TW201925419A - Multicomponent luminophores as colour converters for solid-state light sources - Google Patents

Abstract

What are proposed are multicomponent luminophores comprising or consisting of (i) a core and (ii) at least one shell arranged concentrically around the core, where (a) the core comprises at least one first luminophore doped with Ce<SP>3+</SP> and/or Eu<SP>2+</SP> and (b) the shell includes at least one second luminophore which is a compound containing (b1) Eu<SP>3+</SP> and/or Pr<SP>3+</SP> and/or Sm<SP>3+</SP> and (b2) Tb<SP>3+</SP> and/or Gd<SP>3+</SP>.

Description

Multicomponent luminophore as a color converter for solid state light sources

The invention resides in the field of luminophores and relates to the following: novel multicomponent luminophores, preferably of the core-shell compound type; methods for their production; uses thereof; and components comprising such materials.

Since the invention of the white LED of S. Nakamura et al., the Ce ³⁺ garnet has become the most important radiation converter in solid-state light sources based on (In,Ga)N semiconductors [see TSA et al. " III-Nitride Based" Light Emitting Diodes and Applications ", Springer, Dordrecht, 2013, 26 pp. 11 to (2013); SCHUBERT's" Light-emitting diodes ", 2nd Edition, Cambridge Univ Press, Cambridge, ( 2010)].. Compounds derived from the garnet class have been found to be particularly suitable host compounds. These compounds are characterized by high chemical, thermal and mechanical stability. In addition, garnet-based luminophores typically have extremely high quenching temperatures which make them particularly suitable for use on LED wafers. The standard radiation converter is specifically yellow-emitting to green-emitting Ce ³⁺ garnet Y ₃ Al ₅ O ₁₂ :Ce ³⁺ and Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ . In combination with blue-emitting (In, Ga) N semiconductors, it is possible to implement a cool white light source with a color temperature of about 4000 K [see MOTTIER (eds.) " LEDs for lighting applications ", ISTE Ltd, London, 2009 ; BORN et al. ChiuZ 40, 305 to page 294 (2006)].

In order to realize a warm white light source based on blue (In,Ga)N LED (color temperature of 2700 to 3000 K), in addition to yellowing or green garnet, a red light converter material is additionally required. The red-emitting converter material has sufficiently strong absorption at primary radiation of appropriate wavelength (370 to 480 nm) and exhibits photoluminescence with high quantum yield. At the same time, the stability of such luminophores must be as high as the stability of the garnet so that there is no unwanted shift in the color trajectory during the life of the solid state light source.

For this purpose, a variety of luminophores have been developed that have met these needs over the past 20 years. Luminescent group used so far, that is, (Ca, Sr, Ba) ₂ SiO ₄ :Eu (n-decanoate), (Ca,Sr)S:Eu, (Ca,Sr)AlSiN ₃ :Eu,O and (Ca , Sr,Ba) ₂ Si ₅ N ₈ :Eu,O, both based on the activator Eu ²⁺ , characterized by both broad absorption spectra and broad emission bands [see MÜLLER MACH et al., Phys. Status Solid (A) 202, 1732 to 1727 (2005)].

. J. ALLOYS COMP 708, 5 pp. 1 (2017) in the GUI et al entitled _{"Hydrothermally synthesized β-NaGdF 4: Eu} 3+ @ β-NaGdF 4: Ce 3+, Dy 3+ phosphors with multicolour luminescence The paper of the properties via dual-channel excitation and energy migration procedure reveals a core-shell luminophore with a hexagonal phase. However, such luminophores are exclusively fluorine-containing alkali metal compounds. In these materials, efficient excitation is only possible in the spectral range of about 250 to 300 nm. These compounds are therefore not suitable for use in (In,Ga)N LED wafers.

In this connection, reference is also made to the following publication: Chinese Patent Specification CN 103865535 A (GRIREM ADVANCED MATERIALS) discloses a white light LED having a core-shell structure in which the inner core is composed of YAG and the outer casing is composed of LuAG. For example, a relatively luminescent group having a garnet core and an outer shell containing cerium oxide is known from WO 2008 107062 A1 (MERCK). Two documents US 2012 0032113 A1 and US 2016 0251574 A1 (RHODIA) provide a core-shell luminophore with a mineral core and an outer shell composed of various rare earth metal oxides or aluminates.

A significant disadvantage of these Eu ²⁺ activating materials is their relatively high sensitivity to photodegradation due to the photoionization tendency of Eu ²⁺ , particularly in host materials having relatively small energy band gaps. A further disadvantage is that the half-height width of the Eu ²⁺ emission band is very high, which is manifested as a moderate lumen equivalent (<200 lm/W) when the color trajectory is in the deep red spectral region [see BAUR et al., J. Mater. Chem. C 3, of 2054 to 2064 (2015)].

An alternative that has been developed is the K ₂ SiF ₆ :Mn ⁴⁺ luminophore with narrow-band red light emission, which does not exhibit any emission in the deep red spectral region and therefore has a much higher efficiency (lumen equivalents > 200 lm/ W) [ US 2006 0169998 A1 (SRIVASTAVA)]. However, since the [Ar]3d ³ to [Ar]3d ³ transitions are parity-forbidden for quantum mechanical reasons, the absorber in the blue spectral region has a higher concentration than the Eu ²⁺ -based luminescence. The situation of the regiment is much lower. Therefore, a relatively high usage amount is required to produce warm white light. Furthermore, Mn ⁴⁺ in the fluorine host material has a tendency to participate in the reaction with the oxygen of the F ^- anion, which results in the formation of elemental fluorine and Mn ³⁺ or MnF ₃ associated with degradation of the luminophore. This requires specific post-treatment of the synthesized luminophore particles to ensure adequate stability during operation. In addition, a red light illuminating group which is activated by Sm ³⁺ or Pr ³⁺ can be used as the LED light-emitting group. However, concentration quenching can begin even at very low activator concentrations of the two activators, which is detrimental to the necessary absorption intensity of the LED luminophore.

For this reason, it is necessary to develop a red-emitting luminophore that does not have such disadvantages. For this purpose, the doping of Eu ³⁺ luminophores is especially an option since these luminophores have a high light yield in the red spectral region between about 610 and 630 nm. Due to the parity prohibition and spin inhibition of 4f ⁶ to 4f ⁶ transitions, the absorption intensity in the blue spectral region is still lower than the absorption intensity of Mn ⁴⁺ . A standard method of improved absorption is to use a sensitizer that exhibits strong absorption in the desired spectral region and transfers energy to the Eu3 ⁺ activator. For example, although Ce ³⁺ is a conventional sensitizer for Tb ³⁺ , it cannot be used in combination with Eu ³⁺ because of the so-called metal-metal charge transfer from Ce ³⁺ to Eu ³⁺ . This will significantly reduce the quantum yield. Possible alternative sensitizers are ions having an s ² electronic configuration, such as Pb ²⁺ , Sb ³⁺ or Bi ³⁺ . However, these sensitizers exhibit sufficient absorption only in the UV region of <350 nm and are therefore unsuitable for use in blue- emitting (Al,In,Ga)N semiconductors [ US 8,252,613 B1 (LYONS)]. Despite a large amount of research activity in this field, it has not been possible so far to provide a semiconductor LED with an Eu ^3+-doped luminophore having a sufficiently high absorption intensity.

The problem solved by the present invention is therefore to remedy the above-mentioned disadvantages of the prior art and in particular to provide novel luminophores having a multi-component structure with which a highly popular color rendering index (CRI > 90) can be produced and simultaneously A warm white LED with a very high lumen equivalent.

The present invention first provides a multicomponent luminophore comprising the following or consisting of:
(i) the kernel, and
(ii) at least one outer casing that is concentrically disposed about the core,
among them
(a) the core comprises at least one first inorganic luminophore doped with Ce ³⁺ and/or Eu ²⁺ , and
(b) the outer shell comprises at least one second luminophore, the at least one second luminophore being a compound comprising:
(b1) Eu ³⁺ and/or Pr ³⁺ and/or Sm ³⁺ , and
(b2) Tb ³⁺ and/or Gd ³⁺ .

The multicomponent luminophores are preferably core-shell compounds as described in detail below. In short, it is produced by depositing a substance that forms a shell on the core material. A schematic diagram is shown in FIG.

However, the term "multi-component luminophore" should also be understood to include composite compounds that do not fully conform to the housing and core protocols. For this purpose, in brief, the materials intended for the inner core and the outer casing are separately produced, and then they are compressed together in a weight ratio corresponding to the weight ratio in the core-shell compound and then sintered. These composite compounds have similar performance to core-shell compounds, but are much easier to produce and therefore less costly. The production of the composite compound is also described in detail below.

Surprisingly, it has been found that the core-shell luminophore of the present invention completely solves the complex problems set forth at the outset. This is because if the Ce ³⁺ or Eu ²⁺ ions are spatially close to the Eu ³⁺ ions in a particular crystal, it has been observed that metal-to-metal charge transfer (MMCT) results in a significant reduction in quantum yield. This process hinders the efficient use of Ce ³⁺ or Eu ²⁺ as a sensitizer for Eu ³⁺ . However, if the ions are spatially separated from each other within the crystallite or luminophore particles, the MMCT can be completely or largely prevented. If the ions are still in sufficient spatial proximity for efficient resonance energy transfer (ET) via a mediator (eg Tb ³⁺ or Gd ³⁺ ), it is possible to use Ce ³⁺ or Eu ²⁺ as Eu ³⁺ may also be used for the sensitizer of Pr ³⁺ or Sm ³⁺ without detracting from the quantum yield due to the above MMCT.

Kernel composition

The core of the novel luminophore of the present invention consists of Ce ³⁺ activated or Eu ²⁺ activated first luminophore; in addition, there may be additional luminophore doped with Tb ³⁺ and/or Gd ³⁺ . Preferably, the first luminophore has a garnet, citrate, borate, (oxy) fluoride and/or (oxy) nitride structure. Preferably, the first luminophore has a garnet structure and has been doped with Ce ³⁺ .

A particularly preferred first luminophore is:
Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ (LuAG); Lu ₃ Sc ₂ Al ₃ O ₁₂ :Ce ³⁺ (LSAG); Gd ₃ Al ₅ O ₁₂ :Ce ³⁺ (GdAG); Gd ₃ Sc ₂ Al ₃ O ₁₂ :Ce ³⁺ (GSAG); Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ (TAG); (Ca,Sr,Ba) ₂ SiO ₄ :Eu ²⁺ ;(Ca,Sr,Ba) ₃ SiO ₅ : Eu ²⁺ ;(Ca,Sr,Ba)Si ₂ N ₂ O ₂ :Eu ²⁺ ;(Sr,Ba)(Al,Y,Gd,Lu)Si ₄ N ₇ :Eu ²⁺ ;(La,Gd, Tb) ₃ Si ₆ N ₁₁ :Ce ³⁺ ; and its eutectic. Further suitable garnet structures are known, for example, from EP 2937315 A1 (PANASONIC). Theory on the optical properties of the garnet doped luminophores of cerium, reference INORG CHEM 53, 6614 to pp. 6607 (2014) in GONG et al., Entitled _{"Novel garnet-structure Ca 2 GdZr 2} (AlO 4) 3..: Ce ³⁺ phosphor and its structural tuning of optical properties ".

In addition to these specific luminophores, other compounds which may be doped with Ce ³⁺ and/or Eu ²⁺ are of course also useful, ie for example:
Lu ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , where 0<x≤0.4 and 0<y≤0.4;
Y ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , wherein 0<x≤0.4 and 0<y≤0.4;
Tb ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , wherein 0<x≤0.4 and 0<y≤0.4;
Gd ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , wherein 0<x≤0.4 and 0<y≤0.4;
Ca ₂ (Lu _1-xyz Gd _x Y _y Sc _z )(Zr _1-a Hf _a ) ₂ Al ₃ O ₁₂ , wherein 0<x+y+z≤1 and 0<a≤1;
Ca ₂ (Lu _1-xyz Gd _x Y _y Sc _z Mg _m )(Zr _1-a Hf _a ) ₂ (Al _1-m Si _m ) ₃ O ₁₂ , where 0<x+y+z≤1 and 0< A≤1 and 0<m≤1;
Ca _2-b (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t ) _1+b (Zr _1-a Hf _a ) _2-b Al _3+b O ₁₂ , where 0 <x+y+z≤1 and 0<a≤1 and 0<t≤1 and 0<b≤1;
(Lu _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6;
(Y _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6;
(Tb _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6;
(Gd _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6.

Other materials that can be used as a kernel are listed below:
(Ca,Sr,Ba) ₂ SiO ₄ :Eu ²⁺ ;(Ca,Sr,Ba) ₃ SiO ₅ :Eu ²⁺ ;(Gd,Y)F ₃ :Ce ³⁺ ;(Ca,Sr,Ba)Si ₂ N ₂ O ₂ :Eu ²⁺ ;(Sr,Ba)(Al,Y,Gd,Lu)Si ₄ N ₇ :Eu ²⁺ ;(La,Gd,Tb) ₃ Si ₆ N ₁₁ :Ce ³⁺ ; And mixtures thereof and co-crystals.

This has been found to be very useful when the core material has high chemical, thermal and mechanical stability so that it does not participate in any reaction during the coating operation.

Composition of the outer casing

The coating or shell consists of a second luminophore containing Tb ³⁺ or containing Gd ³⁺ , Eu ³⁺ activated, Pr ³⁺ activated and/or Sm ³⁺ activated. The embodiment in which the second luminophore is activated by Eu ³⁺ is clearly preferred. Further, materials having a high concentration of Tb ³⁺ are particularly preferred. The Ce ³⁺ or Eu ²⁺ ions in the core absorb the emission (340 to 510 nm) from the (Al, In, Ga) N semiconductor wafer and transfer the absorbed energy to the outer casing. Energy transfer from both Ce ³⁺ or Eu ²⁺ to Tb ³⁺ and from Tb ³⁺ to Eu ³⁺ is very efficient; therefore, Tb ³⁺ acts as an essential substance to ensure self-Ce ³⁺ to Eu ³⁺ A mediator with complete energy transfer. This process is shown in schematic form in Figure 10 .

For example, the second luminophore is selected from the group of compounds formed by:
Tb ₂ SiO ₅ ; Tb ₂ Si ₂ O ₇ ; TbBO ₃ ; TbB ₃ O ₆ ; Tb ₂ MoO ₆ ; Tb ₂ Mo ₂ O ₉ ; Tb ₂ Mo ₃ O ₁₂ ; Tb ₂ Mo ₄ O ₁₅ ; Tb ₃ Al ₅ O ₁₂ ; Tb ₃ (Al _1-x Ga _x ) ₅ O ₁₂ , where 0 < x ≤ 0.4; TbAl ₃ [BO ₃ ] ₄ ; CaTbAl ₃ O ₇ ; TbAl [Ge ₂ O ₇ ]; SrTb ₂ Al ₂ O ₇ ; Sr ₂ TbAlO ₅ ; TbAlO ₃ ; Tb ₄ Al ₂ O ₉ ; (Ba, Sr, Ca) ₃ TbB ₉ O ₁₈ ; (Ba, Sr, Ca) ₂ Tb ₂ Si ₄ O ₁₃ ; MgTbB ₅ O ₁₀ ; TbB ₅ O ₉ ; Tb ₂ B ₄ O ₉ ; ZnTbB ₅ O ₁₀ ; Ba ₂ TbNbO ₆ ; Ba ₂ TbTaO ₆ ; TbGa ₃ [BO ₃ ] ₄ ; Sr ₃ Tb ₂ [BO ₃ ] ₄ ; Sr ₃ Tb [BO ₃ ] ₃ ; Ca ₉ Tb[VO ₄ ] ₇ ; Ca ₉ Tb[PO ₄ ] ₇ ; LiTbW ₂ O ₈ ; Tb ₂ Mo ₂ O ₇ ; Tb ₂ Mo ₄ O ₁₅ ; Tb ₂ Sn ₂ O ₇ ; Sr ₂ TbTaO ₆ ; Tb ₂ Ti ₂ O ₇ ; Tb[VO ₄ ]; GdF ₃ ; (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t ) ₂ O ₃ , where 0 < x + y + z ≤ 1 and 0 < t ≤ 1; Ca ₂ (Lu _1-t Tb _t )Zr ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (Gd _1-t Tb _t )Zr ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (Lu _1-t Tb _t )Hf ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (Gd _1-t Tb _t )Hf ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t )(Zr _1-a Hf _a ) ₂ Al ₃ O ₁₂ , where 0 < x + y + z ≤ 1 and 0 < a ≤ 1 and 0 < t ≤ 1; Ca ₂ (Lu _1-xyzt Gd _x Y _y Sc _z Mg _m Tb _t )(Zr _{1- a} Hf _a ) ₂ (Al _1-m Si _m ) ₃ O ₁₂ , where 0 < x + y + z ≤ 1 and 0 < a ≤ 1 and 0 < m ≤ 1 and 0 < t ≤ 1; Ca _2-b (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t ) _1+b (Zr _1-a Hf _a ) _2-b Al _3+b O ₁₂ , where 0 < x + y + z ≤ 1 and 0 < a ≤ 1 and 0 < t ≤ 1 and 0 < b ≤ 1; and its eutectic.

Here, Tb ³⁺ or Gd ³⁺ in at least one of the layers is replaced by Eu ³⁺ at a ratio of 1% to 90%. Compounds having a low melting point are preferred because of the low sintering temperatures at which the core remains stable.

In order to ensure even better spatial separation between Ce ³⁺ or Eu ²⁺ and Eu ³⁺ ions, a particular embodiment of the invention is an embodiment in which the core is surrounded by two concentrically configured outer casings. Preferably, the inner casing contains neither Ce ³⁺ nor Eu ³⁺ luminophores or compounds. Since both shells contain a high concentration of Tb ³⁺ , energy can be transferred from the core via the interlayer to the Eu ^{3 + -doped} outer layer via Tb ³⁺ . If there are additional extra casings, the same construction will be changed as necessary.

method

The invention further provides a method for producing a core-shell luminophore comprising the following steps or consisting of the following steps:
(a) providing a solution (shell material) comprising at least one Eu ³⁺ compound and optionally at least one Tb ³⁺ and/or Gd ³⁺ compound;
(b) providing at least one luminophore (core material) that has been doped with Ce ³⁺ and/or Eu ²⁺ and is insoluble in the solution from step (a);
(c) mixing the solution with the luminophore and the precipitating agent;
(d) precipitating the Eu ³⁺ , Tb ³⁺ and/or Gd ³⁺ compound onto the luminophore;
(e) remove the solvent; and
(f) Densification and/or thermal post-treatment of residues as appropriate.

Preferably, the components according to steps (a) and (b) - that is, the outer shell material and the inner core material - are used in a weight ratio of from about 70:30 to about 90:10 - in each case as a solid Content meter. Particularly preferred is a weight ratio of about 80:20. Suitable solvents include organic and inorganic solvent analogs; in many cases, the starting materials for the outer shell material are water soluble or soluble in the dilute mineral acid. In some cases, complete dissolution is not necessary and the starting material suspension is sufficient. In addition to the Eu ³⁺ , Tb ³⁺ and/or Gd ³⁺ compounds, the solution may also comprise additional components suitable for forming a eutectic or mixed compound, and then likewise precipitated onto the core material. Precipitation can be carried out, for example, in situ or in the form of a reverse sequence of reverse strike. Suitable precipitating agents are, in particular, urea and ammonium hydrogencarbonate. The precipitation is preferably carried out at elevated temperature with reflux of the solvent, and usually requires a reaction time of from 1 to 10 hours. The method is clarified in detail below by means of a plurality of working examples without being limited to such examples.

In a further preferred embodiment of the invention, the precipitated product is subjected to a thermal aftertreatment. This is done to ensure improved energy transfer between the core and the housing. The sintering procedure for densification or crystallization of the outer casing is preferably carried out such that the sintering temperature is lower by 100 to 500 K than the melting point of the outer casing material. This causes the interdiffusion of cations between the core and the outer shell to be locally limited, making the compound "epitaxial" and the energy transfer becomes more efficient. This situation is shown in schematic form in Figure 12 . In practice, the thermal aftertreatment is carried out at a temperature in the range of from about 500 to about 2000 ° C for a period of from about 1 to about 10 hours. If necessary, in order to improve crystallization, the flux is also added in an amount of 0.1% by weight to 5% by weight.

The invention further provides an alternative method for producing a composite luminophore comprising the following steps or consisting of the following steps:
(a) providing a first luminophore doped with Ce ³⁺ and/or Eu ²⁺ ;
(b) providing a second luminophore, the second luminophore being a compound containing (b1) Eu ³⁺ and (b2) Tb ³⁺ and/or Gd ³⁺ ;
(c) mixing the first luminophore with the second luminophore in a weight ratio of about 30:70 to 10:90;
(d) pressing the mixture to obtain a green body;
(e) sintering the green body at a temperature lower than the melting temperature of the first luminophore by 100 to 500 K.

This method produces a ceramic material in which Ce ³⁺ is spatially separated from Eu ³⁺ , but energy transfer from Ce ³⁺ to Eu ³⁺ can be performed due to the "epitaxial" nature of the interface present therein. This procedure is an option when the coating process cannot be performed due to technical or physical properties of the core or housing material for technical reasons. This situation is shown in schematic form in Figure 12 . In practice, the sintering of the green body is carried out at a temperature in the range of from about 500 to about 2000 ° C for a period of from about 1 to about 10 hours. The resulting composite comprising the outer shell material in a large surplus has similar behavior to the core-shell luminophore from the first method, and thus is also considered to be encompassed by the term "multi-component luminophore" in the context of the context of the present invention. .
Industrial applicability

The invention further relates to the use of the compounds of the invention as light-emitting groups or converted luminophores, in particular as radiation converters for blue-emitting or UV-A radiation semiconductor sources, and for reasons of such Compounds are therefore also generally referred to as luminophores.

Launch conversion material

The invention further relates to an emission conversion material comprising a compound of the invention. The emissive conversion material may consist of a compound of the invention and in this case will be equivalent to the term "converting luminophore" as defined above. It is also preferred that the emissive conversion material of the present invention comprises an additional converted luminophore and a compound of the invention. In this case, the emissive conversion material of the present invention preferably comprises a mixture of at least two converted luminophores, at least one of which is a compound of the invention. It is especially preferred that the at least two converted luminophores are luminophores that emit light having complementary wavelengths.

In the context of the present application, ultraviolet light refers to the light with a maximum emission between 100 and 399 nm, and violet light refers to the light with a maximum emission between 400 and 430 nm. The maximum value is between 431 and 480 nm, the cyan is the emission with a maximum between 481 and 510 nm, and the green is the emission with a maximum between 511 and 565 nm. Light, yellow light refers to the light with a maximum emission between 566 and 575 nm, orange light refers to the light with a maximum emission between 576 and 600 nm, and red light refers to the maximum emission value. The light between 601 and 750 nm.

When the compound of the present invention is used in a small amount, it has produced good LED quality. LED quality is described by conventional parameters such as color rendering index (CRI), correlated color temperature (CCT), lumen equivalent or absolute lumen, or color trajectories in CIE x and y coordinates.

The color rendering index (CRI) is a unitless illumination technical parameter familiar to those skilled in the art that compares the color reproduction authenticity of an artificial light source with the color reproduction authenticity of daylight or filament sources (the latter two have a CRI of 100).

Correlated color temperature (CCT) is a lighting technical parameter familiar to those skilled in the art, and the unit is kelvin. The higher the value, the higher the blue component of the light and the white light from the synthetic radiation source appears colder to the observer. The CCT follows the concept of a black radiator whose color temperature is described by the so-called Planck curve in the CIE diagram.

Lumens equivalents are lighting technical parameters familiar to those skilled in the art, in lm/W, which describe the amount of luminosity flux in the lumen from the source at a specific radiation radiant power in watts. The higher the lumen equivalent, the more efficient the source.

Lumens is a photometric illumination parameter familiar to those skilled in the art that describes the flux of light from a source that is a measure of the total visible radiation emitted by the source. The greater the luminous flux, the brighter the light source appears to the observer.

CIE x and CIE y are coordinates in the CIE standard color map (here 1931 standard observer) familiar to those skilled in the art, which describe the color of the light source.

All of the parameters listed above can be calculated from the emission spectrum of the source by methods known to those skilled in the art.

The excitability of the luminophore of the present invention extends over a wide range extending from about 250 to about 550 nm, preferably from about 300 to about 400 nm. Typically, the maximum excitation curve is between 325 and 375 nm.

light source

The invention further provides a light source comprising at least one primary light source and at least one compound of the invention. Here, the emission maximum of the primary source is typically in the range of from about 250 to about 550 nm, preferably in the range of from about 300 to about 400 nm. A particularly preferred range is between 325 and 375 nm, wherein the primary radiation is partially or completely converted to longer wavelength radiation by the luminophore of the invention.

In a preferred embodiment of the light source of the present invention, the primary light source is an indium aluminum gallium nitride, in particular an indium aluminum gallium nitride of the formula In _i Ga _j Al _k N, wherein 0 ≤ i, 0 ≤ j, 0 ≤ k, and i + j + k = 1.

Those skilled in the art are aware of the possible forms of such light sources. These forms can be luminescent LED wafers of different configurations.

In a further preferred embodiment of the light source of the invention, the primary source is a luminescent arrangement based on ZnO, TCO (transparent conductive oxide), ZnSe or SiC, or a configuration based on an organic light-emitting layer (OLED or PLED).

In a further preferred embodiment of the light source of the invention, the primary source is a source exhibiting electroluminescence and/or photoluminescence. In addition, the primary light source can also be a plasma source or a discharge source.

The corresponding light source of the present invention is also referred to as a light emitting diode or LED.

Luminous mixture

The luminophores of the present invention can be used individually or as a mixture with suitable luminophores that are familiar to those skilled in the art. The corresponding luminophores which are suitable in principle for the mixture are, for example:

Ba ₂ SiO ₄ :Eu ²⁺ , Ba ₃ SiO ₅ :Eu ²⁺ , (Ba,Ca) ₃ SiO ₅ :Eu ²⁺ , BaSi ₂ N ₂ O ₂ :Eu,BaSi ₂ O ₅ :Pb ²⁺ ,Ba ₃ Si ₆ O ₁₂ N ₂ :Eu, Ba _x Sr _1-x F ₂ :Eu ²⁺ (where 0 ≤ x ≤ 1), BaSrMgSi ₂ O ₇ :Eu ²⁺ , BaTiP ₂ O ₇ , (Ba, Ti) ₂ P ₂ O ₇ : Ti, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ SiO ₄ : Mn ²⁺ , Bi ₄ Ge ₃ O ₁₂ , CaAl ₂ O ₄ : Ce ³⁺ , CaLa ₄ O ₇ : Ce ³⁺ , CaAl ₂ O ₄ :Eu ²⁺ , CaAl ₂ O ₄ :Mn ²⁺ , CaAl ₄ O ₇ :Pb ²⁺ , Mn ²⁺ , CaAl ₂ O ₄ :Tb ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ :Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ :Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ :Eu ²⁺ , Ca ₂ B ₅ O ₉ Br:Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl:Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl:Pb ²⁺ , CaB ₂ O ₄ :Mn ²⁺ , Ca ₂ B ₂ O ₅ :Mn ²⁺ , CaB ₂ O ₄ :Pb ²⁺ ,CaB ₂ P ₂ O ₉ :Eu ²⁺ , Ca ₅ B ₂ SiO ₁₀ :Eu ³⁺ , Ca _0.5 Ba _0.5 Al ₁₂ O ₁₉ :Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (PO ₄ ) ₃ Cl:Eu ^{2 +,} SiO ₂ in CaBr _2: Eu ^2+, SiO ₂ in CaCl _2: Eu ^2+, SiO ₂ in ^{_{CaCl 2: Eu 2+, Mn 2+}} , CaF 2: Ce 3+, CaF 2: Ce 3+, Mn ²⁺ , CaF ₂ :Ce ³⁺ , Tb ³⁺ , CaF ₂ :Eu ²⁺ , CaF ₂ :Mn ²⁺ , CaGa ₂ O ₄ :Mn ²⁺ , CaGa ₄ O ₇ : Mn ²⁺ , CaGa ₂ S ₄ :Ce ³⁺ , CaGa ₂ S ₄ :Eu ²⁺ , CaGa ₂ S ₄ :Mn ²⁺ , CaGa ₂ S ₄ :Pb ²⁺ , CaGeO ₃ :Mn ²⁺ , SiO ₂ CaI ₂ :Eu ²⁺ , SiO ₂ CaI ₂ :Eu ²⁺ , Mn ²⁺ , CaLaBO ₄ :Eu ³⁺ , CaLaB ₃ O ₇ :Ce ³⁺ , Mn ²⁺ , Ca ₂ La ₂ BO ₆ . ₅ : Pb ²⁺ , Ca ₂ MgSi ₂ O ₇ , Ca ₂ MgSi ₂ O ₇ :Ce ³⁺ , CaMgSi ₂ O ₆ :Eu ²⁺ , Ca ₃ MgSi ₂ O ₈ :Eu ²⁺ , Ca ₂ MgSi ₂ O ₇ :Eu ²⁺ , CaMgSi ₂ O ₆ :Eu ²⁺ ,Mn ²⁺ , Ca ₂ MgSi ₂ O ₇ :Eu ²⁺ ,Mn ²⁺ ,CaMoO ₄ ,CaMoO ₄ :Eu ³⁺ ,CaO:Bi ³⁺ ,CaO : Cd ²⁺ , CaO : Cu ⁺ , CaO : Eu ³⁺ , CaO : Eu ³⁺ , Na ⁺ , CaO : Mn ²⁺ , CaO : Pb ²⁺ , CaO : Sb ³⁺ , CaO : Sm ³⁺ , CaO : Tb ³⁺ , CaO: Tl, CaO: Zn ²⁺ , Ca ₂ P ₂ O ₇ : Ce ³⁺ , α-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , β-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ :Eu ²⁺ , Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F:Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F:Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ F:S ²⁺ , α-Ca ₃ (PO ₄ ) ₂ :Eu ²⁺ , β-Ca ₃ (PO ₄ ) ₂ :Eu ²⁺ , Ca ₂ P ₂ O ₇ :Eu ^{2 +} , Ca ₂ P ₂ O ₇ :Eu ²⁺ , Mn ²⁺ , CaP ₂ O ₆ :Mn ²⁺ , α-Ca ₃ (PO ₄ ) ₂ :Pb ²⁺ , α-Ca ₃ (PO ₄ ) ₂ :Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ :S ²⁺ , β-Ca ₂ P ₂ O ₇ :Sn, Mn, α-Ca ₃ (PO ₄ ) ₂ :Tr, CaS:Bi ³⁺ , CaS:Bi ³⁺ , Na, CaS: Ce ³⁺ , CaS: Eu ²⁺ , CaS: Cu ⁺ , Na ⁺ , CaS: La ³⁺ , CaS: Mn ²⁺ , CaSO ₄ : Bi, CaSO ₄ : Ce ³⁺ , CaSO ₄ : Ce ³⁺ , Mn ²⁺ , CaSO ₄ :Eu ²⁺ , CaSO ₄ :Eu ²⁺ , Mn ²⁺ , CaSO ₄ :Pb ²⁺ , CaS:Pb ²⁺ , CaS:Pb ²⁺ , Cl, CaS:Pb ²⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , Cl, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ , CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , Cl, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ²⁺ , Cl, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg ₂ Si ₃ O ₁₂ :Ce, CaSiO ₃ :Ce ³⁺ , Ca ₃ SiO ₄ Cl ₂ :Eu ²⁺ , Ca ₃ SiO ₄ Cl ₂ :Pb ²⁺ , CaSiO ₃ :Eu ²⁺ , Ca ₃ SiO ₅ : Eu ²⁺ , (Ca,Sr) ₃ SiO ₅ :Eu ²⁺ , (Ca,Sr) ₃ MgSi ₂ O ₈ :Eu ²⁺ , (Ca,Sr) ₃ MgSi ₂ O ₈ :Eu ²⁺ ,Mn ²⁺ , CaSiO ₃ : Mn ²⁺ , Pb, CaSiO ₃ : Pb ²⁺ , CaSiO ₃ : Pb ²⁺ , Mn ²⁺ , CaSiO ₃ : Ti ⁴⁺ , CaSr ₂ (PO ₄ ) ₂ : Bi ³⁺ , β-( Ca,Sr) ₃ (PO ₄ ) ₂ :S ²⁺ Mn ²⁺ , Ca Ti ₀ . ₉ Al ₀ . ₁ O ₃ :Bi ³⁺ , CaTiO ₃ :Eu ³⁺ , CaTiO ₃ :Pr ³⁺ , Ca ₅ (VO ₄ ) ₃ Cl, CaWO ₄ , CaWO ₄ :Pb ²⁺ , CaWO ₄ :W, Ca ₃ WO ₆ :U, CaYAlO ₄ :Eu ³⁺ , CaYBO ₄ :Bi ³⁺ , CaYBO ₄ :Eu ³⁺ , CaYB ₀ . ₈ O ₃ . ₇ :Eu ³⁺ , CaY ₂ ZrO ₆ :Eu ³⁺ , (Ca, Zn, Mg) ₃ (PO ₄ ) ₂ : Sn, (Ce, Mg) BaAl ₁₁ O ₁₈ : Ce, (Ce, Mg) SrAl ₁₁ O ₁₈ : Ce, CeMgAl ₁₁ O ₁₉ : Ce: Tb, Cd ₂ B ₆ O ₁₁ : Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: In, CdS: In, CdS: In, Te, CdS: Te, CdWO ₄ , CsF, Csl, CsI: Na ⁺ , _{CsI: Tl, (ErCl 3)} 0.25 (BaCl 2) 0 75, GaN:. Zn, Gd 3 Ga 5 O 12: Cr 3+, Gd 3 Ga 5 O 12: Cr, Ce, GdNbO 4: Bi 3+, Gd ₂ O ₂ S: Eu ³⁺ , Gd ₂ O ₂ Pr ³⁺ , Gd ₂ O ₂ S: Pr, Ce, F, Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAI ₁₁ O ₁₇ :Tl ⁺ , KGa ₁₁ O ₁₇ :Mn ²⁺ , K ₂ La ₂ Ti ₃ O ₁₀ :Eu, KMgF ₃ :Eu ²⁺ , KMgF ₃ :Mn ²⁺ , K ₂ SiF ₆ :Mn ⁴⁺ , LaAl ₃ B ₄ O ₁₂ :Eu ³⁺ , LaAlB ₂ O ₆ :Eu ³⁺ , LaAlO ₃ :Eu ³⁺ , LaAlO ₃ :Sm ³⁺ ,LaAsO ₄ :Eu ³⁺ ,LaBr ₃ :Ce ³⁺ ,LaBO ₃ :Eu ³⁺ , LaCl ₃ :Ce ³⁺ , La ₂ O ₃ :Bi ³⁺ , LaOBr:Tb ³⁺ ,LaOBr: ^{Tm 3+, LaOCl: Bi 3+,} LaOCl: Eu 3+, LaOF: Eu 3+, La 2 O 3: Eu 3+, La 2 O 3: Pr 3+, La 2 O 2 S: Tb 3+, LaPO ₄ :Ce ³⁺ , LaPO ₄ :Eu ³⁺ , LaSiO ₃ Cl:Ce ³⁺ , LaSiO ₃ Cl:Ce ³⁺ , Tb ³⁺ , LaVO ₄ :Eu ³⁺ , La ₂ W ₃ O ₁₂ :Eu ^{3 +} , LiAlF ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAlO ₂ : Fe ³⁺ , LiAlO ₂ : Mn ²⁺ , LiAl ₅ O ₈ : Mn ²⁺ , Li ₂ CaP ₂ O ₇ : Ce ^{3 +} , Mn ²⁺ , LiCeBa ₄ Si ₄ O ₁₄ : Mn ²⁺ , LiCeSrBa ₃ Si ₄ O ₁₄ : Mn ²⁺ , LiInO ₂ : Eu ³⁺ , LiInO ₂ : Sm ³⁺ , LiLaO ₂ : Eu ³⁺ , LuAlO ₃ : Ce ³⁺ , (Lu, Gd) ₂ SiO ₅ : Ce ³⁺ , Lu ₂ SiO ₅ : Ce ³⁺ , Lu ₂ Si ₂ O ₇ : Ce ³⁺ , LuTaO ₄ : Nb ⁵⁺ , Lu _{1- x} Y _x AlO ₃ :Ce ³⁺ (where 0 ≤ x ≤ 1), (Lu, Y) ₃ (Al, Ga, Sc) ₅ O ₁₂ :Ce, MgAl ₂ O ₄ :Mn ²⁺ , MgSrAl ₁₀ O ₁₇ : Ce, MgB ₂ O ₄ : Mn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : Sn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : U, MgBaP ₂ O ₇ : Eu ²⁺ , MgBaP ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , MgBa ₃ Si ₂ O ₈ :Eu ²⁺ , MgBa(SO ₄ ) ₂ :Eu ²⁺ , Mg ₃ Ca ₃ (PO ₄ ) ₄ :Eu ²⁺ , MgCaP ₂ O ₇ :Mn ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ :Eu ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ :Eu ²⁺ ,Mn ² ,MgCeAl _n O ₁₉ : Tb ³⁺ , Mg ₄ (F) GeO ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) O ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ O ₄ : Mn ²⁺ , Mg ₈ Ge ₂ O ₁₁ F ₂ :Mn ⁴⁺ , MgS:Eu ²⁺ , MgSiO ₃ :Mn ²⁺ , Mg ₂ SiO ₄ :Mn ²⁺ , Mg ₃ SiO ₃ F ₄ :Ti ⁴⁺ , MgSO ₄ :Eu ²⁺ , MgSO ₄ :Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ :Eu ²⁺ , MgSrP ₂ O ₇ :Eu ²⁺ , MgSr ₅ (PO ₄ ) ₄ :Sn ²⁺ , MgSr ₃ Si ₂ O ₈ :Eu ²⁺ , Mn ²⁺ , Mg ₂ Sr(SO ₄ ) ₃ :Eu ²⁺ , Mg ₂ TiO ₄ :Mn ⁴⁺ , MgWO ₄ , MgYBO ₄ :Eu ³⁺ , M ₂ MgSi ₂ O ₇ :Eu ²⁺ ( M = Ca, Sr and/or Ba), M ₂ MgSi ₂ O ₇ :Eu ²⁺ , Mn ²⁺ (M = Ca, Sr and/or Ba), M ₂ MgSi ₂ O ₇ :Eu ²⁺ , Zr ^{4 +} (M = Ca, Sr and/or Ba), M ₂ MgSi ₂ O ₇ :Eu ²⁺ , Mn ²⁺ , Zr ⁴⁺ (M = Ca, Sr and/or Ba), Na ₃ Ce(PO ₄ ) ₂ : Tb ³⁺ , Na ₁ . ₂₃ K _O . ₄₂ Eu ₀ . ₁₂ TiSi ₄ O ₁₁ :Eu ³⁺ , Na _1.23 K _0.42 Eu _0.12 TiSi ₅ O ₁₃ *xH ₂ O:Eu ³⁺ , Na _1.29 K _0.46 Er _0.08 TiSi ₄ O ₁₁ :Eu ³⁺ , Na ₂ Mg ₃ Al ₂ Si ₂ O ₁₀ :Tb, Na(Mg _2-x Mn _x )LiSi ₄ O ₁₀ F ₂ :Mn (where 0 ≤ x ≤ 2), NaYF ₄ : Er ³⁺ , Yb ³⁺ , NaYO ₂ :Eu ³⁺ , P46 (70%)+P47 (30%), β-SiAlON:Eu, SrAl ₁₂ O ₁₉ :C e ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ :Eu ²⁺ , SrAl ₄ O ₇ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Eu ²⁺ , SrAl ₂ S ₄ :Eu ²⁺ ,Sr ₂ B ₅ O ₉ Cl:Eu ²⁺ , SrB ₄ O ₇ :Eu ²⁺ (F,Cl,Br), SrB ₄ O ₇ :Pb ²⁺ , SrB ₄ O ₇ :Pb ²⁺ ,Mn ²⁺ ,SrB ₈ O ₁₃ :Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O _4-z/2 : Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ :Eu ²⁺ , (Sr,Ba) ₃ SiO ₅ :Eu,(Sr,Ca)Si ₂ N ₂ O ₂ :Eu, SiO ₂ Sr(Cl,Br,I) ₂ :Eu ²⁺ , SiO ₂ SrCl ₂ :Eu ²⁺ , Sr ₅ Cl(PO ₄ ) ₃ :Eu,Sr _w F _x B ₄ O _6.5 :Eu ²⁺ , Sr _w F _x B _y O _z :Eu ²⁺ ,Sm ²⁺ ,SrF ₂ :Eu ²⁺ , SrGa ₁₂ O ₁₉ :Mn ²⁺ , SrGa ₂ S ₄ :Ce ³⁺ , SrGa ₂ S ₄ :Eu ²⁺ , Sr _2-y Ba _y SiO ₄ :Eu (where 0 ≤ y ≤ 2), SrSi ₂ O ₂ N ₂ :Eu, SrGa ₂ S ₄ :Pb ²⁺ , SrIn ₂ O ₄ : Pr ³⁺ , Al ³⁺ , (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn, SrMgSi ₂ O ₆ :Eu ²⁺ , Sr ₂ MgSi ₂ O ₇ :Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ :Eu ²⁺ , SrMoO ₄ :U, SrO·3B ₂ O ₃ :Eu ²⁺ ,Cl,β-SrO·3B ₂ O ₃ :Pb ²⁺ ,β-SrO·3B ₂ O ₃ :Pb ²⁺ ,Mn ²⁺ , α-SrO·3B ₂ O ₃ :Sm ²⁺ , Sr ₆ P ₅ BO ₂₀ :Eu,Sr ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , Pr ³⁺ , Sr ₅ (PO ₄ ) ₃ Cl:Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl:Sb ³⁺ , Sr ₂ P ₂ O ₇ :Eu ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :Eu ²⁺ , Sr ₅ ( PO ₄ ) ₃ F: Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Sr ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F: Sn ²⁺ , Sr ₂ P ₂ O ₇ :S ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :S ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :S ²⁺ , Mn ²⁺ (Al), SrS :Ce ³⁺ , SrS:Eu ²⁺ , SrS:Mn ²⁺ , SrS:Cu ⁺ ,Na,SrSO ₄ :Bi, SrSO ₄ :Ce ³⁺ , SrSO ₄ :Eu ²⁺ ,SrSO ₄ :Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ O ₁₀ Cl ₆ :Eu ²⁺ , Sr ₂ SiO ₄ :Eu ²⁺ , Sr ₃ SiO ₅ :Eu ²⁺ , (Sr,Ba) ₃ SiO ₅ :Eu ²⁺ ,SrTiO ₃ : Pr ³⁺ , SrTiO ₃ :Pr ³⁺ , Al ³⁺ , SrY ₂ O ₃ :Eu ³⁺ , ThO ₂ :Eu ³⁺ , ThO ₂ :Pr ³⁺ , ThO ₂ :Tb ³⁺ , YAl ₃ B ₄ O ₁₂ :Bi ³⁺ , YAl ₃ B ₄ O ₁₂ :Ce ³⁺ , YAl ₃ B ₄ O ₁₂ :Ce ³⁺ , Mn, YAl ₃ B ₄ O ₁₂ :Ce ³⁺ , Tb ³⁺ , YAl ₃ B ₄ O ₁₂ :Eu ³⁺ , YAl ₃ B ₄ O ₁₂ :Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ O ₁₂ :Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAlO ₃ :Ce ³⁺ , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₃ Al ₅ O ₁₂ :Cr ³⁺ , YAlO ₃ :Eu ³⁺ , Y ₃ Al ₅ O ₁₂ :Eu ^3r , Y ₄ Al ₂ O ₉ :Eu ³⁺ , Y _{3 ^{al 5 O 12: Mn 4+,}} YAlO 3: Sm 3+ ^{_{YAlO 3: Tb 3+, Y 3}} Al 5 O 12: Tb 3+, YAsO 4: Eu 3+, YBO 3: Ce 3+, YBO 3: Eu 3+, YF 3: Er 3+, Yb 3+, YF ₃ : Mn ²⁺ , YF ₃ : Mn ²⁺ , Th ⁴⁺ , YF ₃ : Tm ³⁺ , Yb ³⁺ , (Y, Gd) BO ₃ : Eu, (Y, Gd) BO ₃ : Tb, ( Y,Gd) ₂ O ₃ :Eu ³⁺ , Y _1.34 Gd _0.60 O ₃ (Eu,Pr), Y ₂ O ₃ :Bi ³⁺ , YOBr:Eu ³⁺ , Y ₂ O ₃ :Ce, Y ₂ O ₃ :Er ³⁺ , Y ₂ O ₃ :Eu ³⁺ , Y ₂ O ₃ :Ce ³⁺ , Tb ³⁺ , YOCl:Ce ³⁺ , YOCl:Eu ³⁺ ,YOF:Eu ³⁺ ,YOF:Tb ³⁺ Y ₂ O ₃ : Ho ³⁺ , Y ₂ O ₂ S: Eu ³⁺ , Y ₂ O ₂ S: Pr ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ O ₃ : Tb ³⁺ , YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO ₄ : Mn ²⁺ , Th ⁴⁺ , YPO ₄ : V ⁵⁺ , Y (P, V) O ₄ :Eu, Y ₂ SiO ₅ :Ce ³⁺ , YTaO ₄ , YTaO ₄ :Nb ⁵⁺ , YVO ₄ :Dy ³⁺ , YVO ₄ :Eu ³⁺ , ZnAl ₂ O ₄ :Mn ²⁺ , ZnB ₂ O ₄ : Mn ²⁺ , ZnBa ₂ S ₃ : Mn ²⁺ , (Zn, Be) ₂ SiO ₄ : Mn ²⁺ , Zn _0.4 Cd _0.6 S: Ag, Zn _0.6 Cd _0.4 S: Ag, (Zn, Cd) S: Ag , Cl, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ O ₄ , ZnGa ₂ O ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ GeO ₄ : Mn ²⁺ _{, (Zn, Mg) F 2} : Mn 2+, ZnMg 2 (PO 4) 2: Mn 2+ _{(Zn, Mg) 3 (PO} 4) 2: Mn 2+, ZnO: Al 3+, Ga 3+, ZnO: Bi 3+, ZnO: Ga 3+, ZnO: Ga, ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag ⁺ , Cl ^- , ZnS: Ag, Cu, Cl, ZnS: Ag, Ni, ZnS: Au, In, ZnS-CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25), ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , Cl, ZnS-CdS: Cu, Br, ZnS-CdS: Cu, I, ZnS:Cl ^- , ZnS:Eu ²⁺ , ZnS:Cu, ZnS:Cu ⁺ ,Al ³⁺ ,ZnS:Cu ⁺ ,Cl ^- ,ZnS:Cu,Sn,ZnS:Eu ²⁺ ,ZnS:Mn ²⁺ , ZnS: Mn, Cu, ZnS: Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ^3- , Cl ^- , ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , Cl ^- , ZnS: Pb, Cu, Zn ₃ (PO ₄ ) ₂ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , As ⁵⁺ , Zn ₂ SiO ₄ : Mn, Sb ₂ O ₂ , Zn ₂ SiO ₄ : Mn ²⁺ , P, Zn ₂ SiO ₄ : Ti ⁴⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS-ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , Cl and ZnWO ₄ .

The compounds of the invention in particular exhibit advantages when mixed with other luminophores of other fluorescent colors or when used in LEDs with such luminophores. It is preferred to use the compound of the invention together with a green-emitting luminophore. It has been found that, especially when the compounds of the invention are combined with a green-emitting luminophore, it is particularly successful to optimize the illumination parameters of white LEDs.

The corresponding green light illuminating group is known to those skilled in the art, or may be selected from the above list by those skilled in the art. Here, a particularly suitable green-emitting luminophore is (Sr, Ba) ₂ SiO ₄ :Eu, (Sr,Ba) ₃ SiO ₅ :Eu, (Sr,Ca)Si ₂ N ₂ O ₂ :Eu, BaSi ₂ N ₂ O ₂ :Eu, (Lu,Y) ₃ (Al,Ga,Sc) ₅ O ₁₂ :Ce, β-SiAlON:Eu, CaSc ₂ O ₄ :Ce, CaSc ₂ O ₄ :Ce,Mg,Ba ₃ Si ₆ O ₁₂ N ₂ :Eu and Ca ₃ (Sc,Mg) ₂ Si ₃ O ₁₂ :Ce. Particularly preferred are Ba ₃ Si ₆ O ₁₂ N ₂ :Eu and Ca ₃ (Sc,Mg) ₂ Si ₃ O ₁₂ :Ce.
In a further preferred embodiment of the invention, it is preferred to use the compounds of the invention as the sole luminophore. Due to the broad emission spectrum with a high red component, the compounds of the invention exhibit excellent results even when used as a single luminophore.

In still another embodiment of the present invention, it is preferred to dispose the luminophore on the primary light source such that the red-emitting luminophore is substantially irradiated by light from the primary light source, and the green-emitting luminophore is substantially Irradiation by a red-emitting luminophore or light that has been scattered therefrom. This can be achieved in that the red-emitting luminophore is assembled between the primary source and the green-emitting luminophore.

The luminophore or luminophore combination of the present invention may be in the form of a bulk material, a powder material, a thick or flake material or a self-supporting material, preferably in the form of a film. In addition, it can also be embedded in the infusion material. Depending on the application, the luminophore or luminophore combination of the present invention may be dispersed in a resin (for example, epoxy resin or polyoxynoxy resin) as a potting material, or may be directly disposed on top of the primary light source or in view of a suitable size ratio or Configured to be at a distance from it (the latter configuration also includes "remote phosphor technology"). Advantage for the distal end of the phosphor technologies known to those skilled in the art, and may be found, for example in the following publications:. JAPANESE J. OF APPL PHYS, vol. 44, No. 21 (2005), L649 to L651..

In a further embodiment, it is preferred to achieve optical coupling between the luminophore and the primary source by means of a light guiding arrangement. It is therefore possible to mount the primary light source at the central location and optically couple the primary light source to the luminophore by means of a light guiding device, such as an optical fiber. In this way, it is possible to achieve an illumination device that has been adapted to the lighting needs and consists of only one or more different luminophores that can be configured to form a light-emitting screen and an optical fiber coupled to the primary source. In this way, it is possible to position the strong primary light source at a location that is beneficial to the electrical installation, and without the need for additional cable laying, but by simply positioning the optical fiber, it is possible to install the illuminating device consisting of the luminophore coupled to the optical fiber to any desired At the site.

Lighting unit

The invention further provides a lighting unit, in particular a primary light source having an emission maximum in the range of 340 to 510 nm.

The particle size of the luminophore of the present invention for use in LEDs is typically between 50 nm and 30 μm, preferably between 1 μm and 20 μm.

For use in LEDs, the luminophores can also be converted to any desired external form, such as spherical particles, thin layers, cubes, diamonds, and structured materials and ceramics. According to the invention, these forms are covered by the term "shaped body". Preferably, the shaped body is a "light-emitting body". Accordingly, the present invention further provides a shaped body comprising the luminophore of the present invention. The production and use of the corresponding shaped body is known from a large number of publications by those skilled in the art.

All variants of the invention described herein can be combined with each other unless the respective embodiments are mutually exclusive. More specifically, in light of the teachings of this document, the obvious processes in the conventional optimization process combine different variants described herein, especially in order to achieve particular particularly preferred embodiments. The following examples are intended to illustrate the invention, and in particular to show the results of such illustrative combinations of the variants of the invention described. However, it should never be considered limiting; instead, it should promote generalization. All of the compounds or components used in the preparation are known or commercially available or can be synthesized by known methods. The temperatures reported in the examples are always in °C. It will also be self-evident that in both embodiments and examples, the amount of ingredients used in the composition will always total 100% in total. The percentage should always be seen within the context of a given content.

The excitation spectra in Figure 13 have each been normalized to the 485 nm Tb ³⁺ line and have been recorded as the 610.5 nm emission of Eu ³⁺ observed. The core-shell particle (--) exhibits a much higher Ce ³⁺ band intensity at 410 nm compared to the conventionally produced particle (-). Since metal-metal charge transfer (MMCT) quenches Ce ³⁺ luminescence, the relative increase in the Ce ³⁺ excitation band can be attributed to a significant reduction in MMCT. Furthermore, the appearance of the Ce ³⁺ excitation band indicates the energy transfer from Ce ³⁺ to Eu ³⁺ . The core/shell particles thus exhibit reduced MMCT compared to conventionally generated particles that retain Ce ³⁺ /Eu ³⁺ energy transfer.

The emission spectrum in Figure 14 shows a significantly higher emission intensity of the core-shell particles (--) compared to the conventionally produced particles (-). It is therefore possible to show the higher efficiency of the core-shell particles. In addition, the emission spectrum shows that Eu ³⁺ emission can be observed at 610 nm under 410 nm excitation. Thus, a Ce ³⁺ /Eu ³⁺ energy transfer occurs, where Tb ³⁺ acts as a bridge.

Figures 15 and 16 compare typical Tb ₃ Al ₅ O ₁₂ :Ce particles prior to coating ( Figure 15 ) and after coating ( Figure 16 ). It is clear that the particles are surrounded by a coating (outer casing).

The invention is illustrated below by working examples, but the working examples should in no way be considered as limiting. A person skilled in the art will recognize that various modifications, additions and changes can be made to the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Instance

Test Methods

The Rigaku Miniflex II operating with the Bregg-Brentano geometry records the x-ray diffraction pattern in 0.02° steps with an integration time of 1 s. The reflectance spectra were recorded on a Teflon coated Spectralon sphere using an Edinburgh Instruments FL 920 spectrometer. The light source used was a 450 W Xe discharge lamp. Samples were measured against the BaSO ₄ standard. Excitation and emission spectra were recorded on an Edinburgh Instruments FLS 920 spectrometer. The excitation source used was a 450 W Xe lamp. The excitation is corrected by means of a reference detector; the emission is corrected by means of a correction spectrum. The calibration spectrum was obtained by measuring a halogen lamp certified by the National Physical Laboratory (UK). The decay curves were recorded on an Edinburgh Instruments FLS 920 spectrometer. The excitation source used was a Xe microsecond scintillation lamp or an Edinburgh Instruments laser diode. SEM imaging was performed on a Zeiss EVO MA 10.

Instance 1
(Tb _0.97 Eu _0.03 ) ₃ Al ₅ O ₁₂ @ Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ It preparation

The synthesis was carried out in the form of in situ precipitation of urea as a precipitant. 0.0355 g (1.009 mmol) of Eu ₂ O ₃ and 1.2195 g (1.6311 mmol) of Tb ₄ O _{7 were} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. 16.1585 g (269.04 mmol) of urea and 4.2053 g (11.21 mmol) of Al(NO ₃ ) ₃ *9H ₂ O were dissolved in 200 ml of deionized water and added to the above solution. Subsequently, 2 g of the core material (Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ ) was dispersed in the overall solution. The bulk solution was then heated to 90 ° C under reflux and stirred for 6 h. The precipitated product was filtered through 415 filter paper, washed three times with about 30 ml of deionized water, and dried at 150 ° C for 3 h in a dry box. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated in air at 1600 ° C for 4 h. Figure 1 shows an x-ray diffraction pattern of the product obtained. FIG 4, FIG 5 and FIG. 6 shows the respective excitation, emission and reflection spectra. Figure 7 shows the corresponding decay curve. Figure 9 shows a scanning electron microscope image.

Instance 2
(Tb _0.94 Ce _0.03 Eu _0.03 ) ₃ Al ₅ O ₁₂ @ Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ Preparation

The synthesis was carried out in the form of in situ precipitation of urea as a precipitant. 0.0356 g (1.011 mmol) of Eu ₂ O ₃ and 1.1845 g (1.5841 mmol) of Tb ₄ O _{7 were} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. Dissolve 16.1964 g (269.64 mmol) of urea, 4.2053 g (11.21 mmol) of Al(NO ₃ ) ₃ *9H ₂ O and 0.0878 g (0.2022 mmol) of Ce(NO ₃ ) ₃ *6H ₂ O in 200 ml Deionized water and added to the above solution. Subsequently, 2 g of the core material (Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ ) was dispersed in the overall solution. The bulk solution was then heated to 90 ° C under reflux and stirred for 6 h. The precipitated product was filtered through 415 filter paper, washed three times with about 30 ml of deionized water, and dried at 150 ° C for 3 h in a dry box. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated in air at 1600 ° C for 4 h. Figure 2 shows an x-ray diffraction pattern of the product obtained. FIG 4, FIG 5 and FIG. 6 shows the respective excitation, emission and reflection spectra. Figure 7 shows the corresponding decay curve.

Instance 3
Tb ₃ Al ₅ O ₁₂ @ Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ Preparation

The synthesis was carried out by the coprecipitation of the ammonium bicarbonate as a precipitant in the form of a precipitate. 3.4891 g (4.6665 mmol) of Tb ₄ O _{7 was} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. 11.6704 g (31.11 mmol) of Al(NO ₃ ) ₃ *9H ₂ O was dissolved in 50 ml of deionized water and added to the above solution. As a precipitation solution, 15.7840 g (199.1040 mmol) of NH ₄ HCO _{3 was} dissolved in 200 ml of deionized water and the solution was adjusted to pH 8 to 9 with about 15 ml of ammonia. Subsequently, 5 g of the core material (Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ ) was dispersed in the precipitation solution. The nitrate solution was then added dropwise to the precipitation solution using a dropping funnel over a period of about 30 minutes. The precipitation solution was maintained at pH 8 to 9 by means of ammonia during the addition. The precipitated product was filtered through 415 filter paper, washed three times with about 30 ml of deionized water, and dried at 150 ° C for 3 h in a dry box. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated in air at 1000 ° C for 4 h. Figure 3 shows an x-ray diffraction pattern of the product obtained.

Instance 4
Gd _0.99 Eu _0.01 F ₃ @ Gd _0.99 Ce _0.01 F ₃ Preparation

0.9260 g of ammonium fluoride (25 mmol) was weighed out and dissolved in a three-necked flask with 160 ml of deionized water. The water bath was heated to 86 ° C by means of a magnetic stirrer and a three-necked flask was immersed therein. During the heating phase, 1.1586 g of Gd(CH ₃ CO ₂ ) ₃ (3.4650 mmol) and 0.0152 g of Ce(NO ₃ ) ₃ *6H ₂ O (0.0350 mmol) were weighed out and dissolved in 80 ml of deionized In the water. This solution was transferred to a dropping funnel and added to the liquid phase (NH ₄ F solution) with vigorous stirring. For the other solution, 1.1586 g of Gd(CH ₃ CO ₂ ) ₃ (3.4650 mmol) and 0.0115 g of Eu(CH ₃ CO ₂ ) ₃ (0.0350 mmol) were weighed out and dissolved in 80 ml of deionized water. Add to the dropping funnel and add dropwise to the suspension. The water bath was removed and once the liquid phase had cooled, the suspension was filtered through a 2 μm filter paper. The filter cake was washed 3 times with 30 ml of deionized water each time and once with 30 ml of ethanol and dried at room temperature. The dried luminophores were weighed and carefully wetted with an agate mortar with a surplus of 40 w% NH ₄ F under acetone. Once the acetone evaporates, the powder is transferred to a porcelain crucible with a lid and transferred to a chamber furnace that has been heated to 700 °C. The sintering time was exactly 1 hour and the sample was removed directly from the chamber furnace after calcination.

Instance 5
Gd _0.985 Eu _0.015 F ₃ @ Gd _0.99 Ce _0.01 F ₃ Preparation

0.9260 g of ammonium fluoride (25 mmol) was weighed out and dissolved in a three-necked flask with 160 ml of deionized water. The water bath was heated to 86 ° C by means of a magnetic stirrer and a three-necked flask was immersed therein. During the heating phase, 1.1586 g of Gd(CH ₃ CO ₂ ) ₃ (3.4650 mmol) and 0.0152 g of Ce(NO ₃ ) ₃ *6H ₂ O (0.0350 mmol) were weighed out and dissolved in 80 ml of deionized In the water. This solution was transferred to a dropping funnel and added to the liquid phase (NH ₄ F solution) with vigorous stirring. For the other solution, 1.1526 g of Gd(CH ₃ CO ₂ ) ₃ (3.4475 mmol) and 0.0174 g of Eu(CH ₃ CO ₂ ) ₃ (0.0525 mmol) were weighed out and dissolved in 80 ml of deionized water. Add to the dropping funnel and add dropwise to the suspension. The water bath was removed and once the liquid phase had cooled, the suspension was filtered through a 2 μm filter paper. The filter cake was washed 3 times with 30 ml of deionized water each time and once with 30 ml of ethanol and dried at room temperature. The dried luminophores were weighed and carefully wetted with an agate mortar with a surplus of 40 w% NH ₄ F under acetone. Once the acetone evaporates, the powder is transferred to a porcelain crucible with a lid and transferred to a chamber furnace that has been heated to 700 °C. The sintering time was exactly 1 hour and the sample was removed directly from the chamber furnace after calcination.

Instance 6
Gd _0.985 Eu _0.015 F ₃ @ Gd _0.98 Ce _0.02 F ₃ Preparation

0.9260 g of ammonium fluoride (25 mmol) was weighed out and dissolved in a three-necked flask with 160 ml of deionized water. The water bath was heated to 86 ° C by means of a magnetic stirrer and a three-necked flask was immersed therein. During the heating phase, 1.1469 g of Gd(CH ₃ CO ₂ ) ₃ (3.4300 mmol) and 0.0304 g of Ce(NO ₃ ) ₃ *6H ₂ O (0.0700 mmol) were weighed out and dissolved in 80 ml of deionized In the water. This solution was transferred to a dropping funnel and added to the liquid phase (NH ₄ F solution) with vigorous stirring. For the other solution, 1.1528 g of Gd(CH ₃ CO ₂ ) ₃ (3.4475 mmol) and 0.0173 g of Eu(CH ₃ CO ₂ ) ₃ (0.0525 mmol) were weighed out and dissolved in 80 ml of deionized water. Add to the dropping funnel and add dropwise to the suspension. The water bath was removed and once the liquid phase had cooled, the suspension was filtered through a 2 μm filter paper. The filter cake was washed 3 times with 30 ml of deionized water each time and once with 30 ml of ethanol and dried at room temperature. The dried luminophores were weighed and carefully wetted with an agate mortar with a surplus of 40 w% NH ₄ F under acetone. Once the acetone evaporates, the powder is transferred to a porcelain crucible with a lid and transferred to a chamber furnace that has been heated to 700 °C. The sintering time was exactly 1 hour and the sample was removed directly from the chamber furnace after calcination.

Instance 7
Na(Tb _0.99 Eu _0.01 )F ₄ ( Six parties ) @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 4 mmol. 3.6951 g of NaF (88.0 mmol; Ln: F 1:22) was dissolved in 160 ml of demineralized water and the pH was adjusted to 8.2 ± 0.2. 0.5 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring, and the pH was maintained at 8.2 ± 0.2. NaOH or nitric acid is used for this purpose. The suspension was heated to 80 ° C in the next step. In the second mixture, 0.0132 of hydrazine (acetic acid) ₃ and 1.7940 g of Tb(NO ₃ ) ₃ *6H ₂ O were dissolved in 160 ml of demineralized water and transferred to a dropping funnel. Once the liquid phase has reached temperature, the solution is gradually added dropwise over a period of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was allowed to dry under a hood for about 1 hour.

Instance 8
Na(Tb _0.49 Y _0.5 Eu _0.01 )F ₄ ( cube ) @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 4 mmol. 1.078 g of NaF (24.0 mmol; Ln: F 1:6) was dissolved in 160 ml of demineralized water and the pH was adjusted to 8.5 ± 0.2. 0.5 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring, and the pH was maintained at 8.5 ± 0.2. NaOH or nitric acid is used for this purpose. The suspension was heated to 80 ° C in the next step. In the second mixture, 0.0132 of hydrazine (acetic acid) ₃ , 0.7760 g of Tb(NO ₃ ) ₃ *6H ₂ O and 0.8879 g of Tb(NO ₃ ) ₃ *6H ₂ O are dissolved in 160 ml of demineralized water. And transferred to the dropping funnel. Once the liquid phase reaches temperature, the solution is gradually added dropwise over a time interval of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was allowed to dry under a hood for about 1 hour.

Instance 9
Coated with Al ₂ O ₃ It Eu ₂ [H ₂ O] ₁₈ Mo ₈ O ₂₇ *6H ₂ O @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 0.8 mmol. 0.9887 g of (NH ₄ ) ₆ Mo ₇ O ₂₄ *4H ₂ O was dissolved in 40 ml of demineralized water. 0.1 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring. In the second mixture, 0.5863 g of hydrazine (acetic acid) _{3 was} dissolved in 30 ml of demineralized water and transferred to a dropping funnel. The solution was gradually added dropwise over a period of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was allowed to dry under a hood for about 1 hour.

Instance 10
EuPO ₄ @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 4 mmol. 0.5282 g of (NH ₄ ) ₂ HPO _{4 was} dissolved in 160 ml of demineralized water. 0.82 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring. In the second mixture, 1.3163 g of hydrazine (acetic acid) _{3 was} dissolved in 160 ml of demineralized water and transferred to a dropping funnel. The solution was gradually added dropwise over a period of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was allowed to dry under a hood for about 1 hour.

Instance 11
Tb _0.95 Eu _0.05 PO ₄ @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 4 mmol. 0.5282 g of (NH ₄ ) ₂ HPO _{4 was} dissolved in 160 ml of demineralized water. 0.82 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring. In the second mixture, 0.0658 g of hydrazine (acetic acid) ₃ and 1.7215 g of Tb(NO ₃ ) ₃ *6H ₂ O were dissolved in 160 ml of demineralized water and transferred to a dropping funnel. The solution was gradually added dropwise over a period of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was allowed to dry under a hood for about 1 hour.

Instance 12
Na ₂ EuPO ₄ WO ₄ @ (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ Preparation

This working example is calculated for a batch of 2 mmol. 0.2641 g of (NH ₄ ) ₂ HPO ₄ and 0.6597 g of Na ₂ WO ₄ *2H ₂ O were dissolved in 160 ml of demineralized water and the pH was set between 7 and 11. 0.87 g of (Ba,Sr) ₂ SiO ₄ :Eu ²⁺ (core) was added to the mixture and suspended by vigorous stirring, and the pH was maintained between 7 and 11. Ammonia or nitric acid is used for this purpose. The suspension was heated to 80 ° C in the next step. In the second mixture, 0.6581 g of hydrazine (acetic acid) _{3 was} dissolved in 160 ml of demineralized water and transferred to a dropping funnel. Once the liquid phase reaches temperature, the solution is gradually added dropwise over a time interval of 1 to 1.5 hours. The suspension was filtered off with suction through a Buchner funnel (2 μm filter paper) and washed 3 times with 30 ml of demineralized water and finally with 30 ml of ethanol. The product was dried at 80 °C.

Instance 13
Ca ₂ (Lu _0.45 Tb _0.5 Eu _0.2 )Zr ₂ Al ₃ O ₁₂ @ Ca ₂ (Lu _0.5 Tb _0.47 Ce _0.03 )Zr ₂ Al ₃ O ₁₂ Preparation

The synthesis was carried out in the form of in situ precipitation of urea as a precipitant. 0.0770 g (0.1935 mmol) of Lu ₂ O ₃ , 0.0454 g (0.1290 mmol) of Eu ₂ O ₃ and 0.1206 g (0.1613 mmol) of Tb ₄ O _{7 were} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. . 9.2973 g (154.8 mmol) of urea, 1.4518 g (3.87 mmol) of Al(NO ₃ ) ₃ *9H ₂ O, 0.6093 g (2.58 mmol) of Ca(NO ₃ ) ₂ *4H ₂ O and 0.8522 g (2.58 Methyl) of ZrO(NO ₃ ) ₂ *5.5H ₂ O was dissolved in 200 ml of deionized water and added to the above solution. Subsequently, 1 g of the core material (Ca ₂ (Lu _0.5 Tb _0.47 Ce _0.03 ) Zr ₂ Al ₃ O ₁₂ ) was dispersed in the overall solution. The bulk solution was then heated to 90 ° C under reflux and stirred for 6 h. The precipitated product was filtered through 415 filter paper, washed three times with about 30 ml of deionized water, and dried at 150 ° C for 3 h in a dry box. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated at 1500 ° C for 8 h in a CO atmosphere. Excitation and emission spectrum of the product of FIG. 13 and FIG. 14 shows the obtained.

Instance 14
Ca ₂ (Lu _0.495 Tb _0.5 Eu _0.05 )Zr ₂ Al ₃ O ₁₂ @ Ca ₂ (Lu _0.5 Tb _0.47 Ce _0.03 )Zr ₂ Al ₃ O ₁₂ Preparation

The synthesis was carried out in the form of in situ precipitation of urea as a precipitant. 0.1270 g (0.3193 mmol) of Lu ₂ O ₃ , 0.0113 g (0.0323 mmol) of Eu ₂ O ₃ and 0.1206 g (0.1613 mmol) of Tb ₄ O _{7 were} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. . 9.2973 g (154.8 mmol) of urea, 1.4518 g (3.87 mmol) of Al(NO ₃ ) ₃ *9H ₂ O, 0.6093 g (2.58 mmol) of Ca(NO ₃ ) ₂ *4H ₂ O and 0.8522 g (2.58 Methyl) of ZrO(NO ₃ ) ₂ *5.5H ₂ O was dissolved in 200 ml of deionized water and added to the above solution. Subsequently, 1 g of the core material (Ca ₂ (Lu _0.5 Tb _0.47 Ce _0.03 ) Zr ₂ Al ₃ O ₁₂ ) was dispersed in the overall solution. The bulk solution was then heated to 90 ° C under reflux and stirred for 6 h. The precipitated product was filtered through 415 filter paper, washed three times with about 30 ml of deionized water, and dried at 150 ° C for 3 h in a dry box. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated at 1500 ° C for 8 h in a CO atmosphere. Excitation and emission spectrum of the product of FIG. 13 and FIG. 14 shows the obtained.

Instance 15
Ca ₂ (Tb _0.8 Eu _0.2 )Hf ₂ Al ₃ O ₁₂ @ Ca ₂ TbHf ₂ Al ₃ O ₁₂ @ Ca ₂ (Lu _0.17 Tb _0.8 Ce _0.03 )Hf ₂ Al ₃ O ₁₂ Preparation ( For 180 weight % It Ca ₂ TbHf ₂ Al ₃ O ₁₂ The synthesis of the interlayer. The quality ratio is based on the quality of the core material. For 90 weight % It Ca ₂ TbHf ₂ Al ₃ O ₁₂ Synthetic layer , The starting weight must be adjusted accordingly. )

The synthesis was carried out in the form of a precipitate of ammonium bicarbonate as a precipitant. 0.7757 g (1.0375 mmol) of Tb ₄ O _{7 was} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. 4.6704 g (12.45 mmol) of Al(NO ₃ ) ₃ *9H ₂ O, 1.96 g (8.3 mmol) of Ca(NO ₃ ) ₂ *4H ₂ O and 3.6083 g (8.3 mmol) of HfOCl ₂ *9.4H ₂ O was dissolved in 50 ml of deionized water and added to the above solution. The combined solution was transferred to a dropping funnel. Subsequently, 11.8116 g (149.4 mmol) of NH ₄ HCO _{3 was} dissolved in 200 ml of deionized water, and 2 g of the core material (Ca ₂ (Lu _0.17 Tb _0.8 Ce _0.03 )Hf ₂ Al ₃ O ₁₂ ) was suspended in among them. At about 2 drops per second nitrate solution was added dropwise to a solution of precipitate, in this process by the addition of NH ₃ at pH was maintained between 6.8 and 7.2. When the addition of the nitrate solution was completed, the stirring was continued for another 30 min. The precipitated product was filtered through a 410 filter paper, washed three times with about 30 ml of ethanol, and dried in a dry box at 150 ° C for 3 h. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated at 1550 ° C for 8 h in a CO atmosphere. Thereafter, 0.1555 g (0.2080 mmol) of Tb ₄ O ₇ and 0.0366 g (0.1040 mmol) of Eu ₂ O _{3 were} dissolved in 10 ml of HNO ₃ and 10 ml of deionized water. 1.1704 g (3.12 mmol) of Al(NO ₃ ) ₃ *9H ₂ O, 0.4912 g (2.08 mmol) of Ca(NO ₃ ) ₂ *4H ₂ O and 0.9043 g (2.08 mmol) of HfOCl ₂ *9.4H ₂ O was dissolved in 50 ml of deionized water and added to the above solution. The combined solution was transferred to a dropping funnel. Subsequently, 2.96 g (37.44 mmol) of NH ₄ HCO _{3 was} dissolved in 200 ml of deionized water, and 1 g of the core-shell material (Ca) produced in the first method and ground with a mortar and pestle (Ca) ₂ TbHf ₂ Al ₃ O ₁₂ @ Ca ₂ (Lu _0.17 Tb _0.8 Ce _0.03 )Hf ₂ Al ₃ O ₁₂ ) was suspended therein. At about 2 drops per second nitrate solution was added dropwise to a solution of precipitate, in this process, by adding NH ₃ pH was maintained between 6.8 and 7.2. When the addition of the nitrate solution was completed, the stirring was continued for another 30 min. The precipitated product was filtered through a 410 filter paper, washed three times with about 30 ml of ethanol, and dried in a dry box at 150 ° C for 3 h. The dried filter cake was ground in a mortar and pestle, transferred to corundum crucible, and heated at 1550 ° C for 8 h in a CO atmosphere. The emission spectrum of the product obtained is shown in FIG. 17 of.

Hereinafter, the present invention will be explained in detail by way of working examples and FIGS. 1 to 16 , without being limited thereto. The figures show the following:

Figure 1 : X-ray diffraction pattern of (Tb _0.97 Eu _0.03 ) ₃ Al ₅ O ₁₂ @ Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ for Cu K-α radiation of Example 1.

Figure 2 : X-ray diffraction pattern of (Tb _0.94 Ce _0.03 Eu _0.03 ) ₃ Al ₅ O ₁₂ @ Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ for Cu K-α radiation of Example 2.

Figure 3 : X-ray diffraction pattern of Tb ₃ Al ₅ O ₁₂ @ Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ for Cu K-α radiation of Example 3.

Figure 4 : Pure TAG: Ce ³⁺ excitation spectrum (-),

Example 1 is coated with TAG:Eu ³⁺ TAG:Ce ³⁺ (- -), and

Example 2 was coated with TAG:Ce ³⁺ , Eu ³⁺ TAG: Ce ³⁺ (···).

Figure 5 : Pure TAG: Ce ³⁺ emission spectrum (-),

Example 1 is coated with TAG:Eu ³⁺ TAG:Ce ³⁺ (- -), and

Example 2 was coated with TAG:Ce ³⁺ , Eu ³⁺ TAG: Ce ³⁺ (···).

Figure 6 : Pure TAG: Ce ³⁺ reflection spectrum (-),

Example 1 is coated with TAG:Eu ³⁺ TAG:Ce ³⁺ (- -), and

Example 2 was coated with TAG: Ce ³⁺ , Eu ³⁺ TAG: Ce ³⁺ (···) (measured against BaSO ₄ as a reference).

Figure 7 : Pure TAG: Ce ³⁺ decay curve (black),

Example 1 is coated with TAG:Eu ³⁺ TAG:Ce ³⁺ (dark gray), and

Example 2 was coated with TAG: Ce ³⁺ , Eu ³⁺ TAG: Ce ³⁺ (light grey).

Figure 8 : Reflectance spectrum (grey line), excitation spectrum (black line) and emission spectrum (dashed line) of Ca ₂ (Lu _0.47 Ce _0.03 Tb _0.5 )Zr ₂ Al ₃ O ₁₂ .

Figure 9 : Scanning electron microscope image of TAG:Ce ³⁺ coated with TAG:Eu ³⁺ of Example 1.

Figure 10 : Schematic representation of a method of illumination for converting blue light radiation into red light radiation in a core-shell particle.

Figure 11 : Schematic structure of possible kernel-shell (-shell) particles.

Figure 12 : Schematic structure of possible ceramic core-shell particles.

Figure 13 : Excitation spectrum normalized to Tb ³⁺ excitation at 485 nm, λ _em = 610.5 nm.

—=Ca ₂ LuZr ₂ Al ₃ O ₁₂ :Ce ³⁺ ,Eu ³⁺ ,Tb ³⁺ (=CLZA:Ce ³⁺ ,Eu ³⁺ ,Tb ³⁺ )

- - - = coated with _{Ca 2 LuZr 2 Al 3 O 12} : Eu 3+, Tb 3+ (= CLZA: Eu 3+, Tb 3+ @ CLZA: Ce 3+, Tb 3+) of Ca ₂ LuZr ₂ Al ₃ O ₁₂ :Ce ³⁺ , Tb ³⁺

Figure 14 : Emission spectrum λ _ex = 410 nm.

—=Ca ₂ LuZr ₂ Al ₃ O ₁₂ :Ce ³⁺ ,Eu ³⁺ ,Tb ³⁺ (=CLZA:Ce ³⁺ ,Eu ³⁺ ,Tb ³⁺ )

- - - = coated with _{Ca 2 LuZr 2 Al 3 O 12} : Eu 3+, Tb 3+ (= CLZA: Eu 3+, Tb 3+ @ CLZA: Ce 3+, Tb 3+) of Ca ₂ LuZr ₂ Al ₃ O ₁₂ :Ce ³⁺ , Tb ³⁺

Figure 15 : Scanning electron microscope image of pure TAG: Ce ³⁺ .

Figure 16 : Scanning electron microscope image of TAG:Eu ³⁺ @ TAG:Ce ³⁺ .

Figure 17 : 90% by weight of Ca ₂ TbHf ₂ Al ₃ O ₁₂ layer (solid line) or 180% by weight of Ca ₂ TbHf ₂ Al ₃ O ₁₂ layer (dashed line) and 90% by weight of Ca ₂ (Tb _{0.8 Eu 0.2) Hf 2 Al 3 O} 12 outer layer _{Ca 2 (Tb 0.8 Eu 0.2)} Hf 2 Al 3 O 12 @ Ca 2 TbHf 2 Al 3 O 12 @ Ca 2 (Lu 0.17 Tb 0.8 Ce 0.03) Hf 2 Al 3 The emission spectrum of O ₁₂ .

Claims (15)

A multicomponent luminophore, preferably of the core-shell luminophore type, comprising or consisting of: (i) a core, and (ii) at least one shell concentrically disposed in the core Surrounding, wherein (a) the inner core comprises at least one first luminophore doped with Ce ³⁺ and/or Eu ²⁺ , and (b) the outer shell comprises at least one second luminophore, the at least one second luminophore It is a compound containing (b1) Eu ³⁺ and/or Pr ³⁺ and/or Sm ³⁺ , and (b2) Tb ³⁺ and/or Gd ³⁺ . The luminophore of claim 1, wherein the core further comprises a luminophore doped with Tb ³⁺ and/or Gd ³⁺ . The luminophore of claim 1 or 2, wherein the first luminophore has a garnet, citrate, nitrate, (oxy) fluoride and/or (oxy) nitride structure. The luminophore of any one of claims 1 to 3, wherein the first luminophore has a garnet structure and has been doped with Ce ³⁺ . The luminophore of any one of claims 1 to 4, wherein the first luminophores are selected from the group consisting of: Lu ₃ Al ₅ O ₁₂ :Ce ³⁺ (LuAG); Lu ₃ Sc ₂ Al ₃ O ₁₂ :Ce ³⁺ (LSAG); Gd ₃ Al ₅ O ₁₂ :Ce ³⁺ (GdAG); Gd ₃ Sc ₂ Al ₃ O ₁₂ :Ce ³⁺ (GSAG); Tb ₃ Al ₅ O ₁₂ :Ce ³⁺ (TAG); (Ca,Sr,Ba) ₂ SiO ₄ :Eu ²⁺ ;(Ca,Sr,Ba) ₃ SiO ₅ :Eu ²⁺ ;(Ca,Sr,Ba)Si ₂ N ₂ O ₂ : Eu;(Sr,Ba)(Al,Y,Gd,Lu)Si ₄ N ₇ :Eu;(La,Gd,Tb) ₃ Si ₆ N ₁₁ :Ce;Lu ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , where 0<x≤0.4 and 0<y≤0.4: Ce ³⁺ and/or Eu ²⁺ ; Y ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , where 0<x≤0.4 and 0<y≤0.4: Ce ³⁺ and/or Eu ²⁺ ; Tb ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , where 0<x≤0.4 and 0<y≤0.4: Ce ³⁺ and / Or Eu ²⁺ ; Gd ₃ (Al _1-xy Ga _x Sc _y ) ₅ O ₁₂ , where 0<x≤0.4 and 0<y≤0.4: Ce ³⁺ and/or Eu ²⁺ ; Ca ₂ (Lu _{1- Xyz} Gd _x Y _y Sc _z )(Zr _1-a Hf _a ) ₂ Al ₃ O ₁₂ , where 0<x+y+z≤1 and 0<a≤1: Ce ³⁺ and/or Eu ²⁺ ;Ca _{2 (Lu 1-xyz Gd x} Y y Sc z Mg m) (Zr 1-a Hf a) 2 (Al 1-m Si m) 3 O 12, where 0 <x + y + z≤1 0 <a≤1, and 0 <m≤1: Ce ³⁺ and / or _{^{Eu 2+; Ca 2-b (}} Lu 1-xyzt Gd x Y y Sc z Tb t) 1 + b (Zr 1-a Hf a _2-b Al _3+b O ₁₂ , where 0<x+y+z≤1 and 0<a≤1 and 0<t≤1 and 0<b≤1: Ce ³⁺ and/or Eu ²⁺ ; (Lu _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6; (Y _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , wherein 0<z≤0.6: Ce ³⁺ and/or Eu ²⁺ ; (Tb _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0<z≤0.6: Ce ³⁺ and/or Eu ²⁺ ; (Gd _1-z Mg _z ) ₃ (Al _1-z Si _z ) ₅ O ₁₂ , where 0 < _z ≤ 0.6: Ce ³⁺ and/or Eu ²⁺ ; (Ca, Sr, Ba) ₂ SiO ₄ :Eu ²⁺ ;(Ca,Sr,Ba) ₃ SiO ₅ :Eu ²⁺ ;(Gd,Y)F ₃ :Ce ³⁺ ;(Ca,Sr,Ba)Si ₂ N ₂ O ₂ :Eu; (Sr, Ba) (Al, Y, Gd, Lu) Si ₄ N ₇ :Eu; (La, Gd, Tb) ₃ Si ₆ N ₁₁ :Ce; and mixtures or cocrystals thereof. The luminophore of any one of claims 1 to 5, wherein the second luminophore is selected from the group consisting of: Tb ₂ SiO ₅ ; Tb ₂ Si ₂ O ₇ ; TbBO ₃ ; TbB ₃ O ₆ ; Tb ₂ MoO ₆ ; Tb ₂ Mo ₂ O ₉ ; Tb ₂ Mo ₃ O ₁₂ ; Tb ₂ Mo ₄ O ₁₅ ; Tb ₃ Al ₅ O ₁₂ ; Tb ₃ (Al _1-x Ga _x ) ₅ O ₁₂ Wherein 0 < x ≤ 0.4; TbAl ₃ [BO ₃ ] ₄ ; CaTbAl ₃ O ₇ ; TbAl [Ge ₂ O ₇ ]; SrTb ₂ Al ₂ O ₇ ; Sr ₂ TbAlO ₅ ; TbAlO ₃ ; Tb ₄ Al ₂ O ₉ (Ba,Sr,Ca) ₃ TbB ₉ O ₁₈ ;(Ba,Sr,Ca) ₂ Tb ₂ Si ₄ O ₁₃ ;MgTbB ₅ O ₁₀ ;TbB ₅ O ₉ ;Tb ₂ B ₄ O ₉ ;ZnTbB ₅ O ₁₀ Ba ₂ TbNbO ₆ ; Ba ₂ TbTaO ₆ ; TbGa ₃ [BO ₃ ] ₄ ; Sr ₃ Tb ₂ [BO ₃ ] ₄ ; Sr ₃ Tb[BO ₃ ] ₃ ; Ca ₉ Tb[VO ₄ ] ₇ ; Ca ₉ Tb [PO ₄ ] ₇ ; LiTbW ₂ O ₈ ; Tb ₂ Mo ₂ O ₇ ; Tb ₂ Mo ₄ O ₁₅ ; Tb ₂ Sn ₂ O ₇ ; Sr ₂ TbTaO ₆ ; Tb ₂ Ti ₂ O ₇ ; Tb [VO ₄ ]; GdF ₃ ; (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t ) ₂ O ₃ , where 0<x+y+z≤1 and 0<t≤1; Ca ₂ (Lu _1-t Tb _t )Zr ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (Gd _1-t Tb _t ) Zr ₂ Al ₃ O ₁₂ , where 0 < t ≤ 1; Ca ₂ (L u _1-t Tb _t )Hf ₂ Al ₃ O ₁₂ , where 0<t≤ 1; Ca ₂ (Gd _1-t Tb _t )Hf ₂ Al ₃ O ₁₂ , where 0<t≤1; Ca ₂ (Lu _{1 - xyzt} Gd _x Y _y Sc _z Tb _t )(Zr _1-a Hf _a ) ₂ Al ₃ O ₁₂ , where 0<x+y+z≤1 and 0<a≤1 and 0<t≤1; Ca ₂ (Lu _1-xyzt Gd _x Y _y Sc _z Mg _m Tb _t )(Zr _1-a Hf _a ) ₂ (Al _1-m Si _m ) ₃ O ₁₂ , where 0<x+y+z≤1 and 0< a ≤ 1 and 0 < m ≤ 1 and 0 < t ≤ 1; Ca _2-b (Lu _1-xyzt Gd _x Y _y Sc _z Tb _t ) _1+b (Zr _1-a Hf _a ) _2-b Al _{3 +b} O ₁₂ , where 0<x+y+z≤1 and 0<a≤1 and 0<t≤1 and 0<b≤1; and its eutectic. The luminophore of any one of claims 1 to 6, wherein the illuminating group comprises a core and two outer casings concentrically disposed around the inner core. The luminophore of claim 7, wherein the inner shell contains neither Ce ³⁺ nor Eu ³⁺ luminophores or compounds. A method for producing a core-shell luminophore comprising the following steps or consisting of: (a) providing at least one Eu ³⁺ compound and optionally at least one Tb ³⁺ and/or Gd ³⁺ compound a solution; (b) providing at least one luminophore that has been doped with Ce ³⁺ and/or Eu ²⁺ and is insoluble in the solution from step (a); (c) mixing the solution with the luminophore and the precipitant (d) precipitating the Eu ³⁺ , Tb ³⁺ and/or Gd ³⁺ compound on the luminophore; (e) removing the solvent; and (f) densifying and/or thermally post-treating the residue as appropriate . The method of claim 9, wherein the components according to steps (a) and (b) are used in each case at a weight ratio of from about 70:30 to about 90:10 in terms of solids. A method for producing a composite luminophore comprising the following steps or consisting of: (a) providing a first luminophore doped with Ce ³⁺ and/or Eu ²⁺ ; (b) providing a second luminophore The second luminophore is a compound containing (b1) Eu ³⁺ and (b2) Tb ³⁺ and/or Gd ³⁺ ; (c) mixing the first luminescence in a weight ratio of about 30:70 to 10:90 And the second luminophore; (d) pressing the mixture to obtain a green body; (e) sintering the green body at a temperature lower than a melting temperature of the first luminophore by 100 to 500 K. A use according to any one of claims 1 to 8 for use as a luminophore or radiation converter in a blue light or UV-A radiation semiconductor light source (ALED, OLED or PLED). An emissive conversion material comprising the luminophore of any one of claims 1 to 8 and optionally at least one additional converted luminophore. A light source comprising a primary light source, and at least one luminophore according to any one of claims 1 to 8 or an emissive conversion material as claimed in claim 13. A lighting unit comprising at least one light source as claimed in claim 14, preferably having an emission maximum in the range of 340 to 510 nm.