA)3(TD)1(XB)4:E, wherein Na, K and Rb are contained in the phosphor. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rb,Na,K) Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. Particularly advantageously, the phosphor has the formula (Rb0.25Na0.50K0.25) (TA)3(TD)1(XB)4:E or (Rb0.25Na0.50K0.25) Li3SiO4:E. The peak wavelength of the phosphor is in the blue spectral range, in particular, and has a full width at half maximum of less than 30 nm.
The phosphors (Rb,Na,Li,Cs)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E and (Rb,Na,K)1(TA)3(TD)1(XB)4:E are suitable in particular for use in conversion LEDs which emit white radiation. To that end, the phosphor can be combined in each case with a red and green phosphor. Moreover, these phosphors are suitable for use in lighting devices such as conversion LEDs which emit a blue radiation.
In accordance with at least one embodiment, the phosphor (Rb,Na,Li,Cs)1(TA)3(TD)1(XB)4:E, (K,Na,Li,Cs)1(TA)3(TD)1(XB)4:E, (Rb,Na,K)1(TA)3(TD)1(XB)4:E, (Cs,Na,K) (TA)3(TD)1(XB)4:E, (K,Na,Li,Cs) Li3SiO4:E, (Rb,Na,Li,Cs) Li3SiO4:E, (Rb,Na,K) Li3SiO4:E or (Cs,Na,K)Li3SiO4:E crystallizes in a tetragonal crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with I4/m.
In accordance with at least one embodiment, the phosphor has the general molecular formula
(K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E,
wherein 0<r″<0.5 and 0<r′″<0.5, for example r″=0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45 and r″′=0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45. Advantageously, 0.1<r′<0.4 and 0.1<r′″<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r′″<0.3. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (K1−r″-r′″Nar″Lir′″)1Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously, E=Eu. Surprisingly, the properties of the phosphor, in particular the peak wavelength and the full width at half maximum, change upon variation of the proportions of Na, Li and K in the phosphor.
As a result, these phosphors can be used in a wide variety of applications. By way of example, the phosphor has the formula (K0.5Na0.25Li0.25)Li3SiO4:Eu. The peak wavelength of the phosphor is in the green spectral range, in particular, and has a full width at half maximum of less than 50 nm.
In accordance with at least one embodiment, the phosphor (K1-r″-r′″Nar″Lir′″)1 (TA)3(TD)1(XB)4:E or (K1−r″-r′″Nar″Lir′″)1Li3SiO4:E crystallizes in a tetragonal or monoclinic crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m or C2/m. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I4/m or in a monoclinic crystal system with the space group C2/m, particularly advantageously in a monoclinic crystal system with the space group C2/m.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<1, for example r*=0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, 0.4; 0.45; 0.5; 0.55; 0.6; 0.65; 0.7; 0.75; 0.8; 0.85; 0.9; 0.95. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rbr*Na1−r*)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously E=Eu.
In accordance with at least one embodiment, the phosphor (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E or (Rbr*Na1−r*) Li3SiO4:E crystallizes in a tetragonal or monoclinic crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m or C2/m. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I4/m or in a monoclinic crystal system with the space group C2/m.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E, wherein 0.4≤r*<1.0, advantageously 0.4≤r*<0.875 or 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6 very particularly advantageously r*=0.5. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rbr*Na1-r*)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously E=Eu. By way of example, the phosphor has the formula (Rb0.5Na0.5)Li3SiO4:Eu. The peak wavelength of the phosphor is in the green spectral range, in particular, and has a full width at half maximum of between 42 and 44 nm.
In accordance with at least one embodiment, the phosphor has the general molecular formula (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<0.4, for example r*=0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25. Advantageously, TA=Li, TD=Si and XB=O and the phosphor has the formula (Rbr*Na1−r*)Li3SiO4:E. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof; advantageously E=Eu. The peak wavelength of the phosphor is advantageously in the blue spectral range and has a full width at half maximum of between 20 and 24 nm.
The phosphor (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E or (Rbr*Na1−r*)Li3SiO4:E where 0<r*<0.4, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25, is suitable in particular for use in conversion LEDs which emit white radiation. To that end, the phosphor can be combined with a red and green phosphor.
Moreover, the phosphor (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)Li3SiO4:E where 0<r*<0.4, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25, is suitable for use in lighting devices such as conversion LEDs which emit a blue radiation.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1−r)Li3SiO4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, particularly advantageously r=0.25 or
(Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E or (Rbr′Li1−r′)Li3SiO4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6. Advantageously, TA=Li, TD=Si and XB=O. The peak wavelength of the phosphor is in the green spectral range, in particular, and has a full width at half maximum of less than 50 nm.
Surprisingly, the phosphors according to the present disclosure (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, (Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, (K1−r″-r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, (K,Na,Li,Cs) (TA)3(TD)1(XB)4:E, and (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<1.0, for example (Rb0.5Li0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu, (Na0.25K0.50Li0.25) Li3SiO4:Eu, (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu and (Rb0.5Na0.5) Li3SiO4:Eu, have a peak wavelength in the green spectral range and a very small full width at half maximum and are therefore suitable in particular for white-emitting lighting devices such as, for example, white-emitting conversion LEDs in conjunction with a semiconductor chip that emits a blue primary radiation and with a red phosphor for backlighting applications in particular for display elements such as displays. Advantageously, a particularly large bandwidth of colors can be achieved with such a white-emitting conversion LED. As a result of the small full width at half maximum of the phosphors according to the present disclosure (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4,
(Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, (K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 where 0<r′″<0.5, (K,Na,Li,Cs) (TA)3(TD)1(XB)4:E and (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<1.0 for example (Rb0.5Li0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu, (Na0.25K0.50Li0.25) Li3SiO4:Eu, (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu and (Rb0.5Na0.5) Li3SiO4:Eu, the emission peaks exhibit a very large overlap with the transmission range of a standard green filter, such that only little light is lost and the achievable color space is large.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E,
wherein 0<y*<0.875; advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1. By way of example, y*=0.01; 0.02; 0.03, 0.04 or 0.05. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof. Advantageously, E=Eu or Eu2+.
Surprisingly, it has been found that the phosphor of the formula NaLi3SiO4:Eu has an isotypic crystal structure with respect to the known phosphor CaLiAl3N4:Eu. The fact that two compounds crystallize in an isotypic crystal structure means, in particular, that the atoms of one compound occupy the same place within the crystal structure as the corresponding atoms of the other compound. As a result, the linkages of structural units within the structures are maintained unchanged. An isotypic crystal structure in the case of oxides and nitrides is atypical since nitrides, in comparison with oxides, usually have a higher degree of condensation of the polyhedra, in particular the tetrahedra, within the crystal structure. This is surprising particularly in the present case since the degree of condensation of the phosphor according to the present disclosure of the formula NaLi3SiO4:Eu is one, whereas typical oxosilicates have a degree of condensation of less than or equal to 0.5. Surprisingly, the inventors have discovered that, proceeding from the phosphor of the molecular formula NaLi3SiO4:Eu, the elements Na, Li, Si, O can be partly replaced by the elements Ca, Li, Al and N, thus resulting in a phosphor of the formula Na1−y*Cay*Li3−2y*Al3y*Si1−yO4−4y*N4y*:Eu. This phosphor is present in a mixed phase, in particular, such that within the crystal structure of NaLi3SiO4:Eu, the lattice sites are partly occupied by the elements Ca, Li, Al and N.
The known phosphor CaLiAl3N4:Eu is a phosphor which emits in the red range of the electromagnetic spectrum, has a peak wavelength at approximately 670 nm, has a full width at half maximum of approximately 60 nm and crystallizes in an isotypic crystal structure with respect to NaLi3SiO4. In comparison therewith, NaLi3SiO4:Eu emits in the blue spectral range of the electromagnetic spectrum with a peak wavelength of approximately 470 nm and exhibits a more narrowband emission, that is to say an emission having a smaller full width at half maximum than 60 nm. The mixed phase according to the present disclosure of these phosphors advantageously makes it possible to provide a phosphor of the formula Na1−y*Cay*Li3−2y*Al3y*Si1−yO4−4y*N4y*:Eu in which the proportion of CaLiAl3N4 can be varied, which is expressed by the index y* in the formula. As a result of this variation, it is possible to provide a phosphor which, as a result of the variable composition, allows the peak wavelength to be set in a range of between 470 nm and 670 nm. The phosphor can thus be set in a targeted manner with regard to the desired color locus, depending on requirements or application. Consequently, with just one phosphor it is possible, surprisingly, to generate almost all colors of the visible range, from blue to red.
The peak wavelength of the phosphor Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E where 0<y*<0.875, advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1, is advantageously in the blue or green spectral range. The phosphor is suitable in particular in combination with a green and red phosphor for white conversion LEDs, in particular for general lighting. Moreover, the phosphor is suitable for colored conversion LEDs.
In accordance with at least one embodiment, the phosphor Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E crystallizes in a tetragonal crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I41/a. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I41/a.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
Na1−y***Sry**Li3−2y***Al3y***Si1−y***O4−4y***N4y***:E,
wherein 0<y***<0.875; advantageously 0<y***≤0.5, particularly advantageously 0<y***≤0.3. By way of example, it holds true that y***=0.01; 0.02; 0.03, 0.04 or 0.05. E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof. Advantageously, E=Eu or Eu2+.
In accordance with at least one embodiment, the phosphor has the formula (MB)b(TA)e(TC)g(TD)h(XB)l(XC)m:E,
wherein
In accordance with at least one embodiment, the phosphor has the formula (MB)b(TA)e(TC)g(TD)h(XB)l(XC)m:E,
wherein
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
(MB)(Si0.25Al−1/8+r**/2Li7/8−r**/2)4(O1−r**Nr**)4:E,
wherein 0.25≤r**≤1, advantageously 0.25<r**<0.875, particularly advantageously 0.4≤r**≤0.8. MB is selected from a group of divalent metals which comprises Mg, Ca, Sr, Ba and combinations thereof, and E=Eu, Ce, Yb and/or Mn, advantageously E=Eu.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4(O1−r**Nr**)4:E,
wherein 0.25≤r**≤1, advantageously 0.25<r**<0.875, particularly advantageously 0.4≤r**≤0.8 and E=Eu, Ce, Yb and/or Mn. The phosphor is, in particular, a mixed phase of the compounds SrSiLi3O3N:Eu (r**=0.25) and Sr2Si2Al3Li3N8:Eu (r**=1).
The mixed phase according to the present disclosure advantageously makes it possible to provide a phosphor in which the proportion of nitrogen can be varied, which is expressed in the formula by the index r**. As a result of this variation, it is possible to provide a phosphor which, as a result of the variable composition, allows the peak wavelength to be set from the yellow to red spectral range. Consequently, the phosphor can be set in a targeted manner with regard to the desired color locus and/or color rendering index, depending on requirements or application. With just one phosphor, surprisingly, it is thus possible to generate many colors of the visible range, in particular from yellow to red.
In accordance with at least one embodiment, the phosphor (MB)(Si0.25Al−1/8+r**/2Li7/8−r**/2)4(O1−r**Nr**)4:E or Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4(O1−r**Nr**)4:E crystallizes in a tetragonal crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I4/m.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E,
wherein 0<y**≤1.0, advantageously 0<y**<0.875 or 0<y**<0.5, particularly advantageously 0.05≤y**≤0.45, very particularly advantageously 0.1≤y**≤0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3. E=Eu, Ce, Yb and/or Mn, advantageously E=Eu.
Surprisingly, it has been found that the phosphor of the formula Na1−y*-Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E, advantageously Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu, can be produced as a mixed phase between NaLi3SiO4:E or NaLi3SiO4:Eu (y**=0) and the compound EuLiAl3N4 (y**=1) and moreover constitutes an efficient phosphor having unique properties. This phosphor is present in particular in a mixed phase, such that within the crystal structure of NaLi3SiO4:Eu the lattice sites are partly occupied by the elements Eu, Li, Al and N.
NaLi3SiO4:Eu emits in the blue spectral range. The mixed phase according to the present disclosure of NaLi3SiO4:Eu and the compound EuLiAl3N4 advantageously makes it possible to provide a phosphor of the formula Na1−y*Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu in which the proportion of EuLiAl3N4 can be varied, which is expressed in the formula by the index y**. As a result of this variation, it is possible to provide a phosphor which, as a result of the variable composition, allows the peak wavelength to be set in a range from the yellow to red range. Consequently, the phosphor can be set in a targeted manner with regard to the desired color locus, depending on requirements or application. With just one phosphor, surprisingly, it is thus possible to generate almost all colors of the visible range, from yellow to red.
In accordance with at least one embodiment, the phosphor Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu crystallizes in a tetragonal crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m.
Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system with the space group I4/m.
In accordance with at least one embodiment, the phosphor has the formula (MB)b(TA)e(TC)g(XB)l(XC)m:E,
wherein
In accordance with at least one embodiment, the phosphor has the formula (MB)b(TA)e(TC)g(XB)l(XC)m:E,
wherein
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
(MB)Li3−2x**Al1+2x**O4−4x**N4x**:Eu
where 0<x**≤1.0, advantageously 0<x**<0.875, particularly advantageously 0.125≤x**<0.875 or 0.125≤x**≤0.5, very particularly advantageously 0.125≤x**≤0.45. MB is selected from a group of divalent metals which comprises Mg, Ca, Sr, Ba, Zn and combinations thereof.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu
where 0<x**≤1.0, advantageously 0<x**<0.875, particularly advantageously 0.125≤x**<0.875 or 0.125≤x**≤0.5, very particularly advantageously 0.125≤x**≤0.45.
Surprisingly, it has been found that the phosphor of the formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu can be produced as a mixed phase between SrLi3AlO4:Eu (x**=0) and the compound SrLiAl3N4 (x**=1) and moreover constitutes an efficient phosphor having unique properties. In particular, the phosphors have a small full width at half maximum.
SrLiAl3N4:Eu is a known phosphor exhibiting narrowband emission in the red spectral range. The mixed phase according to the present disclosure of SrLi3AlO4:Eu and the compound SrLiAl3N4 advantageously makes it possible to provide a phosphor of the formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu in which the proportion of SrLiAl3N4 can be varied, which is expressed in the formula by the index x**. As a result of this variation, it is possible to provide a phosphor which, as a result of the variable composition, allows the peak wavelength to be set in a range from the green to yellow or yellow-orange range. As a result, it is possible to achieve color loci which cannot be achieved with known phosphors. Consequently, the phosphor can be set in a targeted manner with regard to the desired color locus in the green to yellow range, depending on requirements or application.
Surprisingly, it has been found that the phosphor of the formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu, as x**increases, starting from x**≥0.1250, crystallizes in the same crystal structure but in the process the cell volume of the unit cell increases and at the same time, as x**increases, the peak wavelength is shifted into the longer-wavelength range, in particular from the green right into the red spectral range. Thus, the phosphor SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where 0.125≤x**≤1, advantageously 0.125≤x**<0.875, particularly advantageously 0.125≤x**≤0.5, very particularly advantageously 0.125≤x**≤0.45, is usable in diverse ways and is suitable in particular for colored conversion LEDs comprising SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu as sole phosphor. In addition, the phosphors advantageously have small values of full width at half maximum of less than 80 nm.
The phosphor SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu, in particular where x**≥0.1250, is suitable for example for use in lighting devices such as conversion LEDs which emit white radiation, wherein a superimposition of the blue primary radiation and the secondary radiation yields a white overall radiation. The phosphor is very robust and efficient and it is advantageously possible to provide a conversion LED which emits an overall radiation having a color temperature of less than 3600 K, in particular 3400 K±100 K, and a color locus near the Planckian locus.
In accordance with at least one embodiment, the phosphor has the following general molecular formula:
SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu
where 0<x**<0.125, advantageously 0<x**<0.120.
The phosphor SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where 0<x**<0.125 surprisingly does not crystallize in an isotypic crystal structure with respect to the crystal structure of SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where x**≥0.125. In particular, the phosphor where 0<x**<0.125 can form a crystal structure which can be described as a crystallographic superstructure of the crystal structure of variants of the phosphor where x**≥0.125.
Advantageously, the peak wavelength of this phosphor is in the green range of the electromagnetic spectrum. The full width at half maximum is advantageously smaller in comparison with SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where x**≥0.125.
In accordance with at least one embodiment, the phosphor (MB) Li3−2x**Al1+2x**O4−4x**N4x**:Eu or SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu crystallizes in a tetragonal crystal system. Advantageously, the phosphor in accordance with this embodiment crystallizes in the space group I4/m. Particularly advantageously, the phosphor in accordance with this embodiment crystallizes in a tetragonal crystal system in the space group I4/m.
In accordance with at least one embodiment, the phosphor crystallizes in a crystal structure having the same atomic sequence as in UCr4C4, CsKNa2Li12Si4O16 or RbLi5{Li[SiO4]}2. The fact that the phosphor crystallizes in a crystal structure having the same atomic sequence as in UCr4C4, CsKNa2Li12Si4O16 or RbLi5{Li[SiO4]}2 means, here and hereinafter, that the succession of the atoms of the phosphor follows the same pattern as the succession of the atoms in UCr4C4, CsKNa2Li12Si4O16 or RbLi5{Li[SiO4]}2. In other words, the crystal structure exhibits the same structural motifs as UCr4C4, CsKNa2Li12Si4O16 or RbLi5{Li[SiO4]}2. By way of example, the phosphor of the formula (Na0.5K0.5) Li3SiO3:Eu crystallizes in a crystal structure having the same atomic sequence as in CsKNa2Li12Si4O16; in this case, K occupies the sites of Cs and of K, Na occupies the sites of Na, Li occupies the sites of Li, Si occupies the sites of Si, and O occupies the sites of O. As a result of the variation of the ionic radii in the course of substitution with other atomic species, the absolute position (atomic coordinates) of the atoms may change.
The phosphor can also crystallize in a crystal structure having the same atomic sequence as in the structures NaLi3SiO4 or KLi3GeO4 derived from UCr4C4.
In accordance with at least one embodiment, the phosphor crystallizes in the same structure type as
The crystal structures of the embodiments are distinguished in particular by a three-dimensionally linked spatial network. In this case, TA, TB, TC, TD, TE and/or TF are surrounded by XA, XB, XC and/or XD and the resultant structural units, advantageously tetrahedra, are linked via common corners and edges. This arrangement results in a three-dimensionally extending anionic structural unit. MA, MB, MC and/or MD are arranged in the resultant cavities and/or channels.
In accordance with at least one embodiment, the phosphor has a crystal structure in which TA, TB, TC, TD, TE and/or TF are surrounded by XA, XB, XC and/or XD and the resultant structural units are linked via common corners and edges to form a three-dimensional spatial network having cavities and/or channels and MA, MB, MC and/or MD are arranged in the cavities and/or channels. In particular, the structural units are tetrahedra, wherein advantageously XA, XB, XC and/or XD occupy the corners of the tetrahedra and TA, TB, TC, TD, TE and/or TF are arranged in the center of the tetrahedra.
By way of example, in the crystal structure of the embodiment KLi3SiO4:E, which is isotypic with respect to KLi3GeO4, Li and Si are surrounded by O and form the anionic structural unit in the form of a spatial network of distorted (Li/Si)O4 tetrahedra. In the resultant cavities, the K atoms are surrounded by 8 O atoms in a distorted cubic fashion.
In the crystal structure of the exemplary embodiment RbLi5{Li[SiO4]}2:E, one portion of the Li atoms and Si are surrounded by O and form the anionic structural unit in the form of a spatial network. In this case, the Si atoms are surrounded by 4 O atoms in a distorted tetrahedral fashion. The Li atoms which participate in the structural unit are surrounded by 3 O atoms in a distorted trigonal planar fashion in their first coordination sphere. With addition of further O atoms in the vicinity, the coordination can also be described as distorted tetrahedral or distorted trigonal bipyramidal. In the resultant cavities, the Rb atoms are surrounded by 8 O atoms in a distorted cubic fashion, while the other portion of the Li atoms is surrounded by 4 O atoms in a distorted square planar fashion.
Depending on the chemical composition of the phosphors disclosed here, a severe distortion of the coordination sphere around MA, MB, MC and/or MD may occur. In the case of the exemplary embodiment NaLi3SiO4:E, for example, that has the effect that the vicinity of the Na atoms is present as a distorted trigonal prism or, with addition of a further O atom, as a distorted capped cube.
The specified embodiments of the phosphor can be produced in accordance with methods specified below. All features described for the phosphor thus also apply to the method for producing said phosphor, and vice-versa.
A method for producing a phosphor is specified.
In accordance with at least one embodiment, the phosphor has the general molecular formula:
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n:E
In this case, MA is selected from a group of monovalent metals, MB is selected from a group of divalent metals, MC is selected from a group of trivalent metals, MD is selected from a group of tetravalent metals, TA is selected from a group of monovalent metals, TB is selected from a group of divalent metals, TC is selected from a group of trivalent metals, TD is selected from a group of tetravalent metals, TE is selected from a group of pentavalent elements, TF is selected from a group of hexavalent elements, XA is selected from a group of elements which comprises halogens, XB is selected from a group of elements which comprises O, S and combinations thereof, XC=N and XD=C. The following furthermore hold true:
The method comprises the following method steps:
A) mixing starting materials with the phosphor,
B) heating the mixture obtained under A) to a temperature T1 of between 500 and 1400° C., advantageously between 700 and 1400° C.,
C) annealing the mixture at a temperature T1 of 500 to 1400° C., advantageously between 700 and 1400° C., for 0.5 minute to 10 hours.
In one embodiment, the starting materials are present as powder.
In one embodiment, method step C) is followed by a further method step:
D) cooling the mixture to room temperature. Room temperature is understood to mean 20° C., in particular.
In one embodiment, method step D) is followed by method steps B) and C) again, wherein the phosphor obtained in method step D) is then heated and annealed, respectively. The optical properties of the phosphor can be improved by this further annealing process.
In accordance with at least one embodiment, the starting materials melt during the process of heating the mixture obtained under A) in method step B).
The heating and cooling rates can be for example 250° C. per hour.
In one embodiment, method steps B), C) and/or D) take place under forming gas atmosphere. Advantageously, in the forming gas the ratio of nitrogen:hydrogen is 92.5:7.5.
In one embodiment, method steps B), C) and/or D) take place in a tube furnace.
In accordance with at least one embodiment, the method comprises the following method step A):
A) mixing the starting materials comprising K2CO3, Cs2CO3, Na2CO3 and/or Rb2CO3.
In accordance with at least one embodiment, the method comprises the following method step A):
A) mixing the starting materials comprising or consisting of SiO2, Eu2O3, Li2CO3 and at least one carbonate from K2CO3, Cs2CO3, Na2CO3 and Rb2CO3. In particular, with the use of these starting materials it is possible to produce the phosphors (NarK1−r) Li3SiO4:Eu, (Rbr′Li1−r′) Li3SiO4:Eu and (K1−r″-r′″Nar″Lir′″) Li3SiO4:Eu, advantageously NaLi3SiO4:Eu, KLi3SiO4:Eu, (Na0.5K0.5) Li3SiO4:Eu, (Rb0.5Li0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu and (Na0.25K0.5Li0.25) Li3SiO4:Eu.
In accordance with at least one embodiment, the method comprises the following method step A):
A) mixing the starting materials comprising or consisting of CaO, NaF, LiN3, Li2O, LiAlH4, AlF3, SiO2 and EuF3. In particular, with the use of these starting materials it is possible to produce a phosphor of the formula Na1−y*Cay*Li3−2y*Al3y*Si1−yO4−4y*N4y*:Eu, for example Na0.97Ca0.03Li2.94Al0.09Si0.97O3.88N0.12:Eu.
The production method can be carried out very simply in comparison with many other methods for producing phosphors. In particular, no protective gas atmosphere is required since the products are insensitive to moisture or oxygen. Moreover, the synthesis is carried out at moderate temperatures and is therefore very energy-efficient. The requirements made, for example, of the furnace used are thus low. The starting materials are commercially available in a cost-effective manner and are non-toxic.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, emits a white radiation during operation. The radiation can be composed of a superimposition of the primary radiation and the secondary radiation or only of the secondary radiation.
In accordance with at least one embodiment, the phosphor emits a secondary radiation having a peak wavelength in the blue or blue-green spectral range of the electromagnetic spectrum. In order to generate a white overall radiation, the conversion element can comprise a second and a third phosphor. In particular, the second phosphor can be configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum during operation of the lighting device. The third phosphor can be configured in particular partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the green spectral range of the electromagnetic spectrum during operation of the lighting device. A superimposition of the blue, green and red secondary radiation produces a white luminous impression. The lighting device, in particular the conversion LED, in accordance with this embodiment is suitable in particular for general lighting.
The conversion of the UV or blue primary radiation into a secondary radiation having a somewhat longer wavelength in the blue or blue-green range of the electromagnetic spectrum increases the efficiency of the lighting device, in particular of the conversion LED. In comparison with the primary radiation, the peak wavelength of the secondary radiation is closer to the maximum of eye sensitivity at 555 nm, as a result of which the emitted radiation has a higher overlap with the eye sensitivity curve and is thus perceived as brighter.
In accordance with at least one embodiment, the phosphor emits a secondary radiation having a peak wavelength in the green spectral range of the electromagnetic spectrum. In order to generate a white overall radiation, the conversion element can comprise a second phosphor, which can be configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation in the red spectral range of the electromagnetic spectrum during operation of the lighting device. A superimposition of the blue primary radiation and the green and red secondary radiation produces a white luminous impression. The lighting device, in particular the conversion LED, in accordance with this embodiment is suitable in particular for backlighting applications.
The third phosphor having a peak wavelength in the green spectral range can be selected from a group comprising R-SiAlONs, α-SiAlONs, chlorosilicates, orthosilicates, siliconoxynitrides (SiONs), garnets and combinations thereof.
In accordance with one embodiment, the garnet phosphor can be selected from the material system (Y, Lu, Gd)3(Al,Ga)5O12:Ce or (Y,Lu,Gd)3(Al)5O12:Ce. Advantageously, the garnet phosphor is selected from the material system (Y,Lu)3Al5O12:Ce and (Y,Lu)3(Al,Ga)5O12:Ce. By way of example, the phosphor is Y3Al5O12:Ce.
The α-SiAlONs can have for example the following molecular formula: MtSi12−(t′+t″)Al(t′+t″)OnN16−n:Eu where M=Ca, Mg, Y, advantageously Ca.
The chlorosilicates can have for example the following molecular formula: (Ca,Sr,Ba,Eu)8Mg(SiO4)4Cl2.
The siliconoxynitrides can have for example the following molecular formula:
(EA*1-t′″Eut′″)Si2O2N2
where 0<t′″≤0.2, advantageously 0<t′″≤0.15, particularly advantageously 0.02≤t′″≤0.15 and EA*=Sr, Ca, Ba and/or Mg. Preference is given to (Sr1t′″−oEA*oEut′″)Si2O2N2 where EA*=Ba, Ca and/or Mg and 0≤o<0.5.
The second phosphor having a peak wavelength in the red spectral range can be for example a nitridosilicate or a nitridoaluminate. In particular, the nitridosilicate can be selected from the material systems (Ca,Sr,Ba,Eu)2(Si,Al)5(N,O)8, (Ca,Sr,Ba,Eu)AlSi(N,O)3, (Ca,Sr,Ba,Eu)AlSi(N,O)3.Si2N2O, (Ca,Sr,Ba,Eu)2Si5N8, (Ca,Sr,Ba,Eu)AlSiN3 and combinations thereof. The nitridoaluminate can have the formula MLiAl3N4:Eu (M=Ca,Sr).
Furthermore, the second phosphor can be selected from a material system having a peak wavelength in the red spectral range, which is described in the patent application WO2015/052238A1, the disclosure content of which in this regard is hereby incorporated by reference in its entirety. By way of example, the second phosphor has the formula Sr(Sr,Ca)Si2Al2N6:Eu.
The second phosphor having a peak wavelength in the red spectral range can also be a phosphor having the molecular formula A2[SiF6]:Mn4+ where A=Li, Na, K, Rb, Cs, for example K2SiF6:Mn4+.
The second phosphor having a peak wavelength in the red spectral range can also be Mg4GeO5.5F:Mn.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, is configured to emit a white radiation. In this case, the phosphor has the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0≤r≤0.05, advantageously r=0. Advantageously, TA=Li, TD=Si, XB=O and E=Eu, Ce, Yb and/or Mn, advantageously E=Eu. By way of example, the phosphor is KLi3SiO4:Eu. The phosphor exhibits very broadband emission from the blue to red spectral range, thus giving rise to a white-colored luminous impression. In this case, it is advantageously possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment comprises no further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. The lighting device, in particular the conversion LED, has a high efficiency and a high color rendering index. In particular the lighting device, in particular the conversion LED, in accordance with this embodiment emits warm-white radiation having a color temperature of less than 3500 K, in particular less than 3000 K. Thus, this lighting device, in particular this conversion LED, is suitable in particular for general lighting.
In comparison with known white-emitting conversion LEDs which use a blue-emitting semiconductor chip and a red and green phosphor for generating white light, here the complicated binning of the semiconductor chips can be dispensed with or can be carried out at least with a greater tolerance. It is possible to use semiconductor chips which have a primary radiation that is not perceived or is only scarcely perceived by the human eye (300 nm to 430 nm or 440 nm). Production-, temperature- or forward-current-dictated fluctuations of the primary radiations do not adversely affect the overall radiation properties. In comparison with the use of two or more phosphors, color adaptation by varying the concentrations of the phosphors is not necessary since the emission spectrum is generated by only one phosphor and is thus constant. The conversion LEDs can thus be produced with a high throughput since color adaptation or complicated chip binning is not necessary. No color shifts or other adverse effects on the emission spectrum as a result of selective degradation of only one phosphor occur. A partial conversion of the primary radiation can also be carried out depending on the application. Since it is possible to excite the phosphor with a primary radiation in the range of 300 nm to 430 nm or 440 nm, a contribution of the primary radiation, advantageously in the short-wave blue range of the electromagnetic spectrum, to the overall radiation has the effect that objects illuminated thereby appear whiter, more radiant and therefore more attractive. By way of example, optical brightening agents in textiles can thereby be excited.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, is configured to emit a white radiation. In this case, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1-r) Li3SiO4:E where 0.05<r≤0.2, advantageously 0.1<r≤0.2 where E=Eu, Ce, Yb and/or Mn, advantageously E=Eu. By way of example, the phosphor is Na0.125K0.875Li3SiO4:Eu. The phosphor exhibits broadband emission from the green to red spectral range, thus resulting in a white overall radiation through the superimposition of a blue primary radiation and the secondary radiation. In this case, it is advantageously possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment comprises no further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. In contrast to conversion LEDs comprising a plurality of phosphors, therefore, no color shifts or other adverse effects on the emission spectrum as a result of selective degradation of only one phosphor occur.
The lighting device, in particular the conversion LED, has in particular a high color rendering index, even though no further red phosphor is present. In particular, the lighting device, in particular the conversion LED, in accordance with this embodiment emits cold-white radiation having a color temperature of more than 6500 K, advantageously more than 8000 K. The maximum value of the color temperature can be 10 000 K. Therefore, this lighting device, in particular this conversion LED, is suitable in particular for general lighting, for example for office spaces. Studies prove that cold-white overall radiation in the case of general lighting can increase the ability to concentrate, since the production of melatonin can be reduced by the high proportion of blue in the overall radiation.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation, wherein the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, (Rbr′Li1-r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, (K1r″r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, advantageously 0.1<r′<0.4 and 0.1<r′″<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r′″<0.3, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<0.875, advantageously 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6, very particularly advantageously r*=0.5. Advantageously, TA=Li, TD=Si and XB=O. Particularly advantageously, TA=Li, TD=Si, E=Eu and XB=O. The conversion element comprises at least one second phosphor configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum during operation of the lighting device, in particular the conversion LED.
In accordance with at least one embodiment, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, particularly advantageously r=0.25, (Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, (K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, advantageously 0.1<r″<0.4 and 0.1<r′″<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r′″<0.3, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Rbr*Na1-r′)1(TA)3(TD)1(XB)4:E where 0.4≤r*<0.875, advantageously 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6, very particularly advantageously r*=0.5. Advantageously, TA=Li, TD=Si and XB=O. Particularly advantageously, TA=Li, TD=Si, E=Eu and XB=O. The peak wavelength of the phosphor is advantageously in the green spectral range and has a full width at half maximum of less than 50 nm. The conversion element comprises a second phosphor configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum during operation of the lighting device. It is possible for the conversion element to consist of the phosphor and the second phosphor or of the phosphor, the second phosphor and the matrix material. In particular, the conversion element or the conversion LED in accordance with this embodiment does not comprise a further phosphor. The phosphor and the second phosphor can thus be present, therefore, as sole phosphors in the conversion element or the lighting device, in particular the conversion LED. A superimposition of the primary radiation and the secondary radiation in the red and green spectral range gives a white-colored luminous impression.
A particularly large bandwidth of colors can advantageously be rendered with a lighting device, in particular with a conversion LED, in accordance with this embodiment. Therefore, the lighting device, in particular the conversion LED, in accordance with this embodiment is suitable in particular for backlighting applications for display elements such as displays.
In the case of LCD displays (“liquid crystal displays”) and other displays, the colors are rendered by the primary colors red, green and blue. The bandwidth of colors which can be rendered on a display is therefore limited by the spanned color triangle of the colors red, green and blue. These colors are correspondingly filtered out from the spectrum for backlighting by red, green and blue color filters. However, the wavelength range of the transmitted radiation of the color filters is still very wide. Therefore, light sources having very narrowband emissions, that is to say a small full width at half maximum, in the green, blue and red spectral range are required in order to cover the widest possible color space. As light sources for backlighting applications, predominantly a blue-emitting semiconductor chip with a phosphor having a peak wavelength in the green and a phosphor having a peak wavelength in the red spectral range are combined, wherein the phosphors have the smallest possible full width at half maximum for the emission. Ideally the emission peaks are in this case congruent with the transmission range of the respective color filter in order to lose as little light as possible, to achieve the maximum efficiency and to reduce crosstalk or an overlap of the different color channels, which limits the achievable color space.
As a result of the small full width at half maximum of the phosphors according to the present disclosure (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, (Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, (K1−r″−r′″Nar″Lir′″) (TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<0.875, for example (Rb0.5Li0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu, (Na0.25K0.50Li0.25) Li3SiO4:Eu, (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu or (Rb0.5Na0.5) Li3SiO4:Eu, the emission peaks exhibit a very large overlap with the transmission range of a standard green filter (having a full width at half maximum in the range of typically 70 to 120 nm), such that only little light is lost and the achievable color space is large. In particular, a phosphor having a small full width at half maximum, such as K2SiF6:Mn, Mg4GeO5.5F:Mn, SrLiAl3N4:Eu or Sr(Sr, Ca) Si2Al2N6:Eu, is used as second phosphor. In particular, the combination of a green and a red phosphor having a small full width at half maximum results in a large color space being covered.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, is configured to emit a white radiation. In this case, the phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E or (NarK1-r)Li3SiO4:E where 0.05<r≤0.2, advantageously 0.1<r≤0.2 where E=Eu, Ce, Yb and/or Mn, advantageously E=Eu. By way of example, the phosphor is Na0.125K0.87Li3SiO4:Eu. The phosphor advantageously exhibits broadband emission from the green to red spectral range. In conjunction with a blue primary radiation, the overall radiation exhibits a very large overlap with the transmission range of a standard green, red and blue filter, such that only little light is lost and the achievable color space is large. It is thus advantageously possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. Therefore, this lighting device, in particular this conversion LED, is suitable in particular for backlighting applications.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a green radiation; the phosphor has the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, particularly advantageously r=0.25, (Rbr′Li1-r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, (K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, advantageously 0.1<r″<0.4 and 0.1<r′″<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r′″<0.3, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E 0.4≤r*<0.875, advantageously 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6, very particularly advantageously r*=0.5. Advantageously, TA=Li, TD=Si and XB=O. Particularly advantageously, TA=Li, TD=Si, E=Eu and XB=O. The peak wavelength of the phosphor is in the green spectral range, in particular, and has a full width at half maximum of less than 50 nm. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED.
Green light-emitting diodes, which emit a radiation in the green wavelength range, can be obtained firstly by means of semiconductor chips which emit green directly or conversion LEDs having a semiconductor chip and a green phosphor. Semiconductor chips which emit green directly exhibit a very low quantum efficiency. In the case of the conversion LEDs, the primary radiation can on the one hand be converted completely into green secondary radiation (full conversion) or on the other hand be converted only partly into green secondary radiation (partial conversion), and the remaining proportion of primary radiation is filtered out by means of a filter, such that the lighting device emits exclusively or almost exclusively secondary radiation, in particular green secondary radiation.
(Y,Lu)3(Al,Ga)5O12:Ce, orthosilicates or oxonitridoorthosilicates are conventionally used as green phosphors. The conventional conversion LEDs often have a low efficiency and color purity. In order to avoid these disadvantages, filters are used to adapt the emission. However, this adversely affects the total power of the conversion LED.
Lighting devices, in particular conversion LEDs, comprising the green phosphor according to the present disclosure of the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, (Rbr′Li1-r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, (K1-r″-r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<0.875, for example (Rb0.5Li0.5) Li3SiO4:Eu, (Na0.25K0.75) Li3SiO4:Eu, (Na0.25K0.50Li0.25) Li3SiO4:Eu, (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu or (Rb0.5Na0.5) Li3SiO4:Eu, are by contrast very efficient and exhibit a high color purity and a high power even without the use of a color filter.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. The phosphor has the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, advantageously 0.45<r≤1, very particularly advantageously r=0.5 or 1.
Advantageously, TA=Li, TD=Si and XB=O. Alternatively, the phosphor has the formula (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<0.4, for example r*=0.05; 0.1; 0.15; 0.2; 0.25; 0.3; 0.35, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤K 0.3, very particularly advantageously r*=0.25 or (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E and (Rb,Na,K)1(TA)3(TD)1(XB)4:E. Advantageously, TA=Li, TD=Si and XB=O. By way of example, the phosphor has the formula NaLi3SiO4:Eu, (Na0.5K0.5) Li3SiO4:Eu, (Rb0.25Na0.75) Li3SiO4:Eu, (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu or (Rb0.25Na0.5K0.25) Li3SiO4:Eu. The peak wavelength of these phosphors is advantageously in the blue spectral range, in particular in the range of between 450 nm and 500 nm. The conversion element comprises a second and a third phosphor, wherein the second phosphor is configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum, and the third phosphor is configured to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the green spectral range of the electromagnetic spectrum during operation of the lighting device. It is possible for the conversion element to consist of the phosphor, the second and third phosphors or of the phosphor, the second and third phosphors and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor and the second and third phosphors can thus be present, therefore, as sole phosphors in the conversion element or the lighting device, in particular the conversion LED. A superimposition of the secondary radiations in the blue, red and green spectral range gives a white-colored luminous impression. The lighting device, in particular conversion LED in accordance with this embodiment is suitable in particular for general lighting.
Known white-emitting conversion LEDs use a semiconductor chip which emits a blue primary radiation, and at least one red and green phosphor. A superimposition of the blue primary radiation and the red and green secondary radiation gives rise to white light. What is disadvantageous about this solution is that the epitaxially grown semiconductor chips, based for example on GaN or InGaN, may have fluctuations in the peak wavelength of the emitted primary radiation. This leads to fluctuations in the white overall radiation, such as a change in the color locus and the color rendering, since the primary radiation contributes the blue portion to the overall radiation. This is problematic particularly when a plurality of semiconductor chips are used in a device. In order to prevent fluctuations, the semiconductor chips have to be sorted in accordance with their color loci (“binning”). The narrower the tolerances set with regard to the wavelength of the emitted primary radiation, the higher the quality of devices which consist of more than one semiconductor chip. However, even after sorting with narrow tolerances, the peak wavelength of the semiconductor chips can change significantly in the case of variable operating temperatures and forward currents. In general lighting and other applications, this may lead to a change in the optical properties, such as the color locus and the color temperature. An additional factor is that for conventional solutions in the range of 450 nm to 500 nm of the electromagnetic spectrum there is a spectral gap in the emission spectrum in which no or only very little light is emitted. This results in a reduction of the color rendering index in comparison with the reference light source.
The phosphor (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, for example NaLi3SiO4:Eu, (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E, where 0<r*<0.4, (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E or (Rb,Na,K)1(TA)3(TD)1(XB)4:E or (Na0.5K0.5)Li3SiO4:Eu, can be excited efficiently with a primary radiation of 300 nm to 440 nm. The combination of a semiconductor chip with a primary radiation of 300 nm to 440 nm, for example based on GaInN, leads to the emission of a secondary radiation in the blue spectral range which is stable over a significantly wider temperature range and larger ranges for the forward currents. Since the primary radiation of 300 nm to 440 nm is not visible or is scarcely visible, a wide variety of semiconductor chips can be used as primary radiation source and a constant and stable emission spectrum of the conversion LED can nevertheless be obtained. In this regard complex “binning” of the semiconductor chips can be avoided or simplified and the efficiency can be increased. As a result of a peak wavelength of the phosphor in the range of 450 nm and 500 nm, the emission is increased in this range. The color rendering index can thus advantageously be increased.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. The phosphor has the formula Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E where 0<y*<0.875, advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1, for example Na0.97Ca0.03Li2.94Al0.09Si0.97O3.88N0.12:Eu. The peak wavelength of the phosphor is advantageously in the blue or green spectral range, in particular in the range of between 470 nm and 560 nm, advantageously between 470 nm and 520 nm. The conversion element comprises in particular a second and a third phosphor, wherein the second phosphor is configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum, and the third phosphor is configured to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the green spectral range of the electromagnetic spectrum during operation of the lighting device. In this case, the third phosphor has in particular an electromagnetic secondary radiation having a peak wavelength of more than 520 nm. It is possible for the conversion element to consist of the phosphor, the second and third phosphors or of the phosphor, the second and third phosphors and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor and the second and third phosphors can thus be present, therefore, as sole phosphors in the conversion element or the lighting device, in particular the conversion LED. A superimposition of the secondary radiations gives a white-colored luminous impression. Radiation in the range of 450 nm to 500 nm of the electromagnetic spectrum is also emitted as a result of the use of the phosphor Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E. With the use of standard phosphors, a spectral gap in the overall emission spectrum often prevails here, in which therefore no or only very little light is emitted. As a result, the overall radiation almost continuously covers in particular the visible range of the electromagnetic spectrum, whereby the overall radiation has a high color rendering index. The lighting device, in particular conversion LED, in accordance with this embodiment is suitable in particular for general lighting.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. The phosphor has the formula Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4(O1−r**Nr**)4:E, wherein 0.25≤r**≤1, advantageously 0.25<r**<0.875, particularly advantageously 0.4≤r**≤0.8. Advantageously, E=Eu. The peak wavelength of the phosphor is advantageously in the yellow to red spectral range. The conversion element can comprise a further phosphor, wherein a white-colored luminous impression is produced by a superimposition of the secondary radiations and/or the primary radiation and the secondary radiations. Since the peak wavelength of the phosphor Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4 (O1−r**Nr**)4:E can be in the yellow to red spectral range depending on the proportion of r**, the choice of the further phosphor within the conversion LED for generating white light depends on the peak wavelength of the phosphor Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4 (O1−r**Nr**)4:E.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a radiation that is in the yellow to red spectral range. The phosphor has the formula Na1−y*Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu, wherein 0<y**≤1.0, advantageously 0<y**<0.875 or 0<y**<0.5, particularly advantageously 0.05≤y**≤0.45, very particularly advantageously 0.1≤y**≤0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a radiation that is in the yellow or yellow-orange spectral range. The phosphor has the formula Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu, wherein 0.1≤y**≤0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3. Conversion light-emitting diodes of this embodiment are suitable in particular for the use thereof in warning lights and flashing lights in motor vehicles. The inventors have been able to show that the color loci of the overall radiation of the conversion light-emitting diode of this embodiment lie in the color space defined by the ECE/UNECE for flashing lights in motor vehicles in Europe and in the color space defined by the SAE for flashing lights in motor vehicles in North America.
In particular, the electromagnetic primary radiation is almost completely absorbed by the phosphor Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu and emitted in the form of an electromagnetic secondary radiation. The emitted radiation or overall radiation of the lighting device, in particular of the conversion LED, in accordance with this embodiment thus almost completely corresponds to the electromagnetic secondary radiation.
Yellow or orange-yellow light-emitting diodes, which emit a radiation in the yellow or yellow-orange wavelength range, can firstly be obtained by means of semiconductor chips on the basis of InGaAlP which emit directly in this spectral range or conversion LEDs having a semiconductor chip and a yellow phosphor. However, semiconductor chips which emit yellow directly exhibit a very low quantum efficiency in comparison with conversion LEDs.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a blue radiation. The phosphor has the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, advantageously 0.45<r≤1, very particularly advantageously r=0.5. Advantageously, TA=Li, TD=Si and XB=O. Alternatively, the phosphor has the formula (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<0.4, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25 or (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E and (Rb,Na,K)1(TA)3(TD)1(XB)4:E. By way of example, the phosphor has the formula NaLi3SiO4:Eu or (Na0.5K0.5) Li3SiO4:Eu, (Rb0.25Na0.75) Li3SiO4:Eu or (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu or (Rb0.25Na0.5K0.25) Li3SiO4:Eu. The peak wavelength of these phosphors is in the blue spectral range. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor; the phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. With the lighting device, in particular the conversion LED, in accordance with this embodiment it is advantageously possible to obtain many color loci in the blue range of the electromagnetic spectrum which have not been able to be achieved heretofore.
The lighting devices, in particular the conversion LEDs, of this embodiment are suitable for example for signal lights, such as blue lights of, for example, police vehicles, ambulances, emergency doctor vehicles or fire department vehicles. Since said signal lights must firstly be very bright and secondly be in a specific color locus range (the dominant wavelength is usually between 465 nm and 480 nm), not all blue light sources are suitable for this use. On the other hand, lighting devices, in particular conversion LEDs, comprising the phosphor (NarK1−r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, in particular comprising (Na0.5K0.5) Li3SiO4:Eu or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0<r*<0.4 in particular comprising (Rb0.25Na0.75) Li3SiO4:Eu, are suitable for suppressing melatonin production for human beings. (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E and (Rb,Na,K)1(TA)3(TD)1(XB)4:E such as for example (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu or (Rb0.25Na0.5K0.25)Li3SiO4:Eu are likewise suitable for this. TA=Li, TD=Si and XB=O advantageously hold true for the phosphors. The lighting device, in particular conversion LED, in accordance with this embodiment can thus be used in a targeted manner to increase the vigilance and/or ability to concentrate. By way of example, they can contribute to overcoming jetlag more rapidly. Moreover, the phosphor or a lighting device, in particular a conversion LED, comprising the phosphor is suitable for “color on demand” applications, that is to say for lighting devices, in particular conversion LEDs, having blue color loci adapted to consumer desires, for example for realizing certain brand-specific or product-specific colors, for example in advertising or in the design of the interior fittings for automobiles.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a blue or green radiation. The phosphor has the formula Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E where 0<y*<0.875, advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1. By way of example, the phosphor has the formula Na0.97Ca0.03Li2.94Al0.09Si0.97O3.88N0.12:Eu. The peak wavelength of the phosphor is in the blue or green spectral range. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor; the phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. With the lighting device, in particular the conversion LED, in accordance with this embodiment it is advantageously possible to obtain many color loci in the green range of the electromagnetic spectrum. The conversion light-emitting diode or lighting device of this embodiment is suitable in particular for applications in which a saturated green emission is required, such as for video projection, for example in the cinema, office or at home, head-up displays, for light sources having an adjustable color rendering index or color temperature, light sources having a spectrum adapted to the application, such as store lighting or FCI lamps (“feeling of contrast index”). FCI lamps are lighting devices which are geared to generating a white light having a particularly high color contrast index. Conversion light-emitting diodes or lighting devices of this embodiment are also suitable for colored spotlights, wall lighting systems or moving spotlights, in particular in stage lighting.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a yellow to red radiation. The phosphor has the formula Sr(Si0.25Al−1/+r**/2Li7/8−r**/2)4 (O1-r**Nr**)4:E, wherein 0.25≤r**≤1, advantageously 0.25<r**≤0.875, particularly advantageously 0.4≤r**≤0.8. Advantageously, E=Eu. By way of example, the phosphor has the formula SrSiAl0.84Li2.16O1.32N2.68:Eu2+. In particular, the primary radiation is completely or almost completely converted into the secondary radiation by the phosphor, such that the overall radiation completely or almost completely corresponds to the secondary radiation. The peak wavelength of the phosphor is in the yellow to red spectral range. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor; the phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. With the lighting device, in particular the conversion LED, in accordance with this embodiment it is advantageously possible to obtain many color loci in the yellow to red range of the electromagnetic spectrum.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. The phosphor has the following general molecular formula:
SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu
where 0<x**≤1.0, advantageously 0<x**<0.875, particularly advantageously 0.125≤x**<0.875 or 0.125≤x**≤0.5, very particularly advantageously 0.125≤x**≤0.45. Advantageously, E=Eu. In this case, it is advantageously possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. The overall radiation is composed of the primary radiation and the secondary radiation. In particular, the lighting device, in particular the conversion LED, in accordance with this embodiment emits warm-white radiation having a color temperature of less than 3600 K, in particular 3400 K±100 K. Advantageously, the color locus of the overall radiation can be near the Planckian locus. Therefore, this lighting device, in particular this conversion LED, is suitable in particular for general lighting for example for living spaces.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a green to red radiation. The phosphor has the formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where 0<x**≤1.0, advantageously 0<x**<0.875, particularly advantageously 0.125≤x**<0.875 or 0.125≤x**≤0.5, very particularly advantageously 0.125≤x**≤0.45. The peak wavelength of the phosphor is in the green to red spectral range depending on the proportion of x**. It is possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor; the phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. With the lighting device, in particular the conversion LED, in accordance with this embodiment it is advantageously possible to obtain many color loci in the green to red range of the electromagnetic spectrum.
In accordance with at least one embodiment, the lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. The phosphor has the following general molecular formula:
(NarK1−r)1(TA)3(TD)1(XB)4:E
where 0.05<r≤0.2, advantageously 0.1<r≤0.2, in particular Na0.125K0.875Li3SiO4:Eu. In this case, it is advantageously possible for the conversion element to consist of this phosphor or this phosphor and the matrix material. In particular, the conversion element or the lighting device, in particular the conversion LED, in accordance with this embodiment does not have a further phosphor. The phosphor can thus be present, therefore, as sole phosphor in the conversion element or the lighting device, in particular the conversion LED. The overall radiation is composed of the primary radiation and the secondary radiation. In particular, the lighting device, in particular the conversion LED, in accordance with this embodiment emits cold-white radiation having a color temperature of more than 8000 K. Moreover, it is possible to obtain a high color rendering index without a further phosphor being necessary. Therefore, this lighting device, in particular this conversion LED, is suitable in particular for general lighting, for example for office spaces.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, comprises a filter or filter particles absorbing the primary radiation and/or partly the secondary radiation. In particular, the lighting device, in particular conversion LED, comprises a filter or filter particles absorbing the primary radiation and/or partly the secondary radiation if the lighting device, in particular the conversion LED, is used for the backlighting of display elements.
In one embodiment, the filters are color filter systems of the colors red, green and blue.
In one embodiment, the color filter system has a respective full width at half maximum in the range of 70 to 120 nm for the colors red, green, blue.
The color filter system advantageously comprises a blue filter, a green filter and a red filter, which filter the overall radiation to form light of a first, second and third transmission spectrum.
In one embodiment, the emission of the lighting device, in particular of the conversion LED, and the transmission of the color filter system are chosen such that the maxima are at similar wavelengths. As a result, there is only little reabsorption at the color filter system.
In one embodiment, the phosphor(s) is (are) distributed homogeneously in the conversion element.
In one embodiment, the phosphor(s) are distributed with a concentration gradient in the conversion element.
In one embodiment, the phosphor having a shorter peak wavelength is disposed downstream of the phosphor(s) having a longer peak wavelength in order to reduce absorption losses.
In one embodiment, the phosphor or the phosphors is or are particles of the corresponding phosphor.
The particles of the phosphors can have, independently of one another, an average grain size of between 1 μm and 50 μm, advantageously between 5 μm and 40 μm, particularly advantageously between 8 μm and 35 μm, very particularly advantageously between 8 μm and 30 μm. With these grain sizes, the primary radiation or the secondary radiation is advantageously scattered little and/or principally in the forward direction at these particles, which reduces efficiency losses.
In one embodiment, the conversion element consists of the phosphor and the matrix material or the phosphors and the matrix material.
In one embodiment, the conversion element is configured as a lamina.
In one embodiment, the lamina has a thickness of 1 μm to 1 mm, advantageously 10 μm to 150 μm, particularly advantageously 25 μm to 100 μm.
The layer thickness of the entire lamina can be uniform. In this regard, a constant color locus can be obtained over the entire area of the lamina.
In one embodiment, the conversion element can be a ceramic lamina. This should be understood to mean that the lamina consists of sintered-together particles of the phosphor or of the phosphors.
In one embodiment, the lamina comprises a matrix material, for example glass, in which the phosphor(s) is or are embedded. The lamina can also consist of the matrix material, for example of glass, and the phosphor(s). Silicones, epoxy resins, polysilazanes, polymethacrylates and polycarbonates and combinations thereof are also possible as matrix materials for the lamina.
In accordance with one embodiment, the conversion element is configured as a lamina arranged above the primary radiation source or the layer sequence.
The conversion element shaped as a lamina can be fitted directly on the primary radiation source or the layer sequence. It is possible for the lamina to completely cover the entire surface, in particular the radiation exit surface, of the primary radiation source or of the layer sequence.
The lighting device, in particular the conversion LED, can comprise a housing. In the housing, a cutout can be present in the center. The primary radiation source or the layer sequence can be fitted in the cutout. It is also possible for one or more further primary radiation sources or layer sequences to be fitted in the cutout.
It is possible for the cutout to be filled with a potting that covers the primary radiation source or the layer sequence. However, the cutout can also consist of an air space.
In one embodiment, the conversion element is arranged above the cutout of the housing. In this embodiment, there is in particular no direct and/or positively locking contact between the conversion element and the primary radiation source or the layer sequence. That is to say that there may be a distance between the conversion element and the primary radiation source or layer sequence. In other words, the conversion element is disposed downstream of the primary radiation source or the layer sequence and is irradiated by the primary radiation. A potting or an air gap may then be formed between the conversion element and the primary radiation source or the layer sequence. This arrangement may be referred to as “remote phosphor conversion”.
In one embodiment, the conversion element is part of a potting of the primary radiation source or of the layer sequence or the conversion element forms the potting.
In one embodiment, the conversion element is configured as a layer. The layer can be arranged above the radiation exit surface of the primary radiation source or of the layer stack or above the radiation exit surface and the side surfaces of the primary radiation source or of the layer stack.
The use of a lighting device, in particular of a conversion LED, is specified. All features of the lighting device and of the conversion LED are also disclosed for the use thereof, and vice-versa.
The use of a lighting device, in particular of a conversion LED, for the backlighting of display devices, in particular displays, is specified. By way of example, displays of televisions, such as liquid crystal displays, computer monitors, tablets or smartphones are involved.
For the backlighting of display elements, the lighting devices, in particular conversion LEDs, used must firstly have a high brightness and secondly cover a large color space. Known filter systems used in conversion LEDs for backlighting consist of three or four color filters (blue, green and red or blue, green, yellow and red). The filters usually have a full width at half maximum in the range of typically 70 to 120 nm. The transmission results from the superposition of the three color filters; this results in regions of the visible spectrum in which complete transmission is not achieved. That has the effect that, in the case of a broadband spectrum of the conversion LED that backlights the color filters, a proportion of the emitted light is absorbed by the filter. In order to obtain the maximum quantity of light from the conversion LED at the display level, therefore, narrowband phosphors are required. In order moreover to obtain a high color saturation, it is important for the individual emissions of the conversion LEDs to address spectrally in each case as far as possible only one color of the color filter system.
Surprisingly, the lighting devices, in particular conversion LEDs, according to the present disclosure are very well suited to the backlighting of displays. In particular a lighting device, in particular a conversion LED, having a conversion element comprising the phosphor of the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, very particularly advantageously r=0.25, (Rbr′Li1-r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, (K1-r″-r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, advantageously 0.1<r″<0.4 and 0.1<r′″<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r″′<0.3, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E, or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<1.0, advantageously 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6, very particularly advantageously r*=0.5, has proved to be particularly suitable for the backlighting of display elements since the peak wavelength of the phosphor is in the green spectral range of the electromagnetic spectrum and has a full width at half maximum of less than 50 nm. As a result of the small full width at half maximum of the phosphors according to the present disclosure, the emission peaks exhibit a very large overlap with the transmission range of a standard green filter, such that only little light is lost and the achievable color space is large.
Lighting devices, in particular conversion LEDs, having a conversion element comprising the phosphor (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.05<r≤0.2, advantageously 0.1<r≤0.2, are also suitable for the backlighting of displays.
The use of a lighting device, in particular a conversion LED, in warning lights and flashing lights in motor vehicles is specified. The lighting device, in particular the conversion light-emitting diode, is configured to emit an orange or yellow-orange radiation. Advantageously, the phosphor has the formula Na1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu, wherein 0.1≤y**≥0.4, 0.15≤y**≤0.35 or 0.2≤y**≤0.3.
The use of a lighting device, in particular a conversion LED, in blue light sources for reducing melatonin production or for color-on-demand applications is specified. The lighting device, in particular the conversion light-emitting diode, is configured to emit a blue radiation. Advantageously, the phosphor has the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.4<r≤1, advantageously 0.45<r≤1, very particularly advantageously r=0.5. Advantageously, TA=Li, TD=Si and XB=O. By way of example, the phosphor has the formula (Na0.5K0.5)Li3SiO4:Eu. Alternatively, the phosphor has the formula (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<0.4, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25. By way of example, the phosphor has the formula (Rb0.25Na0.75) Li3SiO4:Eu. Alternatively, the phosphor has the formula (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E or (Rb,Na,K)1(TA)3(TD)1(XB)4:E, for example (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu or (Rb0.25Na0.5K0.25) Li3SiO4:Eu. The peak wavelength of the phosphor is in the blue spectral range.
Vigilance and/or the ability to concentrate can be increased by reducing melatonin production.
The use of a lighting device, in particular a conversion LED, for general lighting is specified. The lighting device, in particular the conversion light-emitting diode, is configured to emit a white radiation. In particular, warm-white radiation having a color temperature of less than 3500 K, advantageously less than 3000 K, is involved.
For general lighting, the phosphor in this case has for example the formula (NarK1−r)1(TA)3(TD)1(XB)4:E where 0≤r≤0.05, advantageously r=0. Advantageously, TA=Li, TD=Si and XB=O. By way of example, the phosphor is KLi3SiO4:Eu. The phosphor exhibits very broadband emission from the blue to red spectral range, thus giving rise to a white-colored luminous impression. The lighting device, in particular the conversion LED, in accordance with this embodiment emits a warm-white radiation having a color temperature of less than 3500 K, in particular less than 3000 K.
For general lighting, the phosphor can also have the following formula
(NarK1-r)1(TA)3(TD)1(XB)4:E
where 0.4<r≤1, advantageously 0.45<r≤1, very particularly advantageously r=0.5 or 1. Advantageously, TA=Li, TD=Si and XB=O. By way of example, the phosphor has the formula NaLi3SiO4:Eu or (Na0.5K0.5)Li3SiO4:Eu. Alternatively, the phosphor can have the formula (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E, wherein 0<r*<0.4, advantageously 0.1≤r*≤0.35, particularly advantageously 0.2≤r*≤0.3, very particularly advantageously r*=0.25. By way of example, the phosphor has the formula (Rb0.25Na0.75) Li3SiO4:Eu. Alternatively, the phosphor has the formula (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4:E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E or (Rb,Na,K)1(TA)3(TD)1(XB)4:E, for example (Cs0.25Na0.25Rb0.25Li0.25) Li3SiO4:Eu, (Cs0.25Na0.5K0.25) Li3SiO4:Eu or (Rb0.25Na0.5K0.25) Li3SiO4:Eu. The peak wavelengths of these phosphors are advantageously in the blue spectral range, in particular in the range of between 450 nm and 500 nm. The conversion element comprises a second and a third phosphor, wherein the second phosphor is configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation in the red spectral range and the third phosphor is configured to convert the electromagnetic primary radiation into an electromagnetic secondary radiation in the green spectral range during operation of the lighting device.
For general lighting, the phosphor can also have the following formula
Na1−y*Cay*Li3−2yAl3y*Si1−y*O4−4y*N4y*:E
0<y*≤0.875, advantageously 0<y*≤0.5, particularly advantageously 0<y*≤0.3, very particularly advantageously 0<y*≤0.1. The peak wavelength of the phosphor is advantageously in the blue or green spectral range. The conversion element comprises a second and a third phosphor, wherein the second phosphor is configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation in the red spectral range and the third phosphor is configured to convert the electromagnetic primary radiation into an electromagnetic secondary radiation in the green spectral range during operation of the lighting device.
In accordance with at least one embodiment, the display device is a display, for example of a television, of a smartphone, or a computer monitor or of a tablet.
In accordance with at least one embodiment, the lighting device, in particular the conversion LED, has a conversion element comprising the phosphor of the formula (NarK1-r)1(TA)3(TD)1(XB)4:E where 0.2<r≤0.4, advantageously 0.2<r≤0.3, particularly advantageously r=0.25 or (Rbr′Li1-r′)1(TA)3(TD)1(XB)4:E where 0≤r′≤1, advantageously 0.25≤r′≤0.75, particularly advantageously 0.4≤r′≤0.6, very particularly advantageously r′=0.5, (K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E where 0<r″<0.5 and 0<r′″<0.5, advantageously 0.1<r″<0.4 and 0.1<r″′<0.4, particularly advantageously 0.2<r″<0.3 and 0.2<r″′<0.3, (Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E, advantageously (Cs0.25Na0.25K0.25Li0.25) (TA)3(TD)1(XB)4:E or (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0.4≤r*<1.0, advantageously 0.4≤r*≤0.75, particularly advantageously 0.4≤r*≤0.6, very particularly advantageously r*=0.5. The conversion element comprises a second phosphor configured partly to convert the electromagnetic primary radiation into an electromagnetic secondary radiation that is in the red spectral range of the electromagnetic spectrum during operation of the lighting device.
The first exemplary embodiment (Al) of the phosphor according to the present disclosure has the molecular formula NaLi3SiO4:Eu2+ (2 mol % Eu2+ relative to the substance amount of Na) and is produced as follows: Na2CO3, Li2CO3, SiO2 and Eu2O3 are melted in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 1 below. The nickel crucible with the mixed starting materials is heated for one hour to approximately 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The starting materials of the phosphor are commercially available, stable and moreover very inexpensive. The synthesis at comparatively low temperatures makes the phosphor very inexpensive to produce and, as a result, also economically attractive.
The phosphor of the first exemplary embodiment (AB1) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The second exemplary embodiment (AB2) of the phosphor according to the present disclosure has the molecular formula KLi3SiO4:Eu2+ (2 mol % Eu2+ relative to the substance amount of K) and is produced as follows: K2CO3, Li2CO3, SiO2 and Eu2O3 are melted in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 2 below. The nickel crucible with the mixed starting materials is heated for one hour to approximately 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the second exemplary embodiment (AB2) exhibits a wide emission from the blue to red spectral range of the electromagnetic spectrum and thus emits white, in particular warm-white, radiation having a color temperature of less than 3500 K.
The third exemplary embodiment (AB3) of the phosphor according to the present disclosure has the molecular formula (Na0.5K0.5)Li3SiO4:Eu2+ (2 mol % Eu2+ relative to the substance amount of Na and K) or NaKLi6Si2O8:Eu2+ and is produced as follows: K2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are melted in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 3 below. The nickel crucible with the mixed starting materials is heated for one hour to eight hours to 800° C. to 1100° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the third exemplary embodiment (AB3) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The fourth exemplary embodiment (AB4) of the phosphor according to the present disclosure has the molecular formula (Na0.25K0.75)Li3SiO4:Eu2+ (2 mol % Eu2+ relative to the substance amount of Na and K) or NaK3Li12Si4O16:Eu2+ and is produced as follows: K2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are melted in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 4 below. The nickel crucible with the mixed starting materials is heated for four hours to 900° C. to 1100° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the fourth exemplary embodiment (AB4) exhibits an emission in the green spectral range of the electromagnetic spectrum.
The fifth exemplary embodiment (AB5) of the phosphor according to the present disclosure has the molecular formula (Rb0.5Li0.5) Li3SiO4:Eu2+ (2 mol % Eu2+ relative to the substance amount of (Rb0.5Li0.5)) or RbLiLi6Si2O8:Eu2+ and is produced as follows: Rb2CO3, Li2CO3, SiO2 and Eu2O3 are melted in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 5 below. The nickel crucible with the mixed starting materials is heated for four hours to approximately 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Afterward, the product obtained is ground and a green powder is obtained.
Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the fifth exemplary embodiment (AB5) exhibits an emission in the green spectral range of the electromagnetic spectrum.
The sixth exemplary embodiment (AB6) of the phosphor according to the present disclosure has the molecular formula Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:Eu (where y*=0.03; Eu2+ approximately 2 mol % relative to the substance amount of Na and Ca) and is produced as follows: CaO, NaF, NiN3, Li2O, LiAlH4, AlF3, SiO2 and EuF3 are heated in a stoichiometric ratio corresponding to the molecular formula to a maximum of 950° C. in a welded shut tantalum ampoule. During the heating or firing process, the ampoule is situated in an evacuated glass tube in order to avoid oxidation of the ampoule (reduced stability) and hence bursting, which results from the vapor pressure of evaporated starting materials during heating. After cooling to room temperature, individual crystals of the phosphor can be isolated from byproducts and be structurally and optically examined. The weighed-in quantities of the starting materials are found in table 6 below.
The synthesis at comparatively low temperatures makes the phosphor very inexpensive to produce and, as a result, also economically attractive. By means of energy dispersive X-ray spectroscopy on single crystals of the phosphor, an average Ca proportion of 3 mol % based on the total substance amount of Na and Ca and a nitrogen proportion of 3 mol % relative to the total substance amount of nitrogen and oxygen were determined, which accords with the formula Na0.97Ca0.03Li2.94Al0.09Si0.97O3.88N0.12:Eu.
The phosphor of the sixth exemplary embodiment (AB6) exhibits an emission in the blue-green spectral range of the electromagnetic spectrum.
The seventh exemplary embodiment (AB7) of the phosphor according to the present disclosure has the molecular formula (Na0.25K0.50Li0.25) Li3SiO4:Eu2+ or NaK2Li(Li3SiO4)4:Eu2+ and is produced as follows: K2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are mixed in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 7 below. The nickel crucible with the mixed starting materials is heated for four hours to approximately 750° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor. After cooling, an agglomerate of light green crystals is obtained, which are separated into individual crystals by grinding for example in an agate mortar.
The phosphor of the seventh exemplary embodiment (AB7) exhibits an emission in the green spectral range of the electromagnetic spectrum. By means of single crystal diffractometry, the molecular formula (Na0.25K0.50Li0.25)Li3SiO4:Eu2+ can be allocated to the phosphor.
The eighth exemplary embodiment (AB8) of the phosphor according to the present disclosure has the molecular formula (Rb0.5Na0.5) Li3SiO4:Eu2+ or RbNaLi6Si2O8:Eu2+ and is produced as follows: Rb2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are mixed in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 8 below. The nickel crucible with the mixed starting materials is heated for one to eight hours to between 700° C. and 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. The product obtained is then ground and a green powder is obtained.
Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the eighth exemplary embodiment (AB8) exhibits an emission in the green spectral range of the electromagnetic spectrum.
The ninth exemplary embodiment (AB9) of the phosphor according to the present disclosure has the molecular formula (Rb0.25Na0.75) Li3SiO4:Eu2+ or RbNa3Li12Si4O16:Eu2+ and is produced as follows: Rb2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are mixed in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 9 below. The nickel crucible with the mixed starting materials is heated for one to eight hours to between 700° C. and 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and then cooled. The product obtained is then ground and a green powder is obtained.
Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the ninth exemplary embodiment (AB9) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The tenth exemplary embodiment (AB10) of the phosphor according to the present disclosure has the molecular formula Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4 (O1-r**Nr**)4 where r**=0.67 and thus SrSiAl0.84Li2.16O1.32N2.68:Eu2+ and is produced as follows: NaLi3SiO4, SrO, LiAlH4 and Eu2O3 are mixed in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 10 below. The nickel crucible with the mixed starting materials is heated for one to eight hours, advantageously 2 to six hours, very particularly advantageously for four hours, to a temperature between 800° C. and 1000° C., advantageously 900° C., under a forming gas atmosphere (N2:H2=92.5:7.5) in a tube furnace and then cooled.
Further heating under the same forming gas atmosphere and to temperatures below the melting point of the phosphor can be carried out in order to further improve the optical properties of the phosphor.
The phosphor of the tenth exemplary embodiment (AB10) exhibits an emission in the yellow or yellow-orange spectral range of the electromagnetic spectrum. The composition of the tenth exemplary embodiment was determined by means of energy dispersive X-ray spectroscopy on single crystals and single crystal diffractometry.
The eleventh exemplary embodiment (AB11) of the phosphor according to the present disclosure has the molecular formula Na1−y**Euy*Li3−2y**Al3y**Si1−y**O4−4y**N4y**:Eu where y**=0.2224 and is produced as follows: CaO, LiF, LiN3, Li2O, LiAlH4, SiO2 and EuF3 are heated to a maximum of 900° C. in a welded shut tantalum ampoule. During the heating or firing process, the ampoule is situated in an evacuated glass tube in order to avoid oxidation of the ampoule (reduced stability) and hence bursting, which results from the vapor pressure of evaporated starting materials during heating. After cooling to room temperature, individual orange crystals of the phosphor can be isolated from byproducts and be structurally and optically examined. The weighed-in quantities of the starting materials are found in table 11 below.
The phosphor of the eleventh exemplary embodiment (AB11) exhibits an emission in the yellow-orange spectral range of the electromagnetic spectrum.
The twelfth exemplary embodiment (AB12) of the phosphor according to the present disclosure has the molecular formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu where x**=0.2014 and is produced as follows: SrAl2O4:Eu and LiN3 are heated to a maximum of 900° C. in a welded shut tantalum ampoule. During the heating or firing process, the ampoule is situated in an evacuated glass tube in order to avoid oxidation of the ampoule (reduced stability) and hence bursting, which results from the vapor pressure of evaporated starting materials during heating. After cooling to room temperature, individual yellow/green crystals of the phosphor can be isolated from byproducts and be structurally and optically examined. The weighed-in quantities of the starting materials are found in table 12 below.
The phosphor can be produced at comparatively low temperatures, below 1000° C., which makes possible a cost-saving synthesis.
The phosphor of the twelfth exemplary embodiment (AB12) exhibits an emission in the green to yellow spectral range of the electromagnetic spectrum.
Further exemplary embodiments of the phosphor having the molecular formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu are produced by mixing the starting materials in accordance with table 13 below in an open nickel crucible. The nickel crucible with the mixed starting materials is heated for one to 12 hours, advantageously 4 to 8 hours, to a temperature of between 800° C. and 1200° C., advantageously 900° C., under a forming gas atmosphere (N2:H2=92.5:7.5) under atmospheric pressure or slightly reduced pressure in a tube furnace and is then cooled. After cooling to room temperature, individual yellow/green crystals can be isolated.
The thirteenth exemplary embodiment (AB13) of the phosphor according to the present disclosure has the molecular formula (Cs0.25Na0.25K0.25Li0.25) Li3SiO4:Eu2+ and is produced analogously to the eighth exemplary embodiment. The starting materials are indicated in table 14 below.
The phosphor of the thirteenth exemplary embodiment (AB13) exhibits an emission in the green spectral range of the electromagnetic spectrum.
The fourteenth exemplary embodiment (AB14) of the phosphor according to the present disclosure has the molecular formula (Cs0.25Na0.50K0.25)Li3SiO4:Eu2+ and is produced analogously to the eighth exemplary embodiment. The starting materials are indicated in table 15 below.
The phosphor of the fourteenth exemplary embodiment (AB14) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The fifteenth exemplary embodiment (AB15) of the phosphor according to the present disclosure has the molecular formula (Rb0.25Na0.50K0.25)Li3SiO4:Eu2+ and is produced analogously to the eighth exemplary embodiment. The starting materials are indicated in table 16 below.
The phosphor of the fifteenth exemplary embodiment (AB15) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The sixteenth exemplary embodiment (AB16) of the phosphor according to the present disclosure has the molecular formula (Rb0.25Na0.25Cs0.25Li0.25) Li3SiO4:Eu2+ and is produced analogously to the eighth exemplary embodiment. The starting materials are indicated in table 17 below.
The phosphor of the sixteenth exemplary embodiment (AB16) exhibits an emission in the blue spectral range of the electromagnetic spectrum.
The seventeenth exemplary embodiment (AB17) of the phosphor according to the present disclosure has the molecular formula (Na0.125K0.875)Li3SiO4:Eu2+ or NaK7 (Li3SiO4):Eu2+ and is produced as follows: K2CO3, Na2CO3, Li2CO3, SiO2 and Eu2O3 are mixed in a stoichiometric ratio corresponding to the molecular formula in an open nickel crucible. The weighed-in quantities of the starting materials are found in table 18 below. The nickel crucible with the mixed starting materials is heated for four hours to 1000° C. under a forming gas atmosphere (N2:H2=92.5:7.5) and is then cooled at a constant cooling rate to 300° C. The furnace is switched off and, after cooling to room temperature, yellow-green single crystals are isolated.
The phosphor of the seventeenth exemplary embodiment (AB17) exhibits an emission in the blue-green and in the yellow-orange spectral range of the electromagnetic spectrum.
Further advantageous embodiments and developments of the present disclosure are evident from the exemplary embodiments described below in association with the figures.
In the drawings, like reference characters generally refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the disclosed embodiments. In the following description, various embodiments described with reference to the following drawings, in which:
b, 129, 131, 133, 135, 152b, 154, 161, 163 show emission spectra of exemplary embodiments of the phosphor according to the present disclosure.
a, 177 show X-ray diffraction powder diffractograms using copper Kα1 radiation or molybdenum Kα1 radiation.
In the following description, numerous specific details are given to provide a thorough understanding of embodiments. The embodiments may be practiced without one or several specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the embodiments.
Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
K/S=(1−Rinf)2/2Rinf,
wherein Rinf corresponds to the diffuse reflection of the phosphor.
It is evident from
Two X-ray diffraction powder diffractograms using copper Kα1 radiation are indicated in
A crystallographic evaluation is found in
It is evident from
The use of the phosphor according to the present disclosure in a white-emitting conversion LED has numerous advantages. It is possible to use a primary radiation which is not perceived or is only scarcely perceived by the human eye (300 nm to 430 nm or 440 nm). Fluctuations of the primary radiations thus do not adversely affect the overall radiation properties. No color adaptation is required since the emission spectrum is constant. The conversion LEDs can be produced with a high throughput since color adaptation or complex chip binning is not required. No color shifts or other negative effects on the emission spectrum as a result of selective degradation of only one phosphor or changes in the primary radiation caused by temperature or forward current fluctuations occur. Furthermore, the conversion LED does not have an inherent color, but rather exhibits a white appearance in the switched-off state. Therefore, the phosphor is also suitable for “remote phosphor” arrangements in which a yellow or orange appearance in the switched-off state is not desired. A partial conversion of the primary radiation can also be carried out depending on the application. Since it is possible to excite the phosphor with a primary radiation in the range of 300 nm to 430 nm or 440 nm, a contribution of the primary radiation, advantageously in the short-wave blue range of the electromagnetic spectrum, to the overall radiation has the effect that objects illuminated thereby appear whiter, more radiant and therefore more attractive. By way of example, optical brightening agents in textiles can be excited thereby.
Two X-ray diffraction powder diffractograms using copper Kα1 radiation are indicated in
A crystallographic evaluation is found in
It is evident from
A crystallographic evaluation is found in
The curve designated by smel shows the sensitivity curve for melatonin production, that is to say with what wavelengths melatonin production in the body can best be suppressed (“human response function for melanopic effects”; Lucas et al., Trends in Neurosciences January 2014 Vol. 37 No. 1). As evident, the emission spectrum of AB3 exhibits a high overlap with smel, and so this radiation can be effectively used for suppressing the formation of melatonin. Such irradiation can lead to an increased vigilance or ability to concentrate.
In
The optical data of the phosphors AB7 and BS are shown in
In
A crystallographic evaluation is found in
A crystallographic evaluation is found in
In
Weighed-in quantities of the starting materials for AB-10a
Weighed-in quantities of the starting materials for AB-10b
As is evident, by varying r**in the formula Sr(Si0.25Al−1/8+r**/2Li7/8−r**/2)4 (O1−r**Nr**)4, it is possible for the peak wavelength to be shifted from the yellow into the red spectral range. A comparison of optical properties of AB10, AB-10a and AB-10b is shown in
The diagram illustrates the superimposition of the measured reflections with the calculated reflections for SrSiAl0.84Li2.16O1.32N2.68:Eu. The upper part of the diagram shows the experimentally observed reflections (Cu Kai radiation); the lower part of the diagram shows the calculated reflection positions. The calculation was made on the basis of the structure model for SrSiAl0.84Li2.16O1.32N2.68:Eu, as described in
Optical data for AB11 are shown in
The optical properties of AB14, AB15 and AB16 are similar to those of AB9 and AB3.
In particular, two types of channels are contained in the crystal structure. Exclusively K atoms are arranged in the first channels, while Na and K atoms are arranged in the other channels. SiO4 tetrahedra (closely hatched) are arranged in the form of a helix (
The conversion LED in accordance with
The conversion element 3 can be applied for example by injection molding, transfer molding or by spray coating methods. Moreover, the conversion LED has electrical contacts (not shown), the formation and arrangement of which are known to the person skilled in the art.
The conversion LED 1 in accordance with
The present disclosure is not restricted to the exemplary embodiments by the description on the basis of said exemplary embodiments. Rather, the present disclosure encompasses any novel feature and also any combination of features, which in particular includes any combination of features in the patent claims, even if this feature or this combination itself is not explicitly specified in the patent claims or exemplary embodiments.
While the disclosed embodiments have been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the disclosed embodiments as defined by the appended claims. The scope of the disclosed embodiments is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced.
The following exemplary embodiments pertain to further aspects of this disclosure:
Embodiment 1 is a lighting device comprising a phosphor having the general molecular formula
(MA)a(MB)b(MC)c(MD)d(TA)e(TB)f(TC)g(TD)h(TE)i(TF)j(XA)k(XB)l(XC)m(XD)n:E,
wherein
Embodiment 2 is the lighting device according to embodiment 1, wherein the phosphor has a crystal structure in which TA, TB, TC, TD, TE and/or TF are surrounded by XA, XB, XC and/or XD, and the resultant structural units are linked via common corners and edges to form a three-dimensional spatial network having cavities or channels and MA, MB, MC and/or MD are/is arranged in the cavities or channels.
Embodiment 3 is the lighting device according to embodiment 1 or 2, wherein the phosphor has the following general molecular formula:
(MA)a(MB)b(TA)e(TB)f(TC)g(TD)h(XB)l(XC)m,
wherein
Embodiment 4 is the lighting device according to embodiment 3, wherein
Embodiment 5 is the lighting device according to any of embodiments 1 to 4, wherein the lighting device is a conversion light-emitting diode (1), comprising
Embodiment 6 is the lighting device according to any of embodiments 1 to 5, wherein the following hold true for the phosphor:
Embodiment 7 is the lighting device according to any of embodiments 1 to 6, wherein the phosphor has one of the following general molecular formulae:
(MA)Li3−xSi1−xZnxAlxO4:E
(MA)Li3−xSi1-xMgxAlxO4: E
(MA)1−x′Cax′Li3Si1−x′Alx′O4:E
(MA)1−x″Cax″Li3−x″,Si1−x″Mg2x″O4:E
(MA)Li3−2zMg3zSi1−zO4:E or
(MA)Li3Si1−2z′Alz′Pz′O4:E, wherein
0≤x≤1,
0≤x′≤1,
0≤x″≤1,
0≤z≤1,
0≤z′≤0.5 and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof.
Embodiment 8 is the lighting device according to any of embodiments 1 to 6,
wherein the phosphor has one of the following general molecular formulae:
(MA)1−yZnyLi3−2yAl3ySi1−yO4−4yN4y:E,
(MA)1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E,
(MA)1−y***Sry***Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E
(MA)1−y**Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E
(MA)Li3−y′Aly′SiO4−2y′N2y′:E,
(MA)Li3−y″Mgy″SiO4−y″Ny″:E,
(MA)1−w′″Caw′″Li3SiO4−w′″Nw′″:E,
(MA)Li3−w′Al2w′Si1−w′O4−w′Nw′:E,
(MA)1−w″Caw″Li3−w″Si1−w″Al2w″O4−2w″N2w″:E,
wherein
0<y*<0.875,
0<y**<0.875,
0<y***<0.875,
0≤y<0.875,
0≤y′≤1.75,
0≤y′≤3,
0≤w″′≤1,
0≤w′≤1,
0≤w″≤1 and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof.
Embodiment 9 is the lighting device according to any of embodiments 1 to 6,
wherein the phosphor has the following general molecular formula: (MA)1 (TA)3(TD)1(XB)4:E, wherein
MA is selected from a group of monovalent metals which comprises Li, Na, K, Rb, Cs and combinations thereof,
Embodiment 10 is the lighting device according to embodiment 9,
wherein the phosphor has the general formula
(NarK1−r)1(TA)3(TD)1(XB)4:E,(Rbr′Li1−r′)1(TA)3(TD)1(XB)4:E,(K1−r″−r′″Nar″Lir′″)1(TA)3(TD)1(XB)4:E or (Rbr*Na1−r*)1(TA)3(TD)1(XB)4:E,
wherein
0≤r≤1,
0≤r′≤1,
0<r″<0.5,
0<r′″<0.5,
0<r*<1
and E is selected from a group which comprises Eu, Ce, Yb, Mn and combinations thereof.
Embodiment 11 is the lighting device according to embodiment 9, wherein the phosphor has the formula
(Cs,Na,K,Li)1(TA)3(TD)1(XB)4:E.
Embodiment 12 is the lighting device according to embodiment 9, wherein the phosphor has the formula (NarK1-r)1(TA)3(TD)1(XB)4:E or (NarK1−r)Li3SiO4:E, wherein 0.05<r≤0.2, preferably 0.1<r≤0.2 and E=Eu, Ce, Yb and/or Mn.
Embodiment 13 is the lighting device according to embodiment 8, wherein the phosphor has the formula Na1−y*Cay*Li3−2y*Al3y*Si1−y*O4−4y*N4y*:E, wherein 0<y*<0.875, preferably 0<y*≤0.5 and E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof.
Embodiment 14 is the lighting device according to embodiment 8, wherein the phosphor has the formula Na1−y*Euy**Li3−2y**Al3y**Si1−y**O4−4y**N4y**:E, wherein 0<y**<0.875, preferably 0<y**<0.5 and E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof.
Embodiment 15 is the lighting device according to any of embodiments 1 to 6, wherein the phosphor has the formula (MB)Li3−2x**Al1+2x**O4−4x**N4x**:E, wherein 0<x**<0.875, MB is selected from a group of divalent metals which comprises Mg, Ca, Sr, Ba, Zn and combinations thereof, and E is selected from a group which comprises Eu, Mn, Ce, Yb and combinations thereof.
Embodiment 16 is the lighting device according to embodiment 15, wherein the phosphor has the formula SrLi3−2x**Al1+2x**O4−4x**N4x**:Eu, wherein 0<x**<0.875, preferably 0.125≤x**<0.875 or 0.125≤x**≤0.5, very particularly preferably 0.125≤x**≤0.45.
Embodiment 17 is the lighting device according to any of embodiments 1 to 6, wherein the phosphor has the formula (MB)(Si0.25Al−1/8+r**/2Li7/8−r**/2)4 (O1−r**Nr**)4:E, wherein 0.25≤r**≤1, MB is selected from a group of divalent metals which comprises Mg, Ca, Sr, Ba and combinations thereof, and E=Eu, Ce, Yb and/or Mn.
Embodiment 18 is the lighting device according to embodiment 7,
which is configured to emit a blue radiation, wherein the phosphor has the formula
(NarK1−r)1(TA)3(TD)1(XB)4:E
where 0.4<r≤1 (Rbr*Na1-r*)1(TA)3(TD)1(XB)4:E where 0<r*<0.4 or (Cs,Na,Rb,Li)1(TA)3(TD)1(XB)4: E, (Cs,Na,K)1(TA)3(TD)1(XB)4:E and (Rb,Na,K)1(TA)3(TD)1(XB)4:E.
Embodiment 19 is the use of a lighting device according to any of embodiments 1 to 18 for the backlighting of display devices, in particular of displays.
Embodiment 20 is a display device comprising a lighting device according to any of embodiments 1 to 18.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2016 114 996 | Aug 2016 | DE | national |
| 10 2016 121 694 | Nov 2016 | DE | national |
The present application is a divisional of U.S. patent application Ser. No. 16/302,724, filed on Nov. 19, 2018 which is a National Stage Application of PCT application No. PCT/EP2017/070343 filed on Aug. 10, 2017, which claims priority from German application No. 10 2016 114 996.9 filed on Aug. 12, 2016 and from German application No. 10 2016 121 694.1 filed on Nov. 11, 2016, all of which are incorporated herein by reference in their entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20190157520 A1 | May 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16302724 | US | |
| Child | 16198812 | US |
