EP2454340A1

EP2454340A1 - Co-doped silicooxynitrides

Info

Publication number: EP2454340A1
Application number: EP10725994A
Authority: EP
Inventors: Holger Winkler; Ralf Petry; Tim Vosgroene; Thomas Juestel; Dominik Uhlich; Arturas Katelnikovas
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2009-07-11
Filing date: 2010-06-17
Publication date: 2012-05-23
Also published as: CN102471681A; JP2012532819A; WO2011006565A1; SG177475A1; DE102009032711A1; US8721925B2; CN102471681B; TW201127938A; US20120140438A1; KR20120052974A

Abstract

The invention relates to compounds of the formula (I) (Ca,Sr,Ba)6-X (Si1-yMey)3(O1-zMa2z)6N4: Eux (I) where Me = Th, Ru and/or Os, Ma = F and/or Cl, x < 0.5, y < 1 and z < 0.1, and also to a process for producing these compounds and use as light-emitting substances, and also to conversion light-emitting substances for the conversion of the blue emission or the emission in the near UV from an LED.

Description

Co-doped silicooxynitrides

The invention relates to compounds which consist of thorium, ruthenium, osmium, fluorine and / or chlorine-co-doped 6-3-6-4-Erdalkali- silicooxynitriden, their preparation and their use as

Phosphors and LED conversion phosphors for warm white LEDs or so-called color-on-demand applications.

The color-on-demand concept is the realization of light of a particular color point with a pcLED (= phosphor converted LED) using one or more phosphors. This concept is e.g. used to create certain corporate designs, e.g. for illuminated company logos, brands etc. To achieve high color spaces using LED TV backlighting are deep red

Phosphors having an emission maximum in the range from 620 nm to 660 nm are required. Material systems known and suitable to the person skilled in the art are siliconitrides and aluminosiliconitrile phosphors (Xie, Sei. Technol. Adv. Mater. 2007, 8, 588-600):

1-1-2-Nitrides such as the CaSiN ₂ : Eu ²⁺ (Le Toquin, Cheetham, Chem.

Phys. Lett. 2006, 423, 352.), 2-5-8-nitrides, such as the (Ca ₁ Sr ₁ Ba) ₂ Si ₅ N ₈ ) Eu ²⁺ (Li et al., Chem. Mater. 2005, 15, 4492). and aluminosiliconitrides such as the (Ca, Sr) AISiN ₃ : Eu ²⁺ (K. Uheda et al., Electrochem., Solid State Lett., 2006, 9, H22).

Nitridic phosphors, as mentioned above, have a number of

Disadvantages that lead to these materials being not available in large quantities: In particular, the high level of purity required represents a challenge which can only be realized technically with great difficulty. For example, the lowest concentrations of carbon or oxygen lead to a marked reduction in the efficiency of the phosphors becomes.

However, it is nearly impossible to oxygen contaminants Avoid even the starting materials, such as Si ₃ N ₄ and the metal nitrides

(Erdalkalimetallnitride, Europiumnitrid) are not available oxygen-free. Alternative educts, such as metal hydrides, are extremely oxygen and

Moisture sensitive, so that too about these components

Oxygen is introduced into the phosphor. Common manufacturing processes, such as carbothermic reduction and nitridation lead to

Carbon contaminants in the phosphor, whereby this phosphor undergoes a brightness-reducing graying.

The silicooxynitride Sr ₆ Si ₃ OeN ₄ : Eu was first reported by Sohn et al., Journ. of Electr. Soc. 155 (2), J58-J61 (2008).

The object of the present invention is therefore the o.g. 6-3-6-4 Modify alkaline earth silicooxynitrides so that these compounds achieve even greater light efficiency.

Surprisingly, it has been found that the requirement for an economically significant further increase in the conversion efficiency of the red silicooxynitride phosphors (Ca ₁ Sr ₁ Ba) ₆ Si ₃ O ₆ N ₄ IEu can be fulfilled if a co-doping with thorium, ruthenium, osmium , Fluorine and / or chlorine is carried out.

The present invention thus relates to compounds of the 6-3- 6-4 alkaline earth silicooxynitride type with europium doping which additionally contain co-dopants from the series thorium, rubidium, osmium, fluorine and / or chlorine.

By "6-3-6-4 alkaline earth silicooxynitriden" one understands such

Compositions M ₆ Si ₃ O ₆ N ₄ IEu ²⁺ , where M is an alkaline earth metal

is a mixture of several alkaline earth metals.

Preference is given to compounds of the formula I. (Ca ₁ Sr ₁ Ba) ₆ -X (Si _1-y Me _y ) 3 (O _1-2 Ma 2z) 6 N ₄ : Eu _x (I)

in which

Me = Th, Ru and / or Os

Ma = F and / or Cl

x <0.5

y <1 and

z <0.1

applies.

It is preferable if the x value is 0.003 to 0.2, the y value (which is the atomic concentration of the co-dopants Me) is 0.0001 to 0.2, and the z value is 0.0005 to 0.03.

More preferably, x = 0.005 to 0.15 and / or y = 0.001 to 0.02.

The greater brightness of the compounds according to the invention or

Phosphors according to the formula I compared with those of identical

Composition, but without the co-dopants thorium, rubidium, osmium, fluorine and / or chlorine can be explained with the theories known to the expert. This is due to the higher

Crystal lattice quality generated by the presence of halides. The halides are likely to reduce the

Diffusion barriers, which must overcome the ions in the solid state reaction to occupy the desired lattice sites in the solid state structure can. The heavy metals Th, Ru or Os are likely to cause an increase in the so-called heavy atom effect

Absorption of the phosphor.

The particle size of the compounds according to the invention is between 50 nm and 30 .mu.m, preferably between 1 .mu.m and 20 .mu.m, more preferably between 2 and 15 .mu.m. - A -

Another object of the present invention is a compound obtainable by mixing silicon nitride, europium and calcium and / or strontium and / or barium-containing educts with at least one thorium, osmium, ruthenium, fluoride and / or Chloride-containing co-dopant by solid-state diffusion methods and subsequent thermal aftertreatment, which optionally a flux from the series of alkali or alkaline earth halides or a

Can contain borate compound.

A further subject of the present invention is a process for the preparation of a compound of the 6-3-6-4 alkaline earth silicooxynitride type with europium doping with the following process steps:

a) preparing an Eu-doped 6-3-6-4 alkaline earth silicooxynitride compound which is co-doped with thorium, rubidium, osmium, fluoride and / or chloride containing materials by mixing at least 4 starting materials selected from silicon nitride, europium, calcium, strontium, barium, thorium, rubidium, osmium, fluoride and / or chloride-containing materials,

b) Thermal aftertreatment of thorium, rubidium, osmium,

Fluoride and / or chloride co-doped compound,

c) washing the thermally treated compounds with an HCl and a KOH solution. The starting materials for the preparation of the compound, as mentioned above, consist of silicon nitride (Si ₃ N ₄ ), calcium hydride and europium fluoride and at least one Th, Ru, Os, F and Cl-containing co-dopant. In addition to the preferred nitrides, hydrides and fluorides, other inorganic and / or organic substances such as cyanamides, dicyanamides, cyanides, oxalates, malonates, fumarates, carbonates, citrates,

Ascorbates and acetylacetonates in question. The abovementioned thermal aftertreatment (see process step b) runs for several hours under reducing conditions, for. B with forming gas (eg 90/10), pure hydrogen and / or in an ammonia atmosphere with or without the above mentioned atmospheres. The temperatures during the annealing process amount to several hours

(preferably 8 h) between 1000 ⁰ C and 1800 ⁰ C, preferably from 1400 ° C to 1600 ° C.

Furthermore, it is preferred if the phosphors are transferred to a high-pressure sintering furnace and there at 40 to 70 bar and a temperature of

1400 to 1600 ° C are annealed for 6 to 10 hours.

Furthermore, it is preferred if the phosphors are hot isostatic under

Vacuum be pressed.

In addition, it is preferable that the phosphors are first washed with HCl and then with KOH, whereby amorphous SiO _{2 is} eliminated. This washing step advantageously increases the

Emission intensity as well as the absorption of the phosphors.

With the help of o.g. Methods can be made of any external forms of the compounds or phosphors according to the invention, such as spherical particles, platelets and structured materials and

Ceramics. According to the invention, these forms are combined under the term "shaped body." The shaped body is preferably a "phosphor body".

Another object of the present invention is thus a

Shaped body containing the compounds of the invention, wherein it has a rough surface, the nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or particles with the inventive compound with or without dopants from the series

Europium, osmium, ruthenium, thorium, fluorine and / or chlorine. In a further preferred embodiment, the shaped body on the, an LED chip opposite side of a structured (eg

pyramidal) surface (see WO2008 / 058619, Merck, which is incorporated by reference in its entirety in the context of the present application). Thus, as much light as possible can be coupled out of the phosphor.

The structured surface on the shaped article is formed by subsequent coating with a suitable material, which is already structured, or in a subsequent step by (photo) lithographic

Process, etching or by writing process with energy or matter beams or exposure to mechanical forces produced.

In a further preferred embodiment, the

Moldings of the invention on the, an LED chip

opposite side a rough surface, the nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZnO ₂ , ZrO ₂ and / or Y ₂ O ₃ or combinations of these materials and / or of particles with the phosphor composition according to formula I with or without dopants from the series Th, Ru, Os, F and / or Cl carries. In this case, a rough surface has a roughness of up to several 100 nm. The coated surface has the advantage that total reflection can be reduced or prevented and the light can be better decoupled from the phosphor according to the invention (see WO2008 / 058619 (Merck) is fully incorporated by reference in the context of the present application)

It is further preferred if the shaped bodies according to the invention have a refractive index-adapted layer on the surface facing away from the chip, which facilitates the decoupling of the primary radiation and / or the radiation emitted by the phosphor body.

In a further preferred embodiment, the shaped bodies have a closed surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3, ZnO _, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides and / or of the compounds according to formula I without the activator europium. These

Surface coating has the advantage that a suitable grading of the refractive indices of the coating materials a

Adjustment of the refractive index with the environment can be achieved. In this case, the scattering of light on the surface of the

Luminescent decreases and a greater proportion of the light can penetrate into the phosphor and absorbed and converted there.

It also allows the refractive index-matched

Surface coating that gives more light from the phosphor

is decoupled, because the total internal reflection is reduced.

In addition, a closed layer is advantageous if the

Phosphor must be encapsulated. This may be necessary to one

Sensitivity of the phosphor or parts thereof to diffusing water or other materials in the immediate vicinity. Another reason for the encapsulation with a

closed shell is a thermal decoupling of the actual phosphor from the heat that arises in the chip. This heat leads to a reduction in the fluorescent light output of the phosphor and may also affect the color of the fluorescent light. Finally, it is possible by such a coating to increase the efficiency of the phosphor by preventing lattice vibrations arising in the phosphor from propagating to the environment.

It is furthermore preferred if the shaped body is a porous one

Has surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3, ZnO _, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or of the compounds according to formulas I with or without dopants from the series Eu, Th, Ru,

Os, F and / or Cl exists. These porous coatings offer the possibility of further reducing the refractive index of a single layer. The preparation of such porous coatings can after three

conventional methods, as described in WO 03/027015

which is fully incorporated by reference in the context of the present application: the etching of glass (e.g., soda lime glasses (see US 4019884)), the application of a porous one

Layer and the combination of porous layer and an etching process.

In a further preferred embodiment, the shaped body has a surface which carries functional groups which allow a chemical or physical connection to the environment, preferably consisting of epoxy or silicone resin. These functional groups may e.g. oxo group-attached esters or other derivatives which can form linkages with components based on epoxides and / or silicones. Such surfaces have the advantage that a homogeneous mixing of the phosphors is made possible in the binder. Furthermore, this can be the

Theological properties of the system phosphor / binder and also the pot life can be adjusted to a certain extent. This simplifies the processing of the mixtures. In this context, physical connection to the environment is referred to as electrostatic interactions between the systems

Charge fluctuations or partial charges act.

Since the invention applied to the LED chip

Phosphor layer preferably consists of a mixture of silicone and homogeneous phosphor particles, and the silicone one

Surface tension, this phosphor layer is on

at the microscopic level, or the thickness of the layer is not consistently constant.

The production of platelet-shaped phosphors as further

preferred embodiment is done by conventional methods from the corresponding metal and / or rare earth salts. The

Manufacturing method is described in detail in EP 763573 and WO2008 / 058620, which are fully incorporated by reference into the context of the present application. These platelet-shaped phosphors can be prepared by a natural or synthetically produced highly stable support or a substrate of, for example mica, SiO ₂ , Al ₂ O ₃ , ZrO ₂ , glass or TiO ₂ platelets, which is a very has high aspect ratio, has an atomically smooth surface and an adjustable thickness, can be coated by precipitation reaction in aqueous dispersion or suspension with a phosphor layer. In addition to mica, ZrO ₂ , SiO ₂ , Al ₂ O ₃ , glass or TiO ₂ or mixtures thereof, the platelets may also consist of the phosphor material itself, or be composed of a material. If the plate itself only as a carrier for the

Phosphor coating is used, it must be made of a material that is transparent to the primary radiation of the LED, or the

Absorbs primary radiation and transfers this energy to the phosphor layer. The flake phosphors are dispersed in a resin (e.g., silicone or epoxy) and this dispersion is applied to the LED chip.

The platelet-shaped phosphors can be produced on a large scale in thicknesses of 50 nm up to about 20 μm, preferably between 150 nm and 5 μm. The diameter is from 50 nm to 20 microns. It usually has an aspect ratio (ratio of diameter to particle thickness) of 1: 1 to 400: 1, and in particular 3: 1 to 100: 1.

The platelet extent (length x width) depends on the arrangement. Platelets are also suitable as scattering centers within the conversion layer, especially if they have particularly small dimensions.

The LED chip surface facing the platelet-shaped phosphor according to the invention can be provided with a coating which anti-reflective with respect to the emitted from the LED chip Primary radiation acts. This leads to a reduction in the backscattering of the primary radiation, as a result of which it can be better coupled into the phosphor body according to the invention.

Suitable for this purpose are, for example, refractive index-adapted coatings which must have a following thickness d: d = [wavelength of the

Primary radiation of the LED chip / (4 * refractive index of the phosphor ceramic)], s. for example, Gerthsen, Physik, Springer Verlag, 18th edition, 1995. This coating can also consist of photonic crystals. This also includes a structuring of the surface of the platelet-shaped phosphor in order to achieve certain functionalities.

The production of the shaped bodies according to the invention in the form of ceramic bodies takes place analogously to the process described in WO 2008/017353 (Merck), which is incorporated by reference in its entirety into the context of the present application. In this case, the phosphor is prepared by mixing the corresponding reactants and dopants, then isostatically pressed and applied in the form of a homogeneous thin and non-porous platelets directly on the surface of the chip or at a distance from the chip (remote phosphor concept). The particular arrangement depends i.a. from the architecture of the LED devices, wherein the skilled person is capable of the advantageous

Select arrangement. Thus, no location-dependent variation of the excitation and emission of the phosphor takes place, as a result of which the LED equipped with it emits a homogeneous and color-constant light cone and has a high light output. The ceramic

Phosphor bodies can e.g. be produced industrially as platelets in thicknesses of a few 100 nm up to about 500 .mu.m. The

Platelet expansion (length x width) depends on the arrangement. When directly applied to the chip, the size of the wafer according to the chip size (from about 100 .mu.m * 100 microns to several mm ² ) with a certain excess of about 10% - 30% of the chip surface with a suitable chip arrangement (eg Flip Chip arrangement) or accordingly to choose. If the phosphor plate is placed over a finished LED, the emerging cone of light is completely covered by the plate. The side surfaces of the ceramic phosphor body can with a

Light or precious metal, preferably aluminum or silver are mirrored. The mirroring causes no light to escape laterally from the

Phosphor body exits. Lateral exiting light can reduce the luminous flux to be coupled out of the LED. The mirroring of the

ceramic phosphor body takes place in a process step after the isostatic pressing to bars or plates, which may be done before the mirroring a tailor of the rods or plates in the required size. The side surfaces are for this purpose e.g. wetted with a solution of silver nitrate and glucose and then exposed at elevated temperature to an ammonia atmosphere. Here, e.g. a silver coating on the side surfaces.

Alternatively, there are also electroless metallization processes, see for example Hollemann-Wiberg, Textbook of Inorganic Chemistry, Walter de Gruyter Verlag or Ullmann's Encyclopedia of Chemical Technology.

The ceramic phosphor body may, if necessary, with a

Water-gas solution can be fixed on the substrate of an LED chip.

In a further embodiment, the ceramic has

Phosphor body has a patterned (e.g., pyramidal) surface on the side opposite an LED chip. Thus, as much light as possible can be coupled out of the phosphor body. The structured

Surface on the phosphor body is thereby produced, in which during isostatic pressing, the pressing tool has a structured pressing plate and thereby embosses a structure in the surface.

Structured surfaces are desired when thin phosphor bodies or platelets are to be produced. The Press conditions are known to those skilled in the art (see J. Kriegsmann, Technische keramische Materialien, Chapter 4, Deutscher Wirtschaftsdienst, 1998). It is important that as pressing temperatures 2/3 up to 5/6 of the

Melting temperature of the substance to be pressed are used.

Another object of the present invention is a process for the preparation of a shaped body, preferably phosphor body, with the following process steps:

a) preparing a europium-doped 6-3-6-4 alkaline earth silicooxynitride compound co-doped with thorium, rubidium, osmium, fluoride and / or chloride-containing materials by mixing at least 4 starting materials selected from silicon nitride , Europium, calcium, strontium, barium, ruthenium, thorium, osmium, fluoride and / or chloride containing materials,

b) Thermal aftertreatment with thorium, rubidium, osmium,

Fluoride and / or chloride-codoped compound and formation of a shaped body with a rough surface,

c) coating the surface with nanoparticles of SiO ₂

TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof or with nanoparticles of the compounds according to the invention.

The excitability of the phosphors according to the invention also extend over a wide range, ranging from about 350 nm to 530 nm, preferably 430 nm to about 500 nm. Thus, these phosphors are not only suitable for excitation by UV or blue emitting primary light sources such as LEDs or conventional discharge lamps (eg based on Hg), but also for light sources such as those which exploit the blue In ³⁺ line at 451 nm. Another object of the present invention is a

Lighting unit with at least one primary light source whose emission maximum or maximum in the range 250 nm to 530 nm, preferably 350 nm to about 500 nm ranges. Particularly preferred is a range between 440 and 480 nm, wherein the primary radiation is partially or completely converted by the compounds or phosphors according to the invention into longer-wave radiation. Preferably, this lighting unit emits white or emits light with a certain color point (color-on-demand principle). Preferred embodiments of the lighting units according to the invention are shown in FIGS. 1 to 7. In a preferred embodiment of the invention

Lighting unit is the light source to a

luminescent indium-aluminum gallium nitride, in particular of the formula IniGa _j Al _k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1.

The person skilled in possible forms of such light sources are known. These may be light emitting LED chips

act different construction.

In a further preferred embodiment of the illumination unit according to the invention, the light source is a

luminescent on ZnO, TCO (transparent conducting oxide), ZnSe or

SiC based arrangement or even on an organic light emitting layer based arrangement (OLED).

In a further preferred embodiment of the illumination unit according to the invention, the light source is a source which

Electroluminescence and / or photoluminescence shows. Furthermore, the light source may also be a plasma or discharge source. The phosphors according to the invention can either be dispersed in a resin (for example epoxy or silicone resin) or suitable Depending on the application, size ratios may be arranged directly on the primary light source or may be arranged remotely, depending on the application (the latter arrangement also includes the "remote phosphor technology".) The advantages of the "remote phosphor technology" are known to the person skilled in the art and are, for example, the following Publication: Japanese

Journ. of Appl. Phys. Vol. 44, no. 21 (2005). L649-L651.

In a further embodiment, it is preferred if the optical coupling of the illumination unit between the phosphor and the primary light source is realized by a light-conducting arrangement.

This makes it possible that the primary light source is installed at a central location and this by means of light-conducting devices, such as

for example, light-conducting fibers, to the phosphor optically

is coupled. In this way, the lighting requirements adapted lights can only consist of one or

different phosphors, which may be arranged to form a luminescent screen, and a light guide, which is connected to the primary light source

is connected, realize. In this way, it is possible to place a strong primary light source at a convenient location for electrical installation and without further electrical wiring, but only by

Laying light guides anywhere you want to install lights from phosphors that are coupled to the light guides.

Another object of the present invention is the use of the compounds of the invention and shaped articles as a phosphor or phosphor body.

Another object of the present invention is the use of the compounds of the invention for the partial or complete conversion of the blue or in the near UV emission of a

Emitting diode. Further preferred is the use of the invention

Compounds for the conversion of blue or near UV emission into visible white radiation. Furthermore, the use of the compounds according to the invention for the conversion of the primary radiation into a specific color point according to the "color on demand" concept is preferred.

The compounds of the formula I according to the invention can be used individually or as a mixture with the following phosphors familiar to the person skilled in the art:

Ba ₂ Si0 ₄ : Eu ²⁺ , BaSi ₂ O ₅ Pb ²⁺ , Ba _x Sri _1-x F ₂ : Eu ²⁺ , BaSrMgSi ₂ O ₇ : Eu ²⁺ ,

BaTiP ₂ O ₇ , (Ba ₁ Ti) ₂ P ₂ O ₇ Ti, Ba ₃ WO ₆ : U, BaY ₂ F ₈ Er ³⁺ , Yb ⁺ , Be ₂ SiO ₄ : Mn ²⁺ , Bi ₄ Ge ₃ Oi ₂ , 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 Oe ³⁺ ,

Ca ₃ Al ₂ Si ₃ Oi ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O, ₂ : Eu ²⁺ , Ca ₂ B ₅ O ₉ BrEu ²⁺ ,

Ca ₂ B ₅ O ₉ ChEu ²⁺ , Ca ₂ B ₅ O ₉ ChPb 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⁺ ,

Cao. ₅ Ba _{0 5} Al ₁₂ O ₁₉ : Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (PO 4) ₃ CI: Eu ²⁺ , CaBr ₂ : Eu ²⁺ in SiO ₂ , CaCl ₂ : Eu ²⁺ in SiO ₂ , CaCl ₂ : Eu ²⁺ , Mn ²⁺ in SiO 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⁺ , CaF ₂ : U,

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⁺ , Cal ₂ : Eu ²⁺ in SiO ₂ , Cal ₂ : Eu ²⁺ , Mn ²⁺ in SiO 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 Oe 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⁺ , CaOOd ²⁺ , CaO: Cu ⁺ , CaO: Eu ³⁺ , CaO: Eu ^{3 +} , Na ⁺ , CaO: Mn ²⁺ , CaOPb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaOTb ³⁺ , CaOTI, CaO: Zn ²⁺ , Ca ₂ P ₂ O ₇ Oe 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 _s (PO ₄ ) ₃ F: Sb ³⁺ , Ca _s (PO ₄ ) ₃ F: Sn 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 : Sn 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⁺ , CaSPb ²⁺ , CaSPb ²⁺ , CI, CaSPb ²⁺ , Mn ²⁺ , CaSPr ³⁺ , Pb ²⁺ , CI, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ ,

CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , CI, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ²⁺ , CI, CaSiO ₃ : Ce ³⁺ , Ca ₃ SiO ₄ Cl ₂ ) Eu ²⁺ , Ca ₃ SiO ₄ Cl ₂ Pb ²⁺ , CaSiO ₃ : Eu 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 : Sn ²⁺ Mn ²⁺ , CaTi ₀ . ₉ Alo.iO 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, CaYAIO 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, CeF ₃ , (Ce, Mg) BaAlnO ₁₈ : Ce, (Ce ₁ Mg) SrAI ₁₁ O ₁₈ Oe, CeMgAl ₁₁ O ₁₉ OeTb, Cd ₂ B ₆ O ₁₁ Mn ²⁺ , CdS: Ag ⁺ , Cr,

CdS: ln, CdSMn, CdS: In, Te, CdSTe, CdWO ₄ , CsF, CsI, CsLNa ⁺ , CsITI, (ErCl ₃ ) _o . ₂ 5 (BaCl ₂ ) o.75, GaN: Zn, Gd ₃ Ga ₅ O ₁₂ Or 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 SPr ₁ Ce ₁ F, Gd ₂ O ₂ STb ³⁺ , Gd ₂ SiO ₅ : Ce ^{3 +} , KAl ₁₁ O ₁₇ TI ⁺ , 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 Oi ₂ : Eu ³⁺ , LaAIB ₂ O ₆ : Eu ³⁺ , LaAIO ₃ : Eu ³⁺ ,

LaAIO ₃ : Sm ³⁺ , LaAsO ₄ : Eu ³⁺ , LaBr ₃ : Ce ³⁺ , LaBO ₃ : Eu ³⁺ ,

(La, Ce, Tb) PO ₄ : Ce: Tb, LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBrTb ³⁺ , LaOBrTm ³⁺ , LaOCl: Bi ³⁺ , LaOChEu ³⁺ , LaOF: Eu ³⁺ , La ₂ O ₃ : Eu ³⁺ , La ₂ O ₃ Pr ³⁺ , La ₂ O ₂ STb ³⁺ , LaPO ₄ : Ce ³⁺ , LaPO ₄ : Eu ³⁺ , LaSiO ₃ ChCe ³⁺ , LaSiO ₃ ChCe ³⁺ Tb ³⁺ , LaVO ₄ : Eu ³⁺ , La ₂ W ₃ O ₁₂ : Eu ³⁺ , LiAIF ₄ : Mn ²⁺ , LiAl ₅ O ₈ Pe ³⁺ , LiAIO ₂ Pe ³⁺ , LiAIO 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⁺ , LilnO ₂ : Eu ³⁺ , LilnO ₂ : Sm ³⁺ , LiLaO ₂ : Eu ³⁺ ,

LuAIO ₃ : Ce ³⁺ , (Lu, Gd) ₂ Si0 ₅ : Ce ³⁺ , Lu ₂ SiO ₅ : Ce ³⁺ , Lu ₂ Si ₂ 0 ₇ : Ce ³⁺ ,

LuTaO ₄ : Nb ⁵⁺ , Lu _1-x Y _x AIO ₃ : Ce ³⁺ , 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 Pu ²⁺ ,

MgBaP ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , MgBa ₃ Si ₂ O ₈ Pu 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 Pu ²⁺ ,

MgSO ₄ Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ Pu ²⁺ , MgSrP ₂ O ₇ Pu 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 Pu ^3+, Ce Na ₃ (PO ₄₎ ₂ Tb ^3+, naiti, Na _L23 K ₀₁₄₂ Eu ₀ - _I2 TiSi ₄ O ₁₁ Pu ^3+, Na _{1 23} Co ₄₂ Eu _{0 12} TiSi ₅ O ₁₃ XH ₂ OPu ³⁺ , Na _{1 29} K _{0 46} Er _{0 08} TiSi ₄ O ₁₁ Pu 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, NaYF ₄ : Er ³⁺ , Yb ³⁺ ,

NaYO ₂ Pu ³⁺ , P46 (70%) + P47 (30%), SrAl ₁₂ O ₁₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ Pu ²⁺ , SrAl ₄ O ₇ IEu ³⁺ , SrAl ₁₂ O ₁₉ : Eu ²⁺ , SrAl ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ O ₉ CLEu ²⁺ ,

SrB ₄ O ₇ : Eu ²⁺ (F, CI, Br), SrB ₄ O ₇ Pb ²⁺ , SrB ₄ O ₇ Pb ²⁺ , Mn ²⁺ , SrB ₈ Oi ₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O _4-zy2 : Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ : Eu ²⁺ , Sr (Cl, Br, I) ₂ : Eu ²⁺ in SiO ₂ , SrCl ₂ : Eu ²⁺ in SiO 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⁺ , SrGai ₂ O ₁₉ : Mn ²⁺ , SrGa ₂ S ₄ Oe ³⁺ , SrGa ₂ S ₄ : Eu ²⁺ , 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⁺ , CI, B-SrO SB 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 ) Sn ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Sn ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Sn 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 Oi ₀ Cl ₆ ) Eu ²⁺ , Sr ₂ SiO ₄ ) Eu ²⁺ , SrTiO ₃ ) Pr ³⁺ , SrTiO ₃ : Pr ³⁺ , Al ³⁺ , Sr ₃ WO ₆ ) U, SrY ₂ O. ₃ ) Eu ³⁺ , ThO ₂ ) Eu ³⁺ , ThO ₂ ) Pr ³⁺ , ThO ₂ ) Tb ³⁺ , YAl ₃ B ₄ Oi ₂ ) 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⁺ Jb ³⁺ , YAl ₃ B ₄ O ₁₂ ) Eu ³⁺ , YAI ₃ B ₄ Oi ₂ : Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ Oi ₂ : Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAIO ₃ ) Ce ³⁺ , Y ₃ Al ₅ O ₁₂ ) Ce ³⁺ , Y ₃ Al ₅ O ₁₂ ) Cr ³⁺ , YAIO ₃ ) Eu ³⁺ , Y ₃ Al ₅ O ₂ ) Eu ³ ', Y ₄ Al ₂ O ₉ ) Eu ³⁺ , Y ₃ Al ₅ O ₁₂ ) Mn ^{4 +} , YAIO ₃ ) Sm ³⁺ , YAIO 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⁺ Jh ⁴⁺ , YF ₃ : Tm ³⁺ , Yb ³⁺ ,

(Y ₁ Gd) BO ₃ ) Eu, (Y ₁ Gd) BO ₃ ) Tb, (Y ₁ Gd) ₂ O ₃ ) Eu ³⁺ , Y _{1 34} Gd _{0 60} O ₃ (Eu ₁ Pr) ₁ Y ₂ O ₃ ) Bi ³⁺ , YOBr) Eu ³⁺ , Y ₂ O ₃ ) Ce ₁ Y ₂ O ₃ ) Er ³⁺ , Y ₂ O ₃ ) Eu ³⁺ (YOE),

Y ₂ O ₃ ) Ce ³⁺ Jb 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⁺ Jb ³⁺ , YPO ₄ ) Eu ³⁺ , YPO ₄ ) Mn ²⁺ Jh ⁴⁺ , YPO ₄ ) V ⁵⁺ , Y (P ₁ V) O ₄ ) Eu ₁

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 ₁ Be) ₂ SiO ₄ ) Mn ²⁺ , Zn _{0 4} Cd _{0 6} S) Ag,

Zn _{0 6} Cd _{0 4} S) Ag ₁ (Zn ₁ Cd) S) Ag ₁ Cl, (Zn ₁ 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 ₁ 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 ₁ Cu ₁ Cl ₁ ZnS) Ag ₁ Ni, ZnS) Au ₁ In, ZnS-CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25), ZnS-CdS) Ag ₁ Br ₁ Ni, ZnS-CdS: Ag ⁺ , CI, ZnS-CdS) Cu ₁ Br, ZnS-CdS) Cu ₁ I, ZnS) Cl ^" , ZnS) Eu ²⁺ , ZnS) Cu, ZnS: Cu \ Al ³⁺ , ZnS: Cu ⁺ , Cl ^" , ZnS ) Cu ₁ Sn ₁ ZnS) Eu ²⁺ , ZnS) Mn ²⁺ , ZnS) Mn ₁ Cu, ZnS) Mn ²⁺ ²⁺ , ZnS) P,

ZnS: P ³ , Cr, ZnS) Pb ²⁺ , ZnS: Pb ²⁺ , Cr, ZnS) Pb ₁ Cu ₁ 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 IMn ₁ 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 ⁺ , ZnSTe ₁ Mn, ZnS-ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , Cl, ZnWO ₄

The following examples are intended to illustrate the present invention. However, they are by no means to be considered limiting. Any compounds or components that can be used in the formulations are either known and commercially available or can be synthesized by known methods. Those given in the examples

Temperatures are always ⁰ C. It goes without saying that both in the description and in the examples, the added amounts of the components in the compositions always add up to a total of 100%. Given percentages are always to be seen in the given context. However, they usually refer to the mass of the specified partial or total quantity.

Examples

Example 1: Preparation of 5 g Sr ₅₁₉₄ EUo _1O eSJaOeN ₄

6.8112 g of SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0689 g of Eu ₂ O ₃ (Treibacher, 99.99%) and 0.9159 g of α-Si ₃ N ₄ (UBE, 99%) are packed in dry N ₂

Glove box in an agate mortar thoroughly mixed together. The raw material mixture thus obtained is transferred into a Mo foil-lined Al ₂ O ₃ boat. The mixture is heated at 1200 - 1600 ⁰ C for 8 hours under N ₂ / H ₂ / NH ₃ atmosphere

Example 2: Preparation of 5 g Sr5.9 ₄ Euo, o6 _Si3θ 5l 88N ₄ Fo, 24 6.6736 g SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0689 g Eu ₂ O ₃ (Treibacher, 99.99%), 0.0984 g SrF ₂ (Aldrich, 99.998%) and 0.9159 g Ci-Si ₃ N ₄ (UBE, 99 %) are mixed thoroughly in an agate mortar with a dry N ₂ glove box. The resulting mixture of raw materials is transferred into a Mo foil-lined Al ₂ O ₃ boat. The mixture is heated at 1200 - 1600 ⁰ C for 8 hours under N ₂ / H ₂ / NH ₃ atmosphere.

Example 3: Preparation of 5 g of Sr ₅₁₉₄ EuO ₁₀₆ Si ₃ O ₅₁₈ SN ₄ CIc ₂₄

6.6168 g of SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0683 g of Eu ₂ O ₃ (Treibacher, 99.99%), 0.1231 g of SrCl ₂ (Alfa Aesar, 99.5%) and 0.9081 g of Ct-Si ₃ N ₄ (UBE, 99%) are packed in a glove box filled with dry N ₂

Agate mortar thoroughly mixed together. The thus obtained

Raw material mixture is transferred to a Mo foil-lined Al ₂ O ₃ boat. The mixture is heated at 1200 - 1600 ⁰ C for 8 hours under N ₂ / H ₂ / NH ₃ atmosphere.

Example 4: Preparation of ₅ g of Sr ₅₁₈₂ Th ₀₁₀₆ Eu _01O eSi ₃ O ₆ N ₄

6.6444 g of SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0686 g of Eu ₂ O ₃ (Treibacher, 99.99%), 0.1030 g of ThO ₂ (Merck, 99%) and 0.9119 g of Ci-Si ₃ N ₄ (UBE, 99 %) are mixed thoroughly in an agate mortar with a dry N ₂ glove box. The resulting mixture of raw materials is transferred into a Mo foil-lined Al ₂ O ₃ boat. The mixture is heated at 1200 - 1600 ⁰ C for 8 hours under N ₂ / H ₂ / NH ₃ atmosphere.

Example 5: Preparation of 5 _g Sr ₅₁₈₂ Os _01O eEu _01O eSi ₃ O ₆ N ₄ 6.6658 g of SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0688 g of Eu ₂ O ₃ (Treibacher, 99.99%), 0.0869 g of OsO ₂ (Alfa Aesar, Os 83% min) and 0.9148 g of Q-Si ₃ N ₄ ( UBE, 99%) are placed in a glove box filled with dry N ₂ in one

Agate mortar thoroughly mixed together. The thus obtained

Example 6: Preparation of ₅ g of Sr _{5 82} Ru _{0 O} eEu _{0 O} eSi ₃ O ₆ N ₄

6.7129 g of SrC ₂ O ₄ (Alfa Aesar, 95%), 0.0693 g of Eu ₂ O ₃ (Treibacher, 99.99%), 0.0524 g of RuO ₂ (Alfa Aesar, 99.9%) and 0.9213 g of Ci-Si ₃ N ₄ (UBE, 99%) are placed in a dry N ₂ -filled glove box in one

Agate mortar thoroughly mixed together. The thus obtained

Example 7: High pressure sintering of the phosphors of Examples 1-6

In each case 5 g of the compound from Examples 1-6 are filled into an MO crucible and transferred to a high-pressure sintering furnace. In this, the samples are heated at a nitrogen pressure of 40-70 bar and a heating ramp of 5-10 K / min to a temperature of 1400-1600 ⁰ C, the holding time is 6-10 hours. Example 8: Hot isostatic pressing of the phosphors from the

Examples 1-6 In each case 5 g of the compounds from Examples 1-6 are transferred to an isostatic hot press. The hot press is placed under vacuum and the temperature is raised to 200 ° C. Subsequently, the temperature is increased at 5-10 K / min to 1400-1600 ⁰ C, at the same time, the pressure is readjusted to values between 50 and 200 MPa, the holding time is 6-10 hours.

Example 9: Washing the phosphors of Examples 1-8

In each case 5 g of the compounds from Examples 1-8 are suspended in 100 ml of 1 molar hydrochloric acid and stirred for 3 hours at room temperature. The residue is then filtered off with suction and washed neutral with demineralized water. The washed residue is then suspended in 100 ml of a 1 molar KOH solution and stirred for a further 30 minutes.

The residue is then filtered off with suction and washed again with deionized water until neutral.

Tab. 1: Optical properties of Sr _{5 94} Eu _{0 O} eSi _S OeN ₄ IEu (as a reference) and co-doped phosphors according to the invention

Description of the pictures

In the following the invention will be explained in more detail with reference to several embodiments. Show it:

1 shows a COB (chip on board) package of the type InGaN, which serves as light source (LED) for white light (1 = semiconductor chip, 2.3 = electrical connections, 4 = conversion luminescent material, 7 = board (board) . Of the

Phosphor is dispersed in a binder lens, which simultaneously constitutes a secondary optical element and influences the light emission characteristic as a lens.

2 shows a COB (chip on board) package of the type InGaN, which serves as a light source (LED) for white light (1 = semiconductor chip, 2.3 = electr.

Connections; 4 = conversion phosphor; 7 = board (board) The

Phosphor is distributed in a thin binder layer directly on the LED chip. A secondary optical element consisting of a transparent material can be placed thereon.

Fig.3: shows a Golden Dragon ^® Package that as the light source (LED) for white light (1 = semiconductor chip; 2,3 = electrical connections; 4 =.

Conversion luminescent material in cavity with reflector). The conversion phosphor is dispersed in a binder, the mixture filling the cavity.

Fig. 4: shows an SMD package (Surface mounted package) where 1 = housing; 2, 3 = electr. Connections, 4 = conversion layer means. The semiconductor chip is completely covered with the phosphor according to the invention. The SMD design has the advantage that it has a small design and thus fits into conventional luminaires. FIG. 5: shows a schematic illustration of a light emitting diode with 1 =

Semiconductor chip; 2,3 = electr. Connections; 4 = conversion luminescent material, 5 = bonding wire, wherein the luminescent material is applied in a binder as Top Globe. This form of phosphor / binder layer may act as a secondary optical element and may be e.g. B. influence the light propagation.

FIG. 6: shows a schematic illustration of a light-emitting diode with 1 =

Semiconductor chip; 2,3 = electr. Connections; 4 = conversion luminescent material, 5 =

Bonding wire, wherein the phosphor is applied as a thin layer dispersed in a binder. A further component acting as a secondary optical element, such as a lens, can easily be applied to this layer.

Fig. 7: shows an example of a further application, as already known in principle from US Pat. No. 6,700,322. In this case, the phosphor according to the invention is used together with an OLED. The light source is an organic light-emitting diode 31, consisting of the actual organic film 30 and a transparent substrate 32. The film 30 emits in particular blue primary light, produced for example by means of PVK: PBD: coumarin (PVK, abbreviation for poly (n-vinylcarbazole) PBD, abbreviation for 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1, 3,4-oxadiazole)). The emission is partially converted into a yellow, secondarily emitted light by a cover layer, formed from a layer 33 of the phosphor according to the invention, so that a white emission is achieved overall by color mixing of the primary and secondary emitted light. The OLED consists essentially of at least one layer of a light-emitting

Polymer or so-called. Small molecules between two electrodes, which consist of known materials, such as ITO (abbr

"Indium tin oxide") as an anode and a highly reactive metal, such as Ba or Ca, as a cathode. Often, several layers are used between the electrodes, which either serve as a hole transport layer or serve as electron transport layers in the area of the "small molecules." Polyfluorene or polyspiro materials, for example, are used as emitting polymers.

Claims

claims

1. Compound of the 6-3-6-4 alkaline earth silicooxynitride type with europium doping, which additionally contains co-dopants from the series Th, Ru, Os, F and / or Cl.

2. A compound according to claim 1, characterized by the formula I.

(Ca ₁ Sr ₁ Ba) _6-X (Si _{1 -V} Me ₇ J ₃ (O _1-2 Ma ₂ _Z ) ₆ N ₄ : Eu _x (I)

in which

Me = Th, Ru and / or Os

Ma = F and / or Cl

x <0.5

y <1 and

z <0.1

is.

3. A compound according to claim 1 and / or 2, characterized in that x = 0.003 to 0.2, y = 0.0001 to 0.2 and z = 0.0005 to 0.03.

4. A compound according to one or more of claims 1 to 3, characterized

in that x = 0.005 to 0.15 and / or y = 0.001 to 0.02.

5. A compound according to one or more of claims 1 to 5, obtainable by mixing silicon nitride, europium and calcium and / or strontium and / or barium-containing educts with at least one

Thorium, osmium, ruthenium, fluoride and / or chloride-containing Co dopant by solid-state diffusion methods and subsequent thermal aftertreatment.

6. A process for preparing a compound according to one or more of claims 1 to 5 with the following process steps:

a) preparing a europium-doped 6-3-6-4 alkaline earth silicooxynitride compound which is co-doped with thorium, ruthenium, osmium, fluoride and / or chloride containing materials by mixing at least 4

Starting materials selected from silicon nitride, europium, calcium, strontium, barium, thorium, ruthenium, osmium, fluoride and / or chloride-containing materials,

b) Thermal aftertreatment of the thorium, ruthenium, osmium, fluoride and / or chloride co-doped compound.

c) washing the thermally treated compounds with an HCl and a KOH solution.

7. Shaped body comprising a compound according to one or more of claims 1 to 5, characterized in that it has a rough surface, the nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ and / or Y ₂ O. ₃ or mixed oxides thereof and / or particles with the compound according to one or more of claims 1 to 5 with or without dopants from the series europium, thorium, ruthenium, osmium, fluorine and / or chlorine carries.

8. Shaped body containing a compound according to one or more of claims 1 to 5, characterized in that it has a closed surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3, ZnO _, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or from the compound according to one or more of claims 1 to 5 without the activator europium.

9. Shaped body containing a compound according to one or more of claims 1 to 5, characterized in that it is a porous

Has surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3, ZnO _, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or from the compound according to one or more of claims 1 to 5 with or without dopants Europium, thorium, ruthenium, osmium, fluorine and / or chlorine.

10. Shaped body containing a compound according to one or more of claims 1 to 5, characterized in that the surface

carries functional groups, which allows a chemical or physical connection to the environment, preferably consisting of epoxy or silicone resin.

11.A method for producing a shaped article according to one or more of claims 8 to 10 with the following method steps:

a) preparing a 6-3-6-4 europium-doped alkaline earth silicooxynitride compound which is co-doped with thorium, ruthenium, osmium, fluoride and / or chloride containing materials by mixing at least 4 starting materials selected from silicon nitride, europium, calcium, strontium,

Barium, thorium, ruthenium, osmium, fluorine and / or chlorine-containing materials,

b) thermal aftertreatment of the thorium, ruthenium, osmium, fluorine and / or chlorine codoped compound,

c) coating the surface with nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O _3,

ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof or with nanoparticles of the compound according to one or more of claims 1 to 5 with or without dopants.

12. The method according to claim 11, characterized in that after

Process step b) is still a washing step with a HCl and a KOH solution.

13. Lighting unit with at least one primary light source whose

Emission maximum in the range 250 nm to 530 nm, preferably between 350 nm and 500 nm, wherein this radiation is partially or completely converted into longer-wave radiation by a compound and / or phosphor body according to one or more of claims 1 to 10.

14. Lighting unit according to claim 13, characterized in that it is at the light source to a luminescent

Indiumaluminum gallium nitride, in particular the formula InjGa _j Al _k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1.

15. Lighting unit according to claim 13, characterized in that the light source is a luminescent compound based on ZnO, TCO (Transparent conducting oxide), ZnSe or SiC.

16. Illumination unit according to claim 13, characterized in that the light source is a material based on an organic light-emitting layer.

17. Lighting unit according to claim 13, characterized in that it is the light source is a plasma or discharge lamp.

18. Lighting unit according to one or more of claims 13 to 17, characterized in that the phosphor is arranged directly on the primary light source and / or away from it.

19. Lighting unit according to one or more of claims 13 to 18, characterized in that the optical coupling between the

Phosphor and the primary light source is realized by a light-conducting arrangement.

20. Use of at least one compound according to one or more of claims 1 to 5 as a phosphor.

21. Use of at least one compound according to one or more of claims 1 to 5 as a conversion phosphor for the partial or complete conversion of the blue or in the near UV emission of a light emitting diode.

22. Use of at least one compound according to one or more of claims 1 to 5 as a conversion phosphor for the conversion of the primary radiation into a specific color point according to the color on demand concept.

23. Use of a shaped body according to one or more of claims 7 to 10 as a phosphor body.