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LUMINOPHORE, METHOD FOR PRODUCING A LUMINOPHORE AND RADIATION-EMITTING COMPONENT

20230100663 · 2023-03-30

    Inventors

    Cpc classification

    International classification

    Abstract

    A luminophore may have the general formula A.sub.zE.sub.eX.sub.6:RE, where A is selected from bivalent elements, E is selected from tetravalent elements, X is selected from monovalent elements, and RE is selected from activator elements. In addition, 0.9≤z≤1.1, and 0.9≤e≤1.1. A method for producing such a luminophore is also disclosed. A radiation-emitting component may further include the luminophore.

    Claims

    1. A luminophore having the general formula A.sub.zE.sub.eX.sub.6:RE where A is selected from Ca, Sr, Ba, Zn, Mg, Cd, or combinations thereof, E is Pb, X is selected from F, Cl, Br, I, or combinations thereof, RE is selected from activator elements, 0.9≤z≤1.1, and 0.9≤e≤1.1.

    2. (canceled)

    3. (canceled)

    4. (canceled)

    5. (canceled)

    6. A luminophore having the general formula A.sub.zE.sub.eX.sub.6:RE where A is selected from Ca, Sr, Zn, Mg, Cd, or combinations thereof, E is selected from Ti, Zr, Hf, Ge, Sn, Pb, or combinations thereof, X is selected from F, Cl, Br, I, or combinations thereof, RE is selected from activator elements, 0.9≤z≤1.1, 0.9≤e≤1.1, and wherein the luminophore has a host lattice comprising AX.sub.6 octahedra and EX.sub.6 octahedra that are linked via common X atoms.

    7. The luminophore as claimed in claim 6, wherein E is selected from Ti, Zr, or combinations thereof.

    8. The luminophore as claimed in claim 6, wherein RE is selected from Mn, Cr, Ni, Eu, Cr, or combinations thereof.

    9. The luminophore as claimed in claim 6, wherein a local maxima in the excitation spectrum ranges from 320 nanometers to 420 nanometers inclusive, and from 430 nanometers to 550 nanometers inclusive.

    10. The luminophore as claimed in claim 6, wherein an emission spectrum has a multitude of emission peaks ranging from 600 nanometers to 700 nanometers.

    11. The luminophore as claimed in claim 6, wherein a half-height width of an emission peak ranges from 1 nanometer to 10 nanometers inclusive.

    12. The luminophore as claimed in claim 6, wherein an emission maximum of an emission peak ranges from 625 nanometers to 633 nanometers inclusive.

    13. The luminophore as claimed in claim 6, wherein a dominant wavelength (λ.sub.D) ranges from 610 nanometers to 618 nanometers inclusive.

    14. A process for producing a luminophore having the general formula A.sub.zE.sub.eX.sub.6:RE where A is selected from the group of divalent elements, E is selected from the group of tetravalent elements, X is selected from the group of monovalent elements, RE is selected from activator elements, 0.9≤z≤1.1 and 0.9≤e≤1.1; wherein the process comprises: providing a stoichiometric composition of reactants; homogenizing the reactants to produce a reaction mixture; and heating the reaction mixture to a maximum temperature.

    15. The process for producing a luminophore as claimed in claim 14, wherein the heating takes place in an F.sub.2 stream.

    16. (canceled)

    17. A radiation-emitting component comprising: a semiconductor chip configured to emit electromagnetic radiation in a first wavelength range in operation; and a conversion element including a luminophore as claimed in claim 6 configured to convert electromagnetic radiation in the first wavelength range to electromagnetic radiation in a second wavelength range.

    18. The radiation-emitting component as claimed in claim 17, wherein the conversion element comprises a second luminophore configured to convert electromagnetic radiation in the first wavelength range to electromagnetic radiation in a third wavelength range.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0250] Further advantageous embodiments, configurations and developments of the luminophore, of the process for producing a luminophore and of the radiation-emitting component will be apparent from the working examples that follow, which are described in conjunction with the figures.

    [0251] FIGS. 1, 2 and 31 show details from various viewing directions of the host lattice of the luminophore, each in one working example,

    [0252] FIGS. 3, 5, 7 and 8 show powder diffractograms of the luminophore, each in one working example,

    [0253] FIGS. 4, 6, 9, 27, 28, 29, 30, 35, 38 and 39 show Rietveld-refined powder diffractograms, each in one working example,

    [0254] FIGS. 10, 11 and 12 show excitation spectrum of the luminophore, each in one working example,

    [0255] FIGS. 13, 15, 17, 18, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 and 51 show emission spectrum of luminophore, each in one working example,

    [0256] FIGS. 14 and 16 show emission spectrum of the luminophore, each in one working example and one comparative example,

    [0257] FIGS. 19 and 20 show a comparison of the relative luminous efficacy of radiation of the luminophore, each in one working example and one comparative example,

    [0258] FIG. 21 shows a schematic section diagram for various process stages of a process for producing a luminophore in one working example,

    [0259] FIGS. 22, 23 and 24 show a radiation-emitting component in schematic section view, each in one working example,

    [0260] FIGS. 25 and 26 show simulated LED emission spectrum with the luminophore, each in one working example, and with one comparative example, and

    [0261] FIGS. 32, 33, 34, 36 and 37 show Le Bail-refined powder diffractograms, each in one working example.

    [0262] Elements that are the same, of the same type will have the same effect are given the same reference numerals in the figures. The figures and size ratios of the elements shown in the figures with respect to one another should not be considered to be true to scale. Instead, individual elements, especially layer thicknesses, may be shown in excessively large size for better illustratability and/or the better understanding.

    DETAILED DESCRIPTION

    [0263] FIG. 1 shows a detail of the host lattice of the luminophore 1 A.sub.zE.sub.eX.sub.6:RE according to the working examples CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, CdHfF.sub.6:Mn, ZnZrF.sub.6:Mn and CaSnF.sub.6:Mn in a schematic diagram. The host lattice has a structure with a cubic Fm3m space group. The structure of the host lattice has vertex-linked AX.sub.6 octahedra 2 and EX.sub.6 octahedra 3. In the present case, the host lattice has AX.sub.6 octahedra 2 with A=Ca, Sr, Cd or Zn and X=F, i.e. CaF.sub.6 octahedra, SrF.sub.6 octahedra, CdF.sub.6 octahedra or ZnF.sub.6 octahedra, and EX.sub.6 octahedra 3 with E=Zr, Hf, Pb or Sn, i.e. ZrF.sub.6 octahedra, HfF.sub.6 octahedra, PbF.sub.6 octahedra or SnF.sub.6 octahedra.

    [0264] What is meant here and hereinafter by “vertex-linked” is that two octahedra are joined to one another via a common vertex 4. The vertex 4 in the present case is a common F atom. FIG. 1 extends in the be plane and thus has a viewing direction in [100] direction. The structures of the working examples CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, CdHfF.sub.6:Mn, ZnZrF.sub.6:Mn and CaSnF.sub.6:Mn were ascertained by x-ray structure analysis measurements.

    [0265] The AF.sub.6 octahedron and the EF.sub.6 octahedron each have an octahedral vacancy. The octahedral vacancy is a region within the respective octahedron. The fluorine atoms form the octahedron, with the A atom and E atom present in the octahedral vacancy of the octahedron formed by the fluorine atoms. In this case, preferably all atoms that form the octahedron at a similar distance from the A atom and the E atom present in the octahedral gap.

    [0266] At least one AF.sub.6 octahedron and one EF.sub.6 octahedron are links to one another via a fluorine atom. The fluorine atom that links the AF.sub.6 octahedron and the EF.sub.6 octahedron is a common fluorine atom.

    [0267] FIG. 2, by comparison with FIG. 1, has a viewing direction in the [110] direction. What is shown is a detail of the host lattice of the luminophore 1 A.sub.zE.sub.eX.sub.6:RE according to the working example CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, CdHfF.sub.6:Mn, ZnZrF.sub.6:Mn and CaSnF.sub.6:Mn in a schematic diagram. The most lattice has a structure with a trigonal R3 space group. In the present case, the host lattice of ZnHfF.sub.6:Mn, CaGeF.sub.6:Mn, ZnSnF.sub.6:Mn, MgGeF.sub.6:Mn, CdPbF.sub.6:Mn, ZnPbF.sub.6:Mn and mgPbF.sub.6:Mn has AX.sub.6 octahedra 2 with A=Ca, Mg or Zn and X=F, i.e. CaF.sub.6 octahedra, MgF.sub.6 octahedra or ZnF.sub.6 octahedra, and EX.sub.6 octahedra with E=Hf, Ge, Pb or Sn, i.e. HfF.sub.6 octahedra, GeF.sub.6 octahedra, PbF.sub.6 octahedra or SnF.sub.6 octahedra. The host lattice of CdPbF.sub.6:Mn has AX.sub.6 octahedra 2 and 3 with A=Cd and X=F, and EX.sub.6 octahedra 2 and 3 with E=Pb and X=F. In the case of CdPbF.sub.6:Mn, the octahedra 2 and 3 are consequently CdF.sub.6 octahedra and PbF.sub.6 octahedra respectively. Here too, the octahedra are linked via common fluorine atoms.

    [0268] In FIGS. 1 and 2, for clarity, not all octahedra and atoms are given a reference numeral.

    [0269] Table 1 below shows the crystallographic data of the working examples CaZrF.sub.6:Mn, CaHfF.sub.6:Mn and ZnHfF.sub.6:Mn, CaGeF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, BaPbF.sub.6:Mn, ZnSnF.sub.6:Mn, MgGeF.sub.6:Mn, CdPbF.sub.6:Mn, ZnPbF.sub.6:Mn, MgPbF.sub.6:Mn, CdHfF.sub.6:Mn, CaSnF.sub.6:Mn, ZnZrF.sub.6:Mn of the luminophores 1. The crystallographic data were obtained from a Rietveld refinement or Le Bail refinement, as described in detail in relation to FIGS. 4, 6, 9, 27, 28, 29, 30, 32, 33, 34, 35, 36, 37, 38 and 39. What are described are firstly the lattice parameters a and c, the unit cell volume V of the unit cell, and secondly the space group.

    TABLE-US-00001 TABLE 1 Crystallographic data of CaZrF.sub.6: Mn, CaHfF.sub.6: Mn, ZnHfF.sub.6: Mn, CaGeF.sub.6: Mn, CaPbF.sub.6: Mn, SrSnF.sub.6: Mn, BaPbF.sub.6: Mn, ZnSnF.sub.6: Mn, MgGeF.sub.6: Mn, CdPbF.sub.6: Mn, ZnPbF.sub.6: Mn, MgPbF.sub.6: Mn, CdHfF.sub.6: Mn, CaSnF.sub.6: Mn and ZnZrF.sub.6: Mn. Lumino- Space phore a/Å c/Å V/Å.sup.3 group CaZrF.sub.6: Mn 8.477 — 609.2 Fm3m (1) (1) CaHfF.sub.6: Mn 8.473 — 608.3 Fm3m (5) (4) ZnHfF.sub.6: Mn 5.58 13.79 372.1 R3 (1) (2) (8) CaGeF.sub.6: Mn 5.4507 13.972 359.50 R3 (10) (3) (13) CaPbF.sub.6: Mn 8.48789 — 611.50 Fm3m (19) (2) SrSnF.sub.6: Mn 8.6292 642.6 Fm3m (18) (2) BaPbF.sub.6: Mn 7.46808 7.52926 363.664 R3m (12) (15) (11) ZnSnF.sub.6: Mn 5.2239 13.845 327.20 R3 (9) (2) (8) MgGeF.sub.6: Mn 5.076 13.080 291.9 R3 (3) (10) (2) CdPbF.sub.6: Mn 5.3741 15.094 377.53 R3 (6) (2) (6) ZnPbF.sub.6: Mn 5.21055 14.2174 344.285 R3 (10) (3) (12) MgPbF.sub.6: Mn 5.2683 13.967 335.71 R3 (8) (3) (9) CdHfF.sub.6: Mn 8.348 581.80 Fm3m (2) (11) ZnZrF.sub.6: Mn 7.972 506.6 Fm3m (3) (3) CaSnF.sub.6: Mn 8.3441 580.95 Fm3m (2) (2)

    [0270] The composition of the luminophore 1 according to the working example SrTiF.sub.6:Mn was confirmed by means of elemental analysis (MP-AES, microwave plasma atomic emission spectroscopy). The actual value for Sr is 37.0% by mass and the actual value for Ti in the luminophore SrTiF.sub.6:Mn is 17.8% by mass. The theoretical value for Sr is 35.0% by mass and the theoretical value for Ti is 18.2% by mass. The variances between measured actual values and calculated theoretical values are within the standard experimental error limits for the analysis method used.

    [0271] FIGS. 3, 5, 7 and 8 show, by way of example, the powder diffractograms of different working examples of the luminophore 1 measured using copper-Kai radiation with a wavelength of 154.06 pm. Relative intensity I is plotted here in arbitrary units, in each case against the diffraction angle 20 in degrees between a radiation source of the x-radiation, the luminophore 1 and a detector for the x-radiation.

    [0272] FIG. 3 shows the powder diffractogram P1 of the luminophore 1 of the working example CaZrF.sub.6:Mn. FIG. 3 also shows, in the section of the powder diffractogram SP, the comparative diffractogram calculated from literature data for undoped CaZrF.sub.6. Clear agreement of the two powder diffractograms is apparent, which is attributable to phase purity of the luminophore 1 having the formula CaZrF.sub.6:Mn. CaZrF.sub.6 and a luminophore 1 according to the working example CaZrF.sub.6:Mn crystallize in the same crystal structure. The phase purity and crystal structure of the luminophore 1 according to the working example CaZrF.sub.6:Mn were thus determined by means of x-ray powder diffractometry.

    [0273] FIGS. 4, 6, 9, 27, 28, 29, 30, 35, 38 and 39 each show Rietveld-refined powder diffractograms of various working examples of the luminophore 1. Relative intensity I is likewise plotted here in arbitrary units against the diffraction angle 2θ. The crosses shown in the powder diffractogram are the measured reflections G1 of the working example of the luminophore 1. G3 describes a difference diagram G3, and G2 describes a calculated powder diffractogram G2. The black marks G4 show the calculated reflection positions of the luminophore. G5 and G6 show the calculated reflection positions of any secondary crystalline phases.

    [0274] FIG. 4 shows a Rietveld-refined powder diffractogram are one of the luminophore 1 according to the working example CaZrF.sub.6:Mn. Here too, good agreement of the calculated powder diffractogram G2 with the measure diffractogram G1 is apparent. Aside from the luminophore having the formula CaZrF.sub.6:Mn, there are no secondary crystalline phases. It is thus possible to verify the crystal structure of the working example CaZrF.sub.6:Mn.

    [0275] FIG. 5, analogously to FIG. 3, shows a measured powder diffractogram P2 of the luminophore, here according to working example CaHfF.sub.6:Mn. The crystal structure of the working example CaHfF.sub.6:Mn can be determined therefrom.

    [0276] FIG. 6, analogously to FIG. 4, shows a Rietveld-refined powder diffractogram R2 of the luminophore 1, according to the working example CaHfF.sub.6:Mn. The crystal structure CaHfF.sub.6 was confirmed as being isotypic with CaZrF.sub.6 by means of the Rietveld refinement of the measured x-ray powder data. For this purpose, proceeding from the crystal structure of CaZrF.sub.6, a structure model was created, in which Zr is replaced by Hf, and which was subsequently refined.

    [0277] Aside from the luminophore 1 having the formula CaHfF.sub.6:Mn, no secondary crystalline phases are present. Here too, good agreement of the calculated powder diffractogram G2 with the measure diffractogram G1 is apparent. It was thus confirmed that CaZrF.sub.6:Mn and CaHfF.sub.6:Mn are isotypic with one another. What is meant by the term “isotypic” is that the compounds have the same crystal structure. Thus, the working examples CaZrF.sub.6:Mn and CaHfF.sub.6:Mn of the luminophore 1 have the same crystal structure.

    [0278] FIG. 7, analogously to FIGS. 3 and 5, shows a measured powder diffractogram P3 of the luminophore 1 according to the working example SrTiF.sub.6:Mn. The reflection positions agree with already known reflection positions.

    [0279] FIG. 8 shows a powder diffractogram P4 of the luminophore 1 according to the working example ZnHfF.sub.6:Mn.

    [0280] By subsequent Rietveld refinement, shown in FIG. 9, the phase composition of the luminophore 1 according to the working example ZnHfF.sub.6:Mn was determined. The Rietveld-refined powder diffractogram R4 shows that ZnHfF.sub.6:Mn is isotypic with the compound LiSbF.sub.6. Proceeding from the compound LiSbF.sub.6, a crystal structure model was created for ZnHfF.sub.6, in which Li was replaced by Zn and Sb by Hf. It is apparent in FIG. 9 that, except for a few comparatively weak reflections of HfF.sub.4 and ZnF.sub.2, the experimental powder diffractogram can be well explained by the structure model for ZnHfF.sub.6.

    [0281] FIGS. 10, 11 and 12 each show an excitation spectrum of working examples of the luminophore 1. Intensity I here is plotted here in arbitrary units against wavelength λ in nm. The intensity I of the spectral line was measured here at 628 nm, and the excitation wavelength was tuned continuously. The luminophore 1 shows two excitation bands. One excitation band of the luminophore 1 is in the near-UV region between 320 nm and 420 nm inclusive, and the second excitation band is in the blue spectral region between 430 nm and 550 nm inclusive. The excitation maxima of the two excitation bands are at about 370 nm and at about 490 nm. Thus, the luminophore 1 finds use in radiation-emitting components with blue primary radiation.

    [0282] FIG. 10 shows an excitation spectrum A1 of the luminophore 1 according to the working example CaZrF.sub.6:Mn.

    [0283] FIG. 11 shows an excitation spectrum A2 of the luminophore 1 according to the working example CaHfF.sub.6:Mn.

    [0284] FIG. 12 shows an excitation spectrum A3 of the luminophore 1 according to the working example SrTiF.sub.6:Mn.

    [0285] FIGS. 13 to 18 and 40 to 51 each show emission spectra of various working examples of the luminophore 1 with characteristic Mn.sup.4+ line emissions. The respective luminophore 1 was excited with blue primary radiation having a wavelength of 490 nm in the case of luminophore 1 of the working examples CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, CaPgF.sub.6:Mn and SrTiF.sub.6:Mn, or of 500 nm in the case of luminophore 1 of the working examples ZnHfF.sub.6:Mn, ZnSnF.sub.6:Mn and ZnZrF.sub.6:Mn, or 470 nm in the case of luminophore 1 of the working examples CaGeF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, BaPbF.sub.6:Mn, CdHfF.sub.6:Mn, or of 480 nm in the case of luminophore 1 of the working examples mgGeF.sub.6:Mn, ZnPbF.sub.6:Mn, CaSnF.sub.6:Mn and mgPbF.sub.6:Mn. What is plotted is the relative intensity I in arbitrary units against the wavelength λ in nm. The emission spectra show a multitude of emission peaks between 600 nm and 700 nm, with a half-height width of an emission peak between 2 nanometers and 20 nanometers inclusive.

    [0286] FIG. 13 shows an emission spectrum E1 of the working example CaZrF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max of 628.3 nm. A dominant wavelength λ.sub.D is 615.4 nm.

    [0287] FIG. 14 shows the emission spectra of the luminophore 1 according to the working example CaZrF.sub.6:Mn (E1) and a comparative example (E-VB), a commercial fluoride luminophore of the K.sub.2SiF.sub.6:Mn type. The comparative example E-VB likewise emits in the red spectral region and has a comparable color impression, measured by the dominant wavelength λ.sub.D. However, it is clearly apparent that the emission spectrum E1 of the luminophore according to working example CaZrF.sub.6:Mn, by comparison with the emission spectrum of the comparative example E-VB, has been shifted to shorter wavelengths by about 2 nm, and hence toward the region of better eye sensitivity. This leads to improved spectral efficiency and a gain of almost 10% in luminous efficacy of radiation (LER) compared to the comparative example. Table 2a below compares the optical properties of the luminophore 1 according to the working example CaZrF.sub.6:Mn and the comparative example.

    [0288] FIG. 15 shows an emission spectrum E2 of the luminophore 1 according to the working example CaHfF.sub.6:Mn. The emission peak having the highest intensity has an emission maximum Amax of 628.3 nm. A dominant wavelength λ.sub.D is 617.2 nm.

    [0289] FIG. 16 shows the emission spectra of the luminophore 1 according to the working example CaHfF.sub.6:Mn (E2) and of the comparative example (E-VB), a commercial fluoride luminophore of the K.sub.2SiF.sub.6:Mn type. It is clearly apparent that the emission spectrum E2 of the working example CaHfF.sub.6:Mn here too, by comparison with the emission spectrum of the comparative example E-VB, has been shifted by about 2 nm to shorter wavelengths, and hence toward the region of better eye sensitivity. This leads to improved spectral efficiency and to a gain of almost 10% in luminous efficacy radiation (LER) compared to the comparative example E-VB. Table 2a below compares the optical properties of the luminophore 1 having the formula CaHfF.sub.6:Mn and of the comparative example.

    [0290] FIG. 17 shows an emission peak E3 of the luminophore 1 according to the working example SrTiF.sub.6:Mn. The emission peak having the highest intensity here too has an emission maximum Amax of 628.4 nm. A dominant wavelength λ.sub.D is 612.7 nm.

    [0291] FIG. 18 shows an emission peak E4 of the luminophore 1 according to the working example ZnHfF.sub.6:Mn. The emission peak having the highest intensity has an emission maximum Amax at about 632.7 nm. A dominant wavelength λ.sub.D is at about 617.7 nm.

    [0292] FIG. 19 shows the relative luminous efficacy of radiation LE1 of the luminophore 1, according to the working example CaZrF.sub.6:Mn. By comparison, the relative luminous efficacy of radiation of the comparative example LE-VB of the luminophore K.sub.2SiF.sub.6:Mn is shown. The relative luminous efficacy of radiation LE1 of the luminophore 1 according to the working example CaZrF.sub.6:Mn, by comparison with the relative luminous efficacy of radiation of the comparative example LE-VB, has a gain of nearly 10%.

    [0293] FIG. 20 shows the relative luminous efficacy of radiation LE2 of the luminophore 1, according to the working example CaHfF.sub.6:Mn. By comparison, the relative luminous efficacy of radiation of the comparative example LE-VB is shown. The luminophore 1 having the formula CaHfF.sub.6:Mn, by comparison with the comparative example LE-VB, has a gain of nearly 10% in the relative luminous efficacy of radiation. The values for FIGS. 19 and 20 are likewise shown in table 2a.

    [0294] Tables 2a-2d list of the luminous efficacies of radiation LER, the relative luminous efficacies of radiation LER, the emission maxima λ.sub.max, the dominant wavelengths λ.sub.D and the color loci CIE x and CIE y for the luminophores 1 according to the working examples CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, SrTiF.sub.6:Mn, ZnHfF.sub.6:Mn, CaGeF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, BaPbF.sub.6:Mn, ZnSnF.sub.6:Mn, MgGeF.sub.6:Mn, CdPbF.sub.6:Mn, ZnPbF.sub.6:Mn, MgPbF.sub.6:Mn, CdHfF.sub.6:Mn, CaSnF.sub.6:Mn, ZnZrF.sub.6:Mn and the comparative example K.sub.2SiF.sub.6:Mn. The results from tables 2a-2d show that the inventive luminophores 1 having the formula CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, SrTiF.sub.6:Mn, ZnHfF.sub.6:Mn, CaGeF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, ZnSnF.sub.6:Mn, MgGeF.sub.6:Mn, CdPbF.sub.6:Mn, ZnPbF.sub.6:Mn, MgPbF.sub.6:Mn, CdHfF.sub.6:Mn, CaSnF.sub.6:Mn and ZnZrF.sub.6:Mn have a lower dominant wavelength compared to the comparative example K.sub.2SiF.sub.6:Mn. BaPbF.sub.6:Mn, by contrast, has a greater dominant wavelength K.sub.2SiF.sub.6:Mn. In addition, the luminophores 1 having the formula CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, CdPbF.sub.6:Mn and mgPbF.sub.6:Mn have a higher luminous efficacy of radiation than K.sub.2SiF.sub.6:Mn.

    TABLE-US-00002 TABLE 2a Optical data of the luminophores 1 having the formula CaZrF.sub.6: Mn, CaHfF.sub.6: Mn, SrTiF.sub.6: Mn, ZnHfF.sub.6: Mn and K.sub.2SiF.sub.6: Mn CaZrF.sub.6: CaHfF.sub.6: SrTiF.sub.6: ZnHfF.sub.6: K.sub.2SiF.sub.6: Mn Mn Mn Mn Mn LER/lm 222.2 219.3 190.7 194.9 202.7 W.sub.opt..sup.−1 Rel. 109.6 108.2 94.1 96.2 100 LER/% λ.sub.max/nm 628.3 628.3 628.4 632.7 630.8 λ.sub.D/nm 615.4 617.2 612.7 617.7 619.6 CIE x 0.681 0.685 0.674 0.687 0.691 CIE y 0.319 0.315 0.326 0.313 0.309

    TABLE-US-00003 TABLE 2b Optical data of the luminophores 1 having the formula CaGeF.sub.6: Mn, CaPbF.sub.6: Mn, SrSnF.sub.6: Mn, BaPbF.sub.6: Mn and K.sub.2SiF.sub.6: Mn CaGeF.sub.6: CaPbF.sub.6: SrSnF.sub.6: BaPbF.sub.6: K.sub.2SiF.sub.6: Mn Mn Mn Mn Mn LER/lm 213.4 228.6 191.4 202.7 W.sub.opt..sup.−1 Rel. 105 113 94 100 LER/% λ.sub.max/nm 628.6 629.1 626.6 632.5 630.8 λ.sub.D/nm 597.7 618.6 617.2 620.6 619.6 CIE x 0.616 0.689 0.685 0.693 0.691 CIE y 0.383 0.311 0.314 0.307 0.309

    TABLE-US-00004 TABLE 2c Optical data of the luminophores 1 having the formula ZnSnF.sub.6: Mn, MgGeF.sub.6: Mn, CdPbF.sub.6: Mn, ZnPbF.sub.6: Mn and K.sub.2SiF.sub.6: Mn ZnSnF.sub.6: MgGeF.sub.6: CdPbF.sub.6: ZnPbF.sub.6: K.sub.2SiF.sub.6: Mn Mn Mn Mn Mn LER/lm 202.3 185.6 206.8 181 202.7 W.sub.opt..sup.−1 Rel. 100 92 102 89 100 LER/% λ.sub.max/nm 632.6 632.0 631.5 632.8 630.8 λ.sub.D/nm 615.5 614.5 615.7 616.6 619.6 CIE x 0.681 0.679 0.682 0.684 0.691 CIE y 0.318 0.321 0.318 0.316 0.309

    TABLE-US-00005 TABLE 2d Optical data of the luminophores 1 having the formula MgPbF.sub.6: Mn, CdHfF.sub.6: Mn, CaSnF.sub.6: Mn, ZnZrF.sub.6: Mn and K.sub.2SiF.sub.6: Mn MgPbF.sub.6: CdHfF.sub.6: ZnZrF.sub.6: CaSnF.sub.6: K.sub.2SiF.sub.6: Mn Mn Mn Mn Mn LER/lm 205.2 195.1 229.9 202.7 W.sub.opt..sup.−1 Rel. 101 96 113 100 LER/% λ.sub.max/nm 633.0 627.3 632.8 628.5 630.8 λ.sub.D/nm 613.3 609.9 616.5 609.0 619.6 CIE x 0.675 0.665 0.684 0.663 0.691 CIE y 0.324 0.334 0.316 0.337 0.309

    [0295] In the process according to the working example of FIG. 21, in a first process step S1, a stoichiometric composition selected from the group of the reactants calcium fluoride, hafnium(IV) oxide, manganese(II) chloride tetrahydrate, zinc chloride, strontium carbonate, titanium(IV) sulfide, germanium(IV) oxide, lead(II) chloride, tin(II) chloride dihydrate, barium fluoride, zinc carbonate, magnesium fluoride, cadmium chloride, cadmium fluoride, calcium permanganate tetrahydrate and/or zirconyl chloride octahydrate is provided. The reactants are mixed homogeneously. Subsequently, the resultant reaction mixture is introduced into a corundum boat, which is inserted into a tubular furnace. 5% by volume to 10% by volume of F.sub.2 in argon is passed through the tubular furnace.

    [0296] In a next process step S2, the reaction mixture is heated stepwise in the furnace. This means that the reaction mixture is heated at at least one heating rate to at least one intermediate temperature and kept at an intermediate temperature for at least one hold time. Subsequently, the reaction mixture is cooled to room temperature by a cooling step and mixed.

    [0297] In a further process step S3, the reaction mixture is again inserted into the tubular furnace and heated stepwise. The reaction mixture is heated at at least one heating rate to at least one intermediate temperature or a maximum temperature and kept at an intermediate temperature for maximum temperature for at least one hold time.

    [0298] The heating here is a dry high-temperature method. This means that no additional solvents or acids are added in the course of heating. The hazard potential resulting from the addition of an acid, especially a hydrofluoric acid solution, is accordingly avoided.

    [0299] Preparation of the Luminophore 1 According to the Working Example CaZrF.sub.6:Mn

    [0300] A stoichiometric composition of the reactants calcium fluoride (780.8 mg, 10 mmol), zirconyl chloride octahydrate (3.144 g, 9.8 mmol) and manganese(II) chloride tetrahydrate (39.5 mg, 0.2 mmol) is mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed. The intermediate temperature is increased from 30° C. by 20° C. (0.33° C./min), and this intermediate temperature is kept constant for one hour. The stepwise increase in the intermediate temperature and the hold times are repeated until the temperature reaches 370° C. The intermediate temperature is increased at 4° C./min to 400° C. within three days. After a hold time of five further days, the reaction mixture is cooled down to a minimum temperature of 30° C., crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated up again to 400° C. at a heating rate of 4° C./min and, after two further days, the intermediate temperature is increased at 4° C./min to a maximum temperature of 450° C. and kept at that maximum temperature for a further day. Subsequently, the reaction mixture is removed from the oven and cooled down, and the luminophore 1 having the formula CaZrF.sub.6:Mn is obtained.

    [0301] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaZrF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0302] Preparation of the Luminophore 1 According to the Working Example CaHfF.sub.6:Mn

    [0303] A stoichiometric composition of the reactants calcium fluoride (78.3 mg, 1 mmol), hafnium(IV) oxide (199.9 mg, 0.95 mmol) and manganese(II) chloride tetrahydrate (9.6 mg, 0.05 mmol) is mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed. The intermediate temperature is increased from 30° C. by 20° C. (0.33° C./min), and this intermediate temperature is kept constant for one hour. The stepwise increase in the intermediate temperature and the hold times are repeated until the temperature reaches 370° C. After six days, the reaction mixture is cooled down to a minimum temperature of 30° C. Subsequently, the reaction mixture is removed from the furnace, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated up again to 400° C. at a heating rate of 4° C./min and, after five further days, the reaction mixture is cooled down to a minimum temperature of 30° C., crushed with a mortar and pestle and subjected to heat treatment at 450° C. for a further 14 days at 450° C. in a fluorine stream. The luminophore 1 having the formula CaHfF.sub.6:Mn is obtained.

    [0304] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaHfF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0305] Preparation of Luminophore 1 According to the Working Example SrTiF.sub.6:Mn

    [0306] A stoichiometric composition of the reactants strontium carbonate (590.3 mg, 4 mmol), titanium(IV) sulfide (443.0 mg, 3.96 mmol) and manganese(II) chloride tetrahydrate (10.3 mg, 0.04 mmol) is mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10 ml/min of 10% by volume of F.sub.2 in argon is passed. The intermediate temperature is increased to 100° C. (5° C./h), and this intermediate temperature is maintained for 20 hours. The stepwise increase in the intermediate temperature by 100° C. each time (10° C./h) and the hold times (10 hours) are repeated until the temperature reaches 300° C. After four days, the reaction mixture is cooled down to a minimum temperature of 30° C., and the reaction mixture is removed from the furnace, crushed using a glassy carbon mortar and pestle and put back in the furnace. The furnace is heated again to 300° C. at a heating rate of 4° C./min and the reaction mixture is reacted again with a gas stream of 10 ml/min of 5% by volume of F.sub.2 in argon for a further 10 days. The luminophore 1 having the formula SrTiF.sub.6:Mn is obtained.

    [0307] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaZrF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0308] Preparation of the Luminophore 1 According to the Working Example ZnHfF.sub.6:Mn

    [0309] A stoichiometric composition of the reactants zinc chloride (135.1 mg, 1 mmol), hafnium(IV) oxide (200.5 mg, 0.95 mmol) and manganese(II) chloride tetrahydrate (11.8 mg, 0.05 mmol) is mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed. The intermediate temperature is increased from 30° C. by 20° C. (0.33° C./min), and this intermediate temperature is kept constant for one hour. The stepwise increase in the intermediate temperature and the hold times are repeated until the temperature reaches 370° C. After a hold time of two days, the furnace is cooled down to a minimum temperature of 30° C., the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated up again to 400° C. at a heating rate of 4° C./min and the reaction mixture is fluorinated for a further four days, before being cooled down again to 30° C. and crushed with a mortar and pestle. The reaction mixture is put back in the furnace and heated at 4° C./min to a maximum temperature of 450° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further four days. The luminophore 1 having the formula ZnHfF.sub.6:Mn is obtained.

    [0310] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions.

    [0311] Preparation of the Luminophore 1 According to the Working Example CaGeF.sub.6:Mn

    [0312] For the synthesis of CaGeF.sub.6:Mn, calcium fluoride (236.5 mg, 3.03 mmol), germanium(IV) oxide (GeO.sub.2, 310.6 mg, 2.97 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 8.0 mg, 0.04 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 13 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min to a temperature of 400° C. and subjected to heat treatment in a fluorine stream for a further 15 days. The luminophore 1 having the formula CaGeF.sub.6:Mn is obtained.

    [0313] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaGeF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0314] Preparation of the Luminophore 1 According to the Working Example CaPbF.sub.6:Mn

    [0315] Calcium fluoride (CaF.sub.2, 78.7 mg, 1.00 mmol), lead(II) chloride (PbCl.sub.2, 278.7 mg, 1.00 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 2.2 mg, 0.01 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 6 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min to a temperature of 400° C. and subjected to heat treatment in a fluorine stream for a further 8 days. The luminophore 1 having the formula CaPbF.sub.6:Mn is obtained.

    [0316] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores. Furthermore, lead(IV) in quantitative analysis serves as a detection reagent for manganese ions, which are oxidized under acidic conditions to give the pink permanganate ion. Therefore, the presence of Mn(IV) under acidic conditions alongside Pb(IV) is not possible. Accordingly, it is not possible to prepare CaPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0317] Preparation of the Luminophore 1 According to the Working Example SrSnF.sub.6:Mn

    [0318] For the synthesis of SrSnF.sub.6:Mn, strontium carbonate (SrCO.sub.3, 297.6 mg, 2.02 mmol), tin(II) chloride dihydrate (SnCl.sub.2.2H.sub.2O, 441.4 mg, 1.96 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 9.5 mg, 0.05 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 7 days, the furnace is cooled down to a minimum temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 16 days. The luminophore 1 having the formula SrSnF.sub.6:Mn is obtained.

    [0319] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare SrSnF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0320] Preparation of the Luminophore 1 According to the Working Example BaPbF.sub.6: Mn

    [0321] Barium fluoride (BaF.sub.2, 175.9 mg, 1.01 mmol), tin(II) chloride (SnCl.sub.2, 275.3 mg, 0.99 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 1.5 mg, 0.01 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 6 days, the furnace is cooled down to a minimum temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 8 days. The luminophore 1 having the formula BaPbF.sub.6:Mn is obtained.

    [0322] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of BaF.sub.2 in water, and since Mn(IV) does not exist alongside Pb(IV) in aqueous hydrofluoric acid, it is not possible to prepare BaPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0323] Preparation of the Luminophore 1 According to the Working Example ZnSnF.sub.6:Mn

    [0324] Zinc carbonate (ZnCO.sub.3, 252.8 mg, 2.02 mmol), tin(II) chloride dihydrate (SnCl.sub.2.2H.sub.2O, 442.5 mg, 1.96 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 8.0 mg, 0.04 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 7 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 5 days. After cooling in the furnace to a temperature of 30° C., the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 11 days. The luminophore 1 having the formula ZnSnF.sub.6:Mn is obtained.

    [0325] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions.

    [0326] Preparation of the Luminophore 1 According to the Working Example MgGeF.sub.6:Mn

    [0327] Magnesium fluoride (MgF.sub.2, 61.2 mg, 0.98 mmol), germanium(IV) oxide (GeO.sub.2, 102.4 mg, 0.98 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 4.1 mg, 0.02 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 7 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 5 days. The luminophore 1 having the formula MgGeF.sub.6:Mn is obtained.

    [0328] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of MgF.sub.2 in water, it is not possible to prepare SrSnF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0329] Preparation of the Luminophore 1 According to the Working Example CdPbF.sub.6: Mn

    [0330] Cadmium chloride (CdCl.sub.2, 91.8 mg, 0.50 mmol), lead(II) chloride (PbCl.sub.2, 137.4 mg, 0.49 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 3.1 mg, 0.02 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 6 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 26 days. The luminophore 1 having the formula CdPbF.sub.6:Mn is obtained.

    [0331] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the oxidation of manganese(IV) under acidic conditions to manganese(VII), it is not possible to prepare CdPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0332] Preparation of the Luminophore 1 According to the Working Example ZnPbF.sub.6:Mn

    [0333] Zinc carbonate (ZnCO.sub.3, 63.7 mg, 0.51 mmol), lead(II) chloride (PbCl.sub.2, 135.2 mg, 0.49 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 2.5 mg, 0.01 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 6 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 7 days. The luminophore 1 having the formula ZnPbF.sub.6:Mn is obtained.

    [0334] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the oxidation of manganese(IV) under acidic conditions to manganese(VII), it is not possible to prepare ZnPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0335] Preparation of the Luminophore 1 According to the Working Example MgPbF.sub.6:Mn

    [0336] Magnesium fluoride (MgF.sub.2, 33.1 mg, 0.53 mmol), lead(II) chloride (PbCl.sub.2, 136.3 mg, 0.49 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 4.0 mg, 0.02 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 4 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 9 days. The luminophore 1 having the formula MgPbF.sub.6:Mn is obtained.

    [0337] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of MgF.sub.2 in water and since Mn(IV) does not exist alongside Pb(IV) under acidic conditions, it is not possible to prepare ZnPbF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0338] Preparation of the Luminophore 1 According to the Working Example CdHfF.sub.6:Mn

    [0339] Cadmium fluoride (CdF.sub.2, 151.4 mg, 1.01 mmol) and hafnium(IV) oxide (HfO.sub.2, 211.4 mg, 1.00 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. The temperature is maintained for 10 h and then increased to 450° C. within 10 h. After a hold time of 12 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The furnace is heated at 4° C./min up to 450° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 13 days. The luminophore 1 having the formula CdHfF.sub.6:Mn is obtained. The input of manganese ions is attributable to previous reactions and a manganese species that has remained as a result, which reacts at the synthesis temperature to give volatile manganese(IV) fluoride and is deposited on the CdHfF.sub.6.

    [0340] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions.

    [0341] Preparation of the Luminophore 1 According to the Working Example ZnZrF.sub.6:Mn

    [0342] Zinc carbonate (ZnCO.sub.3, 124.5 mg, 0.99 mmol), zirconyl chloride octahydrate (ZrOCl.sub.2.8H.sub.2O, 316.0 mg, 0.98 mmol) and manganese(II) chloride tetrahydrate (MnCl.sub.2.4H.sub.2O, 3.6 mg, 0.02 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 8 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 10 days. The luminophore 1 having the formula ZnZrF.sub.6:Mn is obtained.

    [0343] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions.

    [0344] Preparation of the Luminophore 1 According to the Working Example CaSnF.sub.6:Mn

    [0345] Calcium fluoride (CaF.sub.2, 154.4 mg, 1.97 mmol), tin(II) chloride dihydrate (SnCl.sub.2.2H.sub.2O, 446.7 mg, 1.98 mmol) and calcium permanganate tetrahydrate (Ca(MnO.sub.4).sub.2.4H.sub.2O, 3.0 mg, 0.01 mmol) are mixed intimately in an agate mortar and introduced into a corundum boat. This corundum boat is placed in a corundum tube heatable by a tubular furnace, through which 10% by volume of F.sub.2 in argon is passed at 5 ml/min. The temperature is increased from 30° C. to 100° C. within 5 h, which is maintained for 20 h, before the temperature is increased stepwise by 100° C. (10° C./h, hold time 10 h) up to 400° C. After a hold time of 18 days, the furnace is cooled down to a temperature of 30° C., and the reaction mixture is removed, crushed using a glassy carbon mortar and pestle, and put back in the furnace. The reaction mixture is heated in the furnace at 4° C./min up to 400° C., and the reaction mixture is subjected to heat treatment in a fluorine stream for a further 13 days. The luminophore 1 having the formula CaSnF.sub.6:Mn is obtained.

    [0346] The synthesis is thus a dry high-temperature process, in which it is possible to dispense with the use of hydrofluoric acid solutions. Owing to the sparing solubility of CaF.sub.2 in water, it is not possible to prepare CaZrF.sub.6:Mn by the process in aqueous HF which is otherwise customary in industry for complex fluoride luminophores.

    [0347] FIG. 22 shows a schematic section diagram of a radiation-emitting component 5 in one working example, having a semiconductor chip 6 which emits primary radiation in operation of the radiation-emitting component 5. The semiconductor chip 6 comprises an active layer sequence and an active region (not shown explicitly here), which serves to generate the primary radiation. The primary radiation is electromagnetic radiation of a first wavelength range. The primary radiation is preferably electromagnetic radiation having wavelengths in the visible region, for example in the blue region. The primary radiation is emitted by the radiation exit face 7. This generates a beam path, meaning that the primary radiation follows a beam path.

    [0348] A conversion element 8 is disposed in the beam path of the primary radiation emitted by the semiconductor chip 6. The conversion element 8 is set up to absorb the primary radiation and convert it at least partly to a secondary radiation having a second wavelength range. In particular, the secondary radiation has a longer wavelength than the primary radiation absorbed.

    [0349] The conversion element 8 includes a luminophore 1 having the general formula A.sub.zE.sub.eX.sub.6:RE. More particularly, the conversion element 8 may include the luminophore 1 having the formula CaZrF.sub.6:Mn, CaHfF.sub.6:Mn, SrTiF.sub.6:Mn, ZnHfF.sub.6:Mn, CaGeF.sub.6:Mn, CaPbF.sub.6:Mn, SrSnF.sub.6:Mn, BaPbF.sub.6:Mn, ZnSnF.sub.6:Mn, MgGeF.sub.6:Mn, CdPbF.sub.6:Mn, ZnPbF.sub.6:Mn, MgPbF.sub.6:Mn, CdHfF.sub.6:Mn, CaSnF.sub.6:Mn and/or ZnZrF.sub.6:Mn. The luminophore 1 may be embedded into a matrix material. The matrix material is, for example, a silicone, a polysiloxane, an epoxy resin or glass. Alternatively, the conversion element 8 may be free of any matrix material. In that case, the conversion element 8 may consist of the luminophore 1, for example of a ceramic of the luminophore 1.

    [0350] Alternatively, the conversion element 8 may include a second luminophore that converts primary radiation, for example to yellow or green secondary radiation. The combination of the blue primary radiation, the red secondary radiation and the yellow or green secondary radiation can generate warm white mixed light having a high color rendering index R.sub.a.

    [0351] In the working example shown in FIG. 22, the semiconductor chip 6 and the conversion element 8 are embedded in a recessed 10 in a housing 9. For better stabilization and for protection of the semiconductor chip 6 and of the conversion element 8, the recess 10 of the housing 9 may be filled with an encapsulant 11.

    [0352] More particularly, the recess 10 is filled completely with the encapsulant 11, and the semiconductor chip 6 and the conversion element 8 are fully enveloped by the encapsulant 11.

    [0353] The conversion element 8 may, as shown in FIG. 22, be arranged in direct mechanical contact atop the semiconductor chip 6. In particular, the radiation exit face 7 forms the common face between the conversion element 8 and the semiconductor chip 6. Alternatively, there may be further layers, for example adhesive layers, between the semiconductor chip 6 and the conversion element 8.

    [0354] In the working example shown in FIG. 23, the conversion element 8 is disposed at a distance from the semiconductor chip 6. In that case, an encapsulant 11 may be disposed between the semiconductor chip 6 and the conversion element 8. Alternatively, the recess 10 between the semiconductor chip 6 and the conversion element 8 may also be free of any encapsulant 11 or further layers or components.

    [0355] In the working example shown in FIG. 24, the conversion element 8 is disposed in a recessed 10. The semiconductor chip 6 is embedded into the conversion element 8. The conversion element 8 comprises the luminophore 1 and the matrix material, which is silicone, for example. Further luminophores may be introduced into the conversion element 8.

    [0356] FIGS. 25 and 26 each show simulated LED emission spectra with the luminophore 1 and with the comparative luminophore of the comparative example S-VB. Here, both for the luminophore 1 and for the comparative example, LED spectra with a color temperature of about 3000 K were simulated. Relative intensity I in arbitrary units is plotted against the wavelength λ in nm. Here, LED emission spectrum were simulated both for the luminophore 1 and for the comparative luminophore. The second luminophore was assumed to be a green-emitting luminophore (Lu,Y).sub.3Al.sub.5O.sub.12:Ce. The green-emitting luminophore (Lu,Y).sub.3Al.sub.5O.sub.12:Ce was combined with a blue-emitting semiconductor chip 6 having a dominant wavelength λ.sub.D of 455 nm and the emission spectrum of luminophore 1. In the simulated LED emission spectrum of the comparative example S-VB, rather than the red-emitting luminophore 1, the red-emitting comparative luminophore K.sub.2SiF.sub.6:Mn was used.

    [0357] In FIG. 25, the red luminophore used was luminophore 1 according to the working example CaZrF.sub.6:Mn. It is clearly apparent that the LED emission spectrum SE1 with luminophore 1 of the formula CaZrF.sub.6:Mn has been shifted to shorter wavelengths compared to the comparative example S-VB.

    [0358] FIG. 26 differs merely in the use of the luminophore 1. In FIG. 26, for the simulation of the luminophore 1 according to the working example, CaHfF.sub.6:Mn was used. Here too, a distinct shift to shorter wavelengths of the LED emission spectrum SE2 with the luminophore 1 CaHfF.sub.6:Mn is found by comparison with the comparative example S-VB.

    [0359] Table 3 compares the optical data of the simulated LED emission spectrum with the luminophores of the working examples CaZrF.sub.6:Mn and CaHfF.sub.6:Mn and of the comparative example K.sub.2SiF.sub.6:Mn as red luminophore. The second luminophore was assumed to be a green-emitting luminophore (Lu,Y).sub.3Al.sub.5O.sub.12:Ce, and the semiconductor chip 6 was assumed to be a blue-emitting semiconductor chip 6 having a dominant wavelength λ.sub.D of 455 nm.

    TABLE-US-00006 TABLE 3 Optical data of the simulated LED emission spectrum with the luminophores of the formula CaZrF.sub.6: Mn, CaHfF.sub.6: Mn and K.sub.2SiF.sub.6: Mn as red luminophore. CaZrF.sub.6: Mn CaHfF.sub.6: Mn K.sub.2SiF.sub.6: Mn LER/lm W.sub.opt..sup.−1 336.5 336.3 331.3 Rel. LER/% 102 102 100 R.sub.a 92 92 89 R.sub.9 97 25 74 CIE x 0.437 0.437 0.437 CIE y 0.404 0.404 0.404 CCT/K 3008 2993 2996

    [0360] By comparison with the comparative example with the red-emitting luminophore K.sub.2SiF.sub.6:Mn, the LEDs with the red-emitting luminophore 1 according to the working example CaZrF.sub.6:Mn or with the red-emitting luminophore 1 according to the working example CaHfF.sub.6:Mn have a higher luminous efficacy of radiation (LER) by 2%. In addition, for the same color locus, i.e. identical CIE x and CIE y, it is possible to achieve a color rendering index R.sub.a which is three points better. Especially in the case of the R.sub.9, which is a measure of the true rendering of saturated red hues, a much higher value is observed.

    [0361] FIG. 27 shows a Rietveld-refined powder diffractogram R5 of the luminophore 1 according to the working example CaGeF.sub.6:Mn. For this purpose, proceeding from the published crystal structure of LiSbF.sub.6 [J. H. Burns, Acta Crystallogr. 1962, 15, 1098-1101] and the published cell parameters of CaGeF.sub.6 (LiSbF.sub.6 type) [D. Reinen, F. Steffens, Z. Anorg. Allg. Chem. 1978, 441, 63-82], a structure model was created, in which Sb is replaced by Ge and Li by Ca, and then refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as luminophore 1 having the formula CaGeF.sub.6:Mn, CaF.sub.2 is present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of CaF.sub.2). It is thus possible to verify the crystal structure of the working example CaGeF.sub.6:Mn. The crystal structure is isotypic with LiSbF.sub.6.

    [0362] FIG. 28 shows a Rietveld-refined powder diffractogram R6 of the luminophore 1 according to the working example CaPbF.sub.6:Mn. For this purpose, proceeding from the published crystal structure of CaPbF.sub.6 [R. Hoppe, J. Inorg. Nucl. Chem. 1958, 8, 437-440; R. Hoppe, K. Blinne, Z. Anorg. Allg. Chem. 1958, 293, 251-263] and the published structure of NaSbF.sub.6 [G. Teufer, Acta Crystallogr. 1956, 9, 539-540], a structure model was created, in which Sb is replaced by Pb and Na by Ca, and then refined. Here too, good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. It is thus possible to verify the crystal structure of the working example CaPbF.sub.6:Mn. It is clearly apparent that there are no secondary crystalline phases. The crystal structure is isotypic with NaSbF.sub.6.

    [0363] FIG. 29 shows a Rietveld-refined powder diffractogram R7 of the luminophore 1 according to the working example SrSnF.sub.6:Mn. For this purpose, proceeding from the published crystal structure of SrSnF.sub.6 [P. J. Moehs, H. M. Haendler, Inorg. Chem. 1968, 7, 2115-2118] and the published crystal structure of NaSbF.sub.6 [G. Teufer, Acta Crystallogr. 1956, 9, 539-540], a structure model was created, in which Sb is replaced by Sn and Na by Sr, and then refined. Here too, good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. It is thus possible to verify the crystal structure of the working example SrSnF.sub.6:Mn. It is clearly apparent that there are no secondary crystalline phases. The crystal structure is isotypic with NaSbF.sub.6.

    [0364] FIG. 30 shows a Rietveld-refined powder diffractogram R8 of the luminophore 1 according to the working example BaPbF.sub.6:Mn. For this purpose, proceeding from the published crystal structure of BaPbF.sub.6 [R. Hoppe, J. Inorg. Nucl. Chem. 1958, 8, 437-440; R. Hoppe, K. Blinne, Z. Anorg. Allg. Chem. 1958, 293, 251-263] and the published structure of BaSiF.sub.6 [J. L. Hoard, W. B. Vincent, J. Am. Chem. Soc. 1940, 62, 3126-3129], a structure model was created, in which Si is replaced by Pb, and then refined. Here too, good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. It is thus possible to verify the crystal structure of the working example BaPbF.sub.6:Mn. It is clearly apparent that there are no secondary crystalline phases. The crystal structure is isotypic with BaSiF.sub.6.

    [0365] FIG. 31 shows a detail of the host lattice of the luminophore 1 A.sub.zE.sub.eX.sub.6:RE according to the working example BaPbF.sub.6:Mn in a schematic diagram in viewing direction in the [010] direction. The host lattice has a structure of a trigonal R3m space group. In the present case, the host lattice has a structure composed of a three-dimensional network of EX.sub.6 octahedra or 3 with E=Pb and X=F, i.e. PbF.sub.6 octahedra, and AX.sub.12 with A=Ba and X=F cuboctahedra, i.e. BaF.sub.12 cube octahedra. For clarity, not all octahedra and atoms are given a reference numeral, and the cuboctahedra are not shown.

    [0366] FIGS. 32, 33, 34, 36 and 37 each show Le Bail-refined powder diffractograms of various working examples of the luminophore 1. Relative intensity I is plotted here in arbitrary units against the diffraction angle 2θ. The crosses shown in the powder X diffractogram are the measured reflections G1 of the working example of the luminophore 1. The dark gray line describes a difference diagram G3, and the black line describes a calculated powder diffractogram G2. The black marks G4 show the calculated reflection positions of the luminophore. G5 and G6 show the calculated reflection positions of any secondary crystalline phases.

    [0367] FIG. 32 shows a Le Bail-refined powder diffractogram R9 of the luminophore 1 according to the working example ZnSnF.sub.6:Mn. For this purpose, proceeding from the published structure of ZnSnF.sub.6 (LiSbF.sub.6 type) [P. J. Moehs, H. M. Haendler, Inorg. Chem. 1968, 7, 2115-2118; R. Hoppe, V. Wilhelm, B. Müller, Z. Anorg. Allg. Chem. 1972, 392, 1-9], the cell parameters were refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as ZnSnF.sub.6:Mn, ZnF.sub.2 is also present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of ZnF.sub.2). It is thus possible to verify the crystal structure of the working example ZnSnF.sub.6:Mn. The unit cell metrics and the crystal system of ZnSnF.sub.6:Mn are comparable to those of LiSbF.sub.6.

    [0368] FIG. 33 shows a Le Bail-refined powder diffractogram R10 of the luminophore 1 according to the working example MgGeF.sub.6:Mn. For this purpose, proceeding from the published structure of MgGeF.sub.6 [D. Reinen, F. Steffens, Z. Anorg. Allg. Chem. 1978, 441, 63-82], the cell parameters were refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as MgGeF.sub.6:Mn, MgF.sub.2 is present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of MgF.sub.2). It is thus possible to verify the crystal structure of the working example MgGeF.sub.6:Mn. The unit cell metrics and the crystal system of MgGeF.sub.6:Mn are comparable to those of LiSbF.sub.6.

    [0369] FIG. 34 shows a Le Bail-refined powder diffractogram R11 of the luminophore 1 according to the working example CdPbF.sub.6:Mn. For this purpose, proceeding from the published structure of VF.sub.3 [D. Reinen, F. Steffens, Z. Anorg. Allg. Chem. 1978, 441, 63-82], the cell parameters were refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. It is clearly apparent that there is no secondary crystalline phases in the sample aside from CdPbF.sub.6:Mn. It is thus possible to verify the crystal structure of the working example CdPbF.sub.6:Mn. The unit cell metrics and the crystal system of CdPbF.sub.6:Mn are comparable to those of VF.sub.3.

    [0370] FIG. 35 shows a Rietveld-refined powder diffractogram R12 of the luminophore 1 according to the working example ZnPbF.sub.6:Mn. For this purpose, refinement proceeded from the published structure of ZnPbF.sub.6 [R. Homann, R. Hoppe, Z. Anorg. Allg. Chem. 1969, 368, 271-278]. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as ZnPbF.sub.6:Mn, ZnF.sub.2 is present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of ZnF.sub.2). It is thus possible to verify the crystal structure of the working example ZnPbF.sub.6:Mn. The unit cell metrics and the crystal system of ZnPbF.sub.6:Mn are comparable to those of LiSbF.sub.6.

    [0371] FIG. 36 shows a Le Bail-refined powder diffractogram R13 of the luminophore 1 according to the working example MgPbF.sub.6:Mn. For this purpose, proceeding from the published structure of MgPbF.sub.6 [R. Homann, R. Hoppe, Z. Anorg. Allg. Chem. 1969, 368, 271-278], the cell parameters were refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as MgPbF.sub.6:Mn, MgF.sub.2 is present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of MgF.sub.2). It is thus possible to verify the crystal structure of the working example MgPbF.sub.6:Mn. The crystal structure is isotypic with LiSbF.sub.6.

    [0372] FIG. 37 shows a Le Bail-refined powder diffractogram R14 of the luminophore 1 according to the working example CdHfF.sub.6:Mn. For this purpose, proceeding from the published structure of NaSbF.sub.6 [G. Teufer, Acta Crystallogr. 1956, 9, 539-540], the cell parameters were refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as CdHfF.sub.6:Mn, CdF.sub.2 and HfF.sub.4 are present as a crystalline, non-luminescent secondary phase (see G5 and G6, which show the calculated reflection positions of CdF.sub.2 and HfF.sub.4). It is thus possible to verify the crystal structure of the working example CdHfF.sub.6:Mn. The unit cell metrics and the crystal system of CdHfF.sub.6:Mn are comparable to those of NaSbF.sub.6.

    [0373] FIG. 38 shows a Rietveld-refined powder diffractogram R15 of the luminophore 1 according to the working example ZnZrF.sub.6:Mn. For this purpose, proceeding from the published crystal structure of ZnZrF.sub.6 [M. Poulain, J. Lucas, C. R. Seances Acad. Sci., Ser. C 1970, 822-824; V. Rodriguez, M. Gonzi, A. Tressaud, J. Grannec, J. P. Chaminade, J. L. Soubeyroux J. Phys.: Condens. Matter 1990, 2, 7373-7386] and the published crystal structure of NaSbFe [G. Teufer, Acta Crystallogr. 1956, 9, 539-540], a structure model was created, in which Sb is replaced by Zr and Na by Zn, and then refined. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is apparent. As well as ZnZrF.sub.6:Mn, ZnF.sub.2 is present as a crystalline, non-luminescent secondary phase (see G5, which shows the calculated reflection positions of ZnF.sub.2). It is thus possible to verify the crystal structure of the working example ZnZrF.sub.6:Mn. The crystal structure is isotypic with NaSbF.sub.6.

    [0374] FIG. 39 shows a Rietveld-refined powder diffractogram R16 of the luminophore 1 according to the working example CaSnF.sub.6:Mn. The starting point used for the refinement was the published structure of CaSnF.sub.6 (NaSbF.sub.6 type) [H. W. Mayer, D. Reinen, G. Heger, J. Solid State Chem. 1983, 50, 213-224]. It is clearly apparent that there is no secondary crystalline phase in the sample aside from the target compound. Good agreement of the calculated powder diffractogram G2 with the measured diffractogram G1 is also apparent. It is thus possible to verify the crystal structure of the working example CaSnF.sub.6:Mn. The crystal structure is isotypic with NaSbF.sub.6.

    [0375] FIG. 40 shows an emission spectrum E5 of the working example CaGeF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 628.6 nm. A dominant wavelength λ.sub.D is 597.7 nm. The emission of CaGeF.sub.6:Mn is short-wave by about 2 nm compared to K.sub.2SiF.sub.6, and hence shifted toward the region of higher eye sensitivity (not shown), which results in a spectral gain. Advantageously, higher spectral efficiencies in LEDs are thus possible for general lighting and display backlighting.

    [0376] FIG. 41 shows an emission spectrum E6 of the working example CaPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 629.1 nm. A dominant wavelength λ.sub.D is 618.6 nm. The emission of CaPbF.sub.6:Mn is short-wave by about 2 nm compared to K.sub.2SiF.sub.6, and hence shifted toward the region of higher eye sensitivity (not shown), which results in a spectral gain. The effect of this is that the luminophore, compared to K.sub.2SiF.sub.6, has a gain of 5% in luminous efficacy of radiation. Advantageously, higher spectral efficiencies in LEDs are thus possible, for example, in LEDs for general lighting and display backlighting.

    [0377] FIG. 42 shows an emission spectrum E6 of the working example SrSnF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 626.6 nm. A dominant wavelength λ.sub.D is 617.2 nm. The emission of SrSnF.sub.6:Mn is short-wave by about 4 nm compared to K.sub.2SiF.sub.6, and hence shifted toward the region of higher eye sensitivity (not shown), which results in a spectral gain. The effect of this is that the luminophore, compared to K.sub.2SiF.sub.6, has a gain of 13% in luminous efficacy of radiation. Advantageously, higher spectral efficiencies in LEDs are thus possible, for example, in LEDs for general lighting and display backlighting.

    [0378] FIG. 43 shows an emission spectrum E8 of the working example BaPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 632.5 nm. A dominant wavelength λ.sub.D is 620.6 nm.

    [0379] FIG. 44 shows an emission spectrum E9 of the working example BaPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 632.6 nm. A dominant wavelength λ.sub.D is 615.5 nm.

    [0380] FIG. 45 shows an emission spectrum E10 of the working example MgGeF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 632 nm. A dominant wavelength λ.sub.D is 614.5 nm. The emission maximum is in the region of the comparative luminophore K.sub.2SiF.sub.6:Mn and is thus suitable, for example, as an alternative luminophore in LEDs for general lighting and display backlighting.

    [0381] FIG. 46 shows an emission spectrum E11 of the working example CdPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 631.5 nm. A dominant wavelength λ.sub.D is 615.7 nm. The emission of CdPbF.sub.6:Mn, compared to that of K.sub.2SiF.sub.6:Mn, has a higher magnitude in the region of 625 nm, as a result of which more photons are emitted in the region of higher eye sensitivity (not shown). The effect of this is that the luminophore, compared to K.sub.2SiF.sub.6, has a gain of 2% in luminous efficacy of radiation.

    [0382] FIG. 47 shows an emission spectrum E12 of the working example ZnPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 632.8 nm. A dominant wavelength λ.sub.D is 616.6 nm.

    [0383] FIG. 48 shows an emission spectrum E13 of the working example MgPbF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 633 nm. A dominant wavelength λ.sub.D is 613.3 nm. The emission of MgPbF.sub.6:Mn and the comparative luminophore K.sub.2SiF.sub.6:Mn are almost at the same position in the spectrum (not shown). The luminous efficacy of radiation is in the region of the comparative luminophore K.sub.2SiF.sub.6:Mn. Thus, MgPbF.sub.6:Mn is suitable, for example, as an alternative luminophore in LEDs for general lighting and display backlighting.

    [0384] FIG. 49 shows an emission spectrum E14 of the working example CdHfF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 627.3 nm. A dominant wavelength λ.sub.D is 609.9 nm. The emission of CdHfF.sub.6:Mn is short-wave by about 3 nm compared to K.sub.2SiF.sub.6, and hence shifted toward the region of higher eye sensitivity (not shown), which results in a spectral gain. Advantageously, higher spectral efficiencies in LEDs are thus possible in LEDs for general lighting and display backlighting.

    [0385] FIG. 50 shows an emission spectrum E15 of the working example ZnZrF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 632.8 nm. A dominant wavelength λ.sub.D is 616.5 nm.

    [0386] FIG. 51 shows an emission spectrum E16 of the working example CaSnF.sub.6:Mn of the luminophore 1. The emission peak having the highest intensity has an emission maximum λ.sub.max at 628.5 nm. A dominant wavelength λ.sub.D is 609 nm. The emission of SrSnF.sub.6:Mn is short-wave by about 2 nm compared to K.sub.2SiF.sub.6, and hence shifted toward the region of higher eye sensitivity (not shown), which results in a spectral gain. The effect of this is that the luminophore, compared to K.sub.2SiF.sub.6, has a gain of almost 13% in luminous efficacy of radiation. Advantageously, higher spectral efficiencies in LEDs are thus possible in LEDs for general lighting and display backlighting.

    [0387] The features and working examples described in conjunction with the figures may be combined with one another in further working examples, even though not all combinations are described explicitly. In addition, working examples described in conjunction with the figures may alternatively or additionally have further features according to the description in the general part.

    [0388] The invention is not limited to the working examples by the description with reference thereto. Instead, the invention encompasses any new feature and any combination of features, which especially include any combination of features in the claims, even if this feature of this combination itself is not explicitly specified in the claims or working examples.

    LIST OF REFERENCE NUMERALS

    [0389] 1 luminophore [0390] 2 AX.sub.6 octahedron [0391] 3 EX.sub.6 octahedron [0392] 4 vertex [0393] 5 radiation-emitting component [0394] 6 semiconductor chip [0395] 7 radiation exit face [0396] 8 conversion element [0397] 9 housing [0398] 10 recess [0399] 11 encapsulant [0400] I intensity [0401] au arbitrary unit [0402] SP simulated powder diffractogram [0403] P1 powder diffractogram of CaZrF.sub.6:Mn [0404] P2 powder diffractogram of CaHfF.sub.6:Mn [0405] P3 powder diffractogram of SrTiF.sub.6:Mn [0406] P4 powder diffractogram of ZnHfF.sub.6:Mn [0407] R1 Rietveld refinement of CaZrF.sub.6:Mn [0408] R2 Rietveld refinement of CaHfF.sub.6:Mn [0409] R4 Rietveld refinement of ZnHfF.sub.6:Mn [0410] R5 Rietveld refinement of CaGeF.sub.6:Mn [0411] R6 Rietveld refinement of CaPbF.sub.6:Mn [0412] R7 Rietveld refinement of SrSnF.sub.6:Mn [0413] R8 Rietveld refinement of BaPbF.sub.6:Mn [0414] R9 Le Bail refinement of ZnSnF.sub.6:Mn [0415] R10 Le Bail refinement of MgGeF.sub.6:Mn [0416] R11 Le Bail refinement of CdPbF.sub.6:Mn [0417] R12 Rietveld refinement of ZnPbF.sub.6:Mn [0418] R13 Le Bail refinement of MgPbF.sub.6:Mn [0419] R14 Le Bail refinement of CdHfF.sub.6:Mn [0420] R15 Rietveld refinement of ZnZrF.sub.6:Mn [0421] R16 Rietveld refinement of CaSnF.sub.6:Mn [0422] G1 measured reflection positions [0423] G2 calculated powder diffractogram [0424] G3 difference diagram [0425] G4 calculated reflection position [0426] G5 calculated reflection position of secondary phases [0427] G6 calculated reflection position of secondary phases [0428] A1 excitation spectrum of CaZrF.sub.6:Mn [0429] A2 excitation spectrum of CaHfF.sub.6:Mn [0430] A3 excitation spectrum of SrTiF.sub.6:Mn [0431] E1 emission spectrum of CaZrF.sub.6:Mn [0432] E2 emission spectrum of CaHfF.sub.6:Mn [0433] E3 emission spectrum of SrTiF.sub.6:Mn [0434] E4 emission spectrum of ZnHfF.sub.6:Mn [0435] E5 emission spectrum of CaGeF.sub.6:Mn [0436] E6 emission spectrum of CaPbF.sub.6:Mn [0437] E7 emission spectrum of SrSnF.sub.6:Mn [0438] E8 emission spectrum of BaPbF.sub.6:Mn [0439] E9 emission spectrum of ZnSnF.sub.6:Mn [0440] E10 emission spectrum of MgGeF.sub.6:Mn [0441] E11 emission spectrum of CdPbF.sub.6:Mn [0442] E12 emission spectrum of ZnPbF.sub.6:Mn [0443] E13 emission spectrum of MgPbF.sub.6:Mn [0444] E14 emission spectrum of CdHfF.sub.6:Mn [0445] E15 emission spectrum of ZnZrF.sub.6:Mn [0446] E16 emission spectrum of CaSnF.sub.6:Mn [0447] E-VB emission spectrum of the comparative example K.sub.2SiF.sub.6 [0448] SE1 simulated LED spectrum with CaZrF.sub.6:Mn [0449] SE2 simulated LED spectrum with CaHfF.sub.6:Mn [0450] S-VB simulated LED spectrum with the comparative example K.sub.2SiF.sub.6 [0451] S1 process step 1 [0452] S2 process step 2 [0453] S3 process step 3 [0454] LE1 relative luminous efficacy of radiation of CaZrF.sub.6:Mn [0455] LE2 relative luminous efficacy of radiation of CaHfF.sub.6:Mn [0456] LE-VB relative luminous efficacy of radiation of the comparative example K.sub.2SiF.sub.6 [0457] R.sub.a color rendering index