EP2935510A1

EP2935510A1 - Phosphors

Info

Publication number: EP2935510A1
Application number: EP13799214.5A
Authority: EP
Inventors: Ralf Petry; Holger Winkler; Aleksander ZYCH; Christof Hampel; Andreas Benker
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2012-12-21
Filing date: 2013-12-02
Publication date: 2015-10-28
Also published as: CN104870605A; TW201435046A; KR20150100801A; US20160152891A1; WO2014094974A1; JP2016507605A

Abstract

The invention relates to compounds comprising an anionic scaffold structure, dopants and cations, in which a. the anionic scaffold structure features coordination tetrahedra GL4, where G stands for silicon, which may be partly replaced by C, Ge, B, Al or In, and L stands for N and O, with the proviso that N makes up at least 60 atom% of L; b. the cations are selected from the alkaline earth metals, with the proviso that strontium and barium together make up less than 75 atom% of the cations; c. dopant present comprises trivalent cerium or a mixture of trivalent cerium and divalent europium; d. charge compensation of the cerium doping is accomplished i) through corresponding replacement of alkaline earth metal cations by alkali metal cations, and/or ii) by a corresponding increase in the nitrogen content, and/or iii) by a corresponding reduction in the cations; and to processes for preparing these compounds, and to their use as conversion phosphors.

Description

phosphors

The present invention relates to novel compounds, a process for their preparation and their use as conversion phosphors. The present invention also relates to an emission-converting material comprising at least the invention

Conversion luminescent material and its use in light sources, in particular so-called pc-LEDs (phosphor converted light emitting devices). Further objects of the present invention are

Light sources, in particular pc LEDs, and lighting units containing a primary light source and the emission-converting material according to the invention.

For more than 100 years, inorganic phosphors have been developed to spectrally adapt emissive screens, X-ray amplifiers, and radiation or light sources to meet the requirements of each

Application area as optimally meet and at the same time consume as little energy. The nature of the excitation, i. the nature of the primary radiation source and the required emission spectrum are crucial for the selection of host lattices and activators.

Especially for fluorescent light sources for general lighting, ie for low-pressure discharge lamps and light emitting diodes, new phosphors are constantly being developed in order to further increase energy efficiency, color rendering and stability.

To obtain white emitting inorganic LEDs (light emitting diodes) through additive color mixing, there are basically three different approaches:

(1) The so-called RGB LEDs (red + green + blue LEDs), in which white light by mixing the light of three different emitting in the red, green and blue spectral range

Light emitting diodes is generated. (2) The systems UV LED + RGB phosphor, in which a semiconductor emitting in the UV range (primary light source) emits the light to the environment, in the three different phosphors

(Conversion phosphors) are excited to emit in the red, green and blue spectral range.

(3) So-called complementary systems in which an emissive semiconductor (primary light source) emits blue light, for example, which excites one or more phosphors (conversion luminescent material) to emit light in the yellow area, for example. By mixing the blue and the yellow light then z. B. white light.

Binary-complementary systems have the advantage that they can be used with only one primary light source and - in the simplest case - with only one

Conversion luminescent are able to produce white light. The best known of these systems consists of an indium-aluminum nitride chip as a primary light source emitting light in the blue spectral range, and a cerium-doped yttrium-aluminum garnet (YAG: Ce) as

Conversion luminescent, which is excited in the blue area and emits light in the yellow spectral range. However, improvements in the color rendering index as well as the stability of the color temperature are

desirable.

Thus, when using a blue-emitting semiconductor as the primary light source, these so-called binary-complementary systems require a yellow conversion luminescent substance or green and red-emitting one

Conversion phosphors to reflect white light. Alternatively, using a semiconductor emitting in the violet spectral region or in the near UV spectrum as the primary light source, either an RGB phosphor mixture or a dichroic mixture of two complementary light emitting conversion phosphors must be used to obtain white light.

When using a system with a primary light source in the violet or UV range and two complementary conversion phosphors, light emitting diodes with a particularly high lumen equivalent to be provided. Another advantage of a dichromatic

Phosphor mixing is the lower spectral interaction and the associated higher "package gain".

Therefore, in particular inorganic fluorescent powders, which can be excited in the blue and / or UV region of the spectrum, are becoming increasingly important as conversion phosphors for light sources, in particular for pc LEDs.

Meanwhile, many conversion phosphors are known, for example, alkaline earth orthosilicates, thiogallates, garnets, and nitrides each doped with Ce ³⁺ or Eu ²⁺ .

However, there is a constant need for new conversion phosphors that can be excited in the blue or UV range, and then deliver light in the visible range, especially in the yellow spectral range.

A first embodiment of the present invention is therefore a compound containing an anionic skeleton structure, dopants and cations, wherein

a. the anionic skeleton structure of coordination tetrahedra GL ₄ - is characterized in which G is silicon which may be partially replaced by C, Ge, B, Al or In and L is N and O, with the proviso that N is at least 60 atomic% of L, b. the cations are selected from the alkaline earth metals, with the proviso that strontium and barium together make up less than 75 atomic% of the cations,

c. as a dopant trivalent cerium or a mixture of

trivalent cerium and divalent europium,

d. the charge balance of the cerium doping i) over a

appropriate replacement of alkaline earth cations by alkali cations and / or ii) via a corresponding increase in the

Nitrogen content and / or iii) a corresponding reduction of alkaline earth cations takes place. The term anionic skeleton structure refers to the structural motif in the composition in which G is usually in

Coordinated tetrahedra is present. These tetrahedra can be linked together via one or more common L atoms and so on

form extended anionic Teilstrukturelemete in the solid. Corresponding structural motifs are usually with

Crystallographic methods for structure determination or detected by spectroscopic methods and are well known to those skilled in particular from the silicate chemistry.

In general, the structure determination is inorganic

Solid state materials based on a combination of crystallographic data, possibly spectroscopic data and information about the

Element composition, which may result from quantitative reaction either from the composition of the starting materials or by

Methods of elemental analysis is determined. Corresponding methods are well established in chemical analysis and can therefore be considered the

Be known to one skilled in the art. Quantities in atomic% refer to ratios of atoms of certain chemical elements to larger groups, which are usually the same

Can occupy lattice sites in crystal structures, such as

Nitrogen and oxygen as L.

The compounds according to the invention are usually excitable in the blue spectral range, preferably at 450 nm, and usually emit in the yellow spectral range. In this case, the compounds according to the invention otherwise have properties comparable to those of 2-5-8-nitrides, these having substantially lower requirements with regard to oxygen content and pure phase purity to the production processes or having a lower sensitivity to moisture. In the context of this application is defined as emission in the red or red light such light whose intensity maximum between 600 nm and 670 nm wavelength is correspondingly green or emission in the green region such light is called, the maximum between 508 nm and 550 nm wavelength lies and as yellow green or emission in the yellow area such light whose maximum lies between 551 nm and 599 nm wavelength.

In a preferred variant of the invention, the alkaline earth metal cations are strontium, magnesium, calcium and / or barium, with calcium and magnesium together making up 25 atomic% or more of the alkaline earth metal cations and calcium and magnesium together in the same or an alternative embodiment from 30 at% to 80 at% of the alkaline earth metal cations.

In a further alternative or identical variant of the invention, magnesium is present as one of the alkaline earth metal cations.

G stands in the same or another variant of the invention more of 80 atomic% of silicon or more of 90 atomic% of silicon. It may also be preferred according to the invention if G is formed by silicon. Alternatively, it may be preferred if silicon is partially replaced by C or Ge.

In particular, the compound according to the invention may be a compound,

A2-0.5y-x + 1, 5zMo, 5xCeo, 5xG5N8-y + _z Oy (| _a ) where

A is one or more elements selected from Ca, Sr, Ba, Mg, M is one or more elements selected from Li, Na, K,

G is Si, which may be partially replaced by C, Ge, B, Al or In, x is a value in the range of 0.005 to 1 and y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

Alternatively, the compound according to the invention may be a compound of the formula Ib,

A2-0,5y-0,75x + 1.özCeo.SxGöNs-y + zOy (| t>)

act, being

A is one or more elements selected from Ca, Sr, Ba, Mg,

M is one or more elements selected from Li, Na, K,

G is Si, which may be partially replaced by C, Ge, B, Al or In, x is a value in the range of 0.005 to 1 and

y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

Alternatively, the compound according to the invention may be a compound of the formula Ic,

A2-0,5y ₊ 1,5zCeo, 5xG5N8 ₊ 0.5x ₊ y-zO _y (Ic)

act, being

A is one or more elements selected from Ca, Sr, Ba, Mg,

M is one or more elements selected from Li, Na, K,

y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

In said compounds of formulas Ia, Ib and Ic, it may be desirable for x to be in the range of 0.01 to 0.8, alternatively in the range of 0.02 to 0.7, and further alternatively in Range 0.05 to 0.6.

At the same time or alternatively, it may be desirable for y to be in the range of 0.1 to 2.5, preferably in the range of 0.2 to 2, and more preferably in the range of 0.22 to 1.8. At the same time or alternatively, it may be desirable for z to represent the value 0, or a value from the range of 0.1 to 2.5, preferably from the range 0.2 to 2 and particularly preferably from the range 0.22 to 1.8. It has proved to be essential according to the invention that cerium is present as dopant. In various variants of the invention, cerium may be the only dopant or be used in combination with other dopants. The dopants used in this case are customary 2- or 3-valent rare earth ions or subgroup metal ions. In a variant, it is preferred if europium is present in addition to cerium in the dopant. In this variant, it has been found to increase stability when the cations contain barium so that this combination may be preferred. The compound may be present as a pure substance or in a mixture. Another object of the present invention is therefore a mixture containing at least one compound as defined above, and at least one further silicon and oxygen-containing compound. In such mixtures, the compound is usually one

Weight fraction from the range of 30 to 95 wt .-%, preferably from the range of 50 to 90 wt .-% and particularly preferably from the range of 60 to 88 wt .-%. The at least one compound containing silicon and oxygen in preferred embodiments of the invention are X-ray amorphous or glassy phases, which are distinguished by a high silicon and oxygen content but may also contain metals, in particular alkaline earth metals, such as strontium. In this case, it may again be preferred if these phases completely or partially envelop the particles of the compound. According to the invention, it is preferred if the at least one further silicon-containing and oxygen-containing compound is a reaction by-product of the preparation of the compound and this does not affect the application-relevant optical properties of the compound.

Therefore, a mixture containing a compound of the formula I which is obtainable by a process in which in a step a) suitable starting materials selected from binary nitrides, halides and oxides or corresponding reactive forms are mixed thereto and the mixture in a step b ) is thermally treated under reductive conditions, a further subject of the invention.

The corresponding process for the preparation of the compounds and the inventive use of the compounds as a phosphor or conversion luminescent material, in particular for partial or complete

Conversion of the blue or in the near UV emission of a primary light source, preferably a light emitting diode or a laser, are further subjects of the invention. In the following, the compounds according to the invention are also referred to as

Refers to phosphors.

Inventive compounds used in small amounts already give good LED qualities. The LED quality is over usual parameters, such as the Color Rendering Index, the Correlated

Color temperature, lumen equivalents or absolute lumens, or the color point in CIE x and CIE y coordinates described.

Color rendering index, or CRI, is a unitary photometric quantity known to those skilled in the art, which is the color fidelity of an artificial light source to that of sunlight Filament light sources compare (the latter two have a CRI of 100).

The CCT or Correlated Color Temperature is a photometric quantity with the unit Kelvin familiar to the person skilled in the art. The higher the numerical value, the colder the viewer sees the white light of an artificial radiation source. The CCT follows the concept of the black light emitter, whose color temperature is the so-called Planckian curve in the CIE diagram.

The lumen equivalent is a photometric quantity known to the person skilled in the art with the unit Im W, which describes how large the photometric luminous flux in lumens of a light source is at a certain radiometric radiation power with the unit Watt. The higher the lumen equivalent, the more efficient a light source is.

The lumen is a photometrical photometric quantity which is familiar to the person skilled in the art and describes the luminous flux of a light source, which is a measure of the total visible radiation emitted by a radiation source. The larger the luminous flux, the brighter the light source appears to the observer.

CIE x and CIE y represent the coordinates in the familiar CIE standard color diagram (in this case normal observer 1931), which describes the color of a light source.

All the variables listed above are calculated from emission spectra of the light source according to methods familiar to the person skilled in the art.

The excitability of the phosphors according to the invention also extends over a wide range, ranging from about 410 nm to 530 nm, preferably 430 nm to about 500 nm. A further advantage of the phosphors according to the invention is the stability to moisture and water vapor, which can pass through diffusion processes from the environment into the LED package and thus to the surface of the phosphor as well as the stability to acidic media, as by-products during curing of the binder in the LED package or as additives in the LED package. In this case, preferred phosphors according to the invention have stabilities which are higher than the hitherto customary nitride phosphors.

The phosphors according to the invention can be analogous to previously known

Processes for the production of non-doped or Eu-doped nitrides and oxynitrides are carried out, whereby the skilled person has no problems replacing the respective Eu source with a corresponding cerium source.

Known processes for the preparation of M ₂ Si ₅ N ₈ : Eu are, for example:

(1) (2-x) M + x Eu + 5 Si (NH ₂ ) -> M _2- xEu _x Si ₅ N 8 + 5 H ₂

(Schnick et al., Journal of Physics and Chemistry of Solids (2000), 61 (12), 2001-2006)

(2) (2-x) M ₃ N ₂ + 3x EuN + 5 Si ₃ N ₄ -> 3 M ₂ -xEu _x Si ₅ N 8 + 0.5x N ₂

(Hintzen et al., Journal of Alloys and Compounds (2006), 417 (1-2), 273-279)

(3) (2-x) MO + 1, 666 Si ₃ N ₄ + 0.5x Eu ₂ O ₃ + (2 + 0.5x) C + 1, 5 N ₂ - »

M _2-x EuxSi ₅ N ₈ + (2 + 0.5x) CO

(Piao et al., Applied Physics Letters 2006, 88, 161908)

(4) 2 Si ₃ N ₄ + 2 (2-x) MCO ₃ + x / 2 Eu ₂ O ₃ - M _2-x Eu _x Si ₅ N ₈ + M ₂ SiO ₄ + CO ₂ (Xie et al. Chemistry of Materials, 2006, 18, 5578)

(5) (2-x) M + x Eu + 5 SiCl ₄ + 28 NH ₃ -> M _2-x Eu _x Si ₅ N ₈ + 20 NH ₄ Cl + 2 H ₂ (Jansen et al., WO 2010 / 029184 A1). Silicooxynitrides are accessible, for example, by stoichiometric mixing of SiO 2, M 3 N 2, Si 3 N 4 and EuN and subsequent calcination at temperatures of about 1600 ° C. (for example according to WO 2011/091839).

Of the above methods for the production of silicon nitrides, the method (2) is particularly suitable because the corresponding starting materials are commercially available, in the synthesis no secondary phases and the efficiency of the resulting materials is high.

In a process according to the invention for the production of phosphors according to the invention, suitable starting materials selected from binary nitrides, halides and oxides or corresponding reactive forms are therefore mixed in step a) and the mixture is thermally treated under non-oxidizing conditions in step b).

In this process, often a second calcination step is connected, which increases the efficiency of the material even more. In this second calcination step, it may be helpful to add alkaline earth nitrite. Here, in a variant of the invention presintered oxynitride to Erdalkalinitrid in the ratio 2: 1 to 20: 1, in an alternative variant in the ratio 4: 1 to 9: 1 used. With this Nachkalzination the emission maximum of the target compound can shift, so that a targeted Erdalkalinitridzusatz can be used to set a desired emission maximum exactly.

The reaction in step b) and also the optional postcalzination are usually carried out at a temperature above 800.degree. C., preferably at a temperature above 1200.degree. C. and particularly preferably in the range from 1400.degree. C. to 1800.degree. Usual durations for these steps are 2 to 14 hours, alternatively 4 to 12 hours and again alternatively 6 to 10 hours. The non-oxidizing conditions are set here, for example, with inert gases or carbon monoxide, forming gas or hydrogen or vacuum or oxygen-deficient atmosphere, preferably in a nitrogen stream, preferably in the N ₂ / H ₂ stream and particularly preferably in N ₂ / H ₂ / NH ₃ - Current adjusted.

The calcining can be carried out, for example, so that the resulting mixtures are introduced, for example, in a vessel made of boron nitride in a high-temperature furnace. The high-temperature furnace is in a preferred embodiment, a tube furnace, which is a carrier plate

Molybdenum foil contains.

After calcination, the compounds obtained are treated in a variant of the invention with acid to wash unreacted alkaline earth metal nitride. Hydrochloric acid is preferably used as the acid. Here, the resulting powder is suspended, for example, for 0.5 to 3 hours, more preferably 0.5 to 1.5 hours in 0.5 molar to 2 molar hydrochloric acid, more preferably 1 molar hydrochloric acid, then filtered off and at a temperature in the range of 80 to 150 ° C dried.

In a further alternative embodiment of the invention, after the calcination and the workup, which can be carried out by acid treatment as described above, another calcination step is connected again. This preferably takes place in a temperature range from 200 to 400.degree. C., more preferably from 250 to 350.degree. This further

Calcination step is preferably carried out under a reducing atmosphere. The duration of this calcination step is usually between 15 minutes and 10 hours, preferably between 30 minutes and 2 hours. In yet another embodiment, the compounds obtained by any of the above-mentioned methods of the invention can be coated. All coating processes are suitable for this purpose. as known to those skilled in the art and used for phosphors according to the prior art. Suitable materials for the coating are, in particular, metal oxides and nitrides, in particular earth metal oxides, such as Al 2 O 3, and earth metal nitrides, such as AlN, and also SiO 2. The coating can be carried out, for example, by fluidized bed processes. Further suitable coating methods are known from JP 04-304290, WO 91/10715, WO 99/27033, US 2007/0298250, WO 2009/065480 and WO 2010/075908.

Another object of the present invention is a light source with at least one primary light source containing at least one compound of the invention. The emission maximum of the normal light source is usually in the range from 410 nm to 530 nm, preferably 430 nm to about 500 nm. Particular preference is given to a range between 440 and 480 nm, the primary radiation partially or completely converted by the phosphors according to the invention into longer-wave radiation becomes.

In a preferred embodiment of the light source according to the invention, the primary light source is a luminescent indium-aluminum gallium nitride, in particular of the formula

LniGa _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 of different construction.

In a further preferred embodiment of the light source according to the invention, the primary light source is a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC or else an arrangement based on an organic light-emitting layer (OLED). In a further preferred embodiment of the light source according to the invention, the primary light source is a source which exhibits electroluminescence and / or photoluminescence. Furthermore, the primary light source can also be a plasma or discharge source.

Corresponding light sources according to the invention are also referred to as light-emitting diodes or LEDs. The phosphors according to the invention can be used individually or as a mixture with the following phosphors familiar to the person skilled in the art. Corresponding phosphors which are suitable in principle for mixtures are, for example:

Ba ₂ Si0: Eu ^2+, BaSi ₂ 0 _5: Pb ^2+, Sr _1-x Ba _x F2: Eu ^2+, BaSrMgSi ₂ 0 _7: Eu ^2+, BaTiP ₂ 0 _7, (Ba, Ti) ₂ P ₂ 0 ₇ : Ti, Ba ₃ W0 ₆ : U, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ SiO ₄ : Mn ² \ Bi ₄ Ge ₃ 0 ₁₂ ,

CaAl ₂ 0 ₄ : Ce ³⁺ , CaLa ₄ 0 ₇ : Ce ³⁺ , CaAl ₂ 0 ₄ : Eu ²⁺ , CaAl ₂ 0 ₄ : Mn ²⁺ , CaAl ₄ 0 ₇ : Pb ²⁺ , Mn ²⁺ , CaAl ₂ 0 ₄ : Tb ³⁺ , Ca ₃ Al ₂ Si ₃ Oi ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ 0i ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ 0, ₂ : Eu ²⁺ , Ca ₂ B ₅ O ₉ Br: Eu ²⁺ , Ca ₂ B ₅ O ₉ CI: Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl: Pb ²⁺ , CaB ₂ O ₄ : Mn ²⁺ , Ca ₂ B ₂ O ₅ : Mn ²⁺ , CaB ₂ O ₄ : Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ⁺ , Ca ₅ B ₂ SiO ₁₀ : Eu ³⁺ ₎ Ca ₂ Ba ₃ (PO ₄ ) ₃ CI: Eu ²⁺ ,

CaBr ₂ : Eu ²⁺ in Si0 _2l 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 0: Mn ²⁺ , CaGa ₄ 0 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 Si0 ₂ , CaLaB0 ₄ : Eu ³⁺ , CaLaB ₃ O ₇ : Ce ³⁺ , Mn ²⁺ ,

Ca ₂ La ₂ B0 ₆ . _5: Pb ^2+, Ca ₂ MgSi ₂ 0 _7, Ca ₂ MgSi ₂ 0 _7: Ce ^3+, CaMgSi ₂ O _6: Eu ^2+, Ca ₃ MgSi ₂ 0 _8: Eu ^2+, Ca ₂ MgSi ₂ 0 ₇ Eu ²⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Mn ²⁺ ,

Ca ₂ MgSi ₂ 0 _7: Eu ^2+, Mn ^2+, CaMo0 _4, CaMoO _4: Eu ^3+, CaO: Bi ^3+, CaO: Cd ^2+, CaO: Cu ^+, CaO: Eu ^3+, CaO: Eu ³⁺ , Na ⁺ , CaO: Mn ²⁺ , CaO: Pb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaO: Tb ³⁺ , CaO: TI, CaO: Zn ²⁺ , Ca ₂ P ₂ 0 _7: Ce ^3+, cc-Ca ₃ (P0 ₄₎ _2: Ce ^3+, beta-Ca ₃ (PO ₄₎ _2: Ce ^3+, Ca ₅ (P0 ₄₎ ₃ Cl: Eu ^2+, Ca ₅ (PO ₄₎ ₃ Cl: Mn ^+, Ca ₅ (PO ₄₎ ₃ Cl: Sb ^3+, Ca ₅ (P0 ₄₎ ₃ Cl: Sn ^2+, beta-Ca ₃ (PO ₄₎ _2: Eu ²⁺ , Mn ^2+, Ca ₅ (PO ₄₎ ₃ F: Mn ^2+, Ca _s (P0 ₄₎ ₃ F: Sb ^3+, Ca _s (PO ₄₎ ₃ F: Sn ^2+, a-Ca ₃ (P0 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 0 _6: Mn ^2+, a-Ca ₃ (P0 ₄₎ _2: Pb ^2+, a-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⁺ CaS: Pb ²⁺ , CaS: Pb ²⁺ , CI, CaS: Pb ²⁺ , Mn ²⁺ , CaS: Pr 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 Si0 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 (P0 ₄ ) ₂ : Bi ³⁺ , β- (Ca, Sr) ₃ (PO ₄ ) ₂ : Sn ²⁺ Mn ²⁺ CaTi ₀ . ₉ Al ₀ .iO ₃ : Bi ³⁺ , CaTi0 ₃ : Eu ³⁺ , CaTi0 ₃ : Pr ³⁺ , Ca ₅ (V0 ₄ ) ₃ Cl, CaW0 ₄ CaW0 ₄ : Pb ²⁺ , CaW0 ₄ : W, Ca ₃ W0 ₆ : U, CaYAI0 ₄ : Eu ³⁺ , CaYB0 ₄ : Bi ³⁺

CaYB0 ₄ : Eu ³⁺ , CaYBo. ₈ 0 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, Mg) SrAI _† Oi ₈ : Ce, CeMgAlnOi ₉ : Ce: Tb Cd ₂ B ₆ On: Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: In, CdS: In, CdS: In, Te, CdS: Te, CdW0 ₄ CsF, Csl, Csl: Na ⁺ , Csl: TI, (ErCl ₃ ) ₀ . ₂ 5 (BaCl ₂ ) ₀ .75, GaN: Zn, Gd ₃ Ga ₅ O ₁₂ : Cr ³⁺ Gd ₃ Ga ₅ O ₁₂ : Cr, Ce, GdNbO ₄ : Bi ³⁺ , Gd ₂ 0 ₂ S: Eu ^{3 +} , Gd ₂ O ₂ Pr ³⁺ , Gd ₂ 0 ₂ S: Pr, Ce, F

Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAInO ₁₇ : Tf, KGanOi ₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ O ₁₀ : Eu KMgF ₃ : Eu ²⁺ , KMgF ₃ : Mn ²⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , LaAl ₃ B ₄ O ₂ : Eu ³⁺ , LaAIB ₂ O ₆ : Eu ³⁺ LaAlO ₃ : Eu ³⁺ , LaAlO ₃ : Sm ³⁺ , LaAsO ₄ : Eu ³⁺ , LaBr ₃ : Ce ³⁺ , LaBO ₃ : Eu ³⁺ (La, Ce, Tb) PO ₄ : Ce: Tb, LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³ \ LaOBr: Tm ³⁺ LaOCI: Bi ^3+, LaOCI: Eu ^3+, LaOF: Eu ^3+, La ₂ O _3: Eu ^3+, La ₂ 0 _3: Pr ^3+, La ₂ O ₂ S: Tb ³⁺

LaP0 ₄ : Ce ³⁺ , LaP0 ₄ : Eu ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , Tb ³⁺ , LaVO ₄ : Eu ³⁺ La ₂ W ₃ O ₁₂ : Eu ³⁺ , LiAl ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAlO ₂ : Fe ³⁺ , LiAlO ₂ : Mn ²⁺ LiAl ₅ O ₈ : Mn ²⁺ , Li ₂ CaP ₂ O ₇ : Ce ³⁺ , Mn ²⁺ , LiCeBa ₄ Si ₄ Oi ₄ : Mn ²⁺

LiCeSrBa ₃ Si ₄ 0 _14: Mn ^2+, Liln0 _2: Eu ^3+, Liln0 _2: Sm ^3+, LiLa0 _2: Eu ^3+, LuAI0 _3: Ce ³⁺ (l_u, Gd) ₂ Si0 _5: Ce ³⁺ , Lu ₂ Si0 ₅ : Ce ³⁺ , Lu ₂ Si ₂ 0 ₇ : Ce ³⁺ , LuTa0 ₄ : Nb ⁵⁺ , Lui xY _x Al0 ₃ : Ce ³⁺ , MgAl ₂ 0 ₄ : Mn ²⁺ , MgSrAl ₁₀ O. ₁₇ : Ce, MgB ₂ O ₄ : Mn ²⁺ MgBa ₂ (PO ₄ ) ₂ : Sn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : U, MgBaP ₂ O ₇ : Eu ²⁺ , MgBaP ₂ 0 ₇ : Eu ^{2 +} , Mn ²⁺ MgBa ₃ Si ₂ O ₈ : Eu ²⁺ , MgBa (SO ₄ ) ₂ : Eu ²⁺ , Mg ₃ Ca ₃ (PO ₄ ) ₄ : Eu ²⁺ , MgCaP ₂ O ₇ : Mn ²⁺ Mg ₂ Ca (S0 ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ca (S0 ₄ ) ₃ : Eu ²⁺ , Mn ² , MgCeAl _n 0 ₁₉ : Tb ³⁺ Mg ₄ (F) Ge0 ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) 0 ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ O ₄ : Mn ²⁺

Mg ₈ Ge ₂ O ₂ F ₂ : Mn ⁴⁺ , MgS: Eu ²⁺ , MgSiO ₃ : Mn ²⁺ , Mg ₂ SiO ₄ : Mn ²⁺ , Mg ₃ SiO ₃ F ₄ : Ti ⁺ MgS0 ₄ : Eu ²⁺ , MgSO 4 ₄ : Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ : Eu ²⁺ , MgSrP ₂ O ₇ : Eu ²⁺ MgSr ₅ (PO ₄ ) ₄ : Sn ²⁺ , MgSr ₃ Si ₂ O ₈ : Eu ²⁺ , Mn ^{2 +} , Mg ₂ Sr (SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ TiO ₄ : Mn ⁺ MgWO _4l MgYB0 ₄ : Eu ³⁺ , Na ₃ Ce (PO ₄ ) ₂ : Tb ³⁺ , Nal: TI Nai. ₂₃ Ko. ₄₂ Euo.i ₂ TiSi ₄ On: Eu ³⁺ , Na _{1 23} Ko.42Euo _. i ₂ TiSi ₅ 0 ₁₃ -xH ₂ O: Eu ³⁺ Na ₂ Mg ₃ Al ₂ Si ₂ O ₁₀ : Tb, Na (Mg ₂ _x Mn _x ) LiSi ₄ O ₁ oF ₂ : Mn _I NaYF ₄ : Er ³⁺ , Yb ³⁺ , NaYO ₂ : Eu ³⁺ , P46 (70%) + P47 (30%) SrAl ₁₂ O ₁₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ 0 ₄ : Eu ²⁺ , SrAl ₄ 0 ₇ : Eu ³⁺ , SrAl ₁₂ O ₁₉ : Eu ²⁺ SrAl ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ O ₉ Cl: Eu ^{2 +} , SrB ₄ O ₇ : Eu ²⁺ (F ₎ Cl, Br) _I SrB ₄ O ₇ : Pb ²⁺ SrB ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ 0 ₁₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O ₄ -z / 2: 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⁺ , SrGa ₁₂ Oi ₉ : Mn ²⁺ SrGa ₂ S ₄ : Ce ³⁺ , SrGa ₂ S ₄ : Eu ²⁺ , SrGa ₂ S ₄ : Pb ²⁺ , Srln ₂ O ₄ : Pr ³⁺ , Al ³⁺ (Sr, Mg) ₃ (PO) 2: Sn, Sr MgSi ₂ 0 _6: Eu ^2+, Sr ₂ MgSi ₂ O _7: Eu ^2+, Sr ₃ MgSi ₂ 0 _8: Eu ²⁺ SrMo0 _4: U, SrO-3B ₂ 0 _3: Eu ^2+, Cl, ß-SrO -3B ₂ 0 ₃ : Pb ²⁺ , β-SrO-3B ₂ O ₃ : Pb ²⁺ , Mn ²⁺ a-SrO-3B ₂ O ₃ : Sm ²⁺ , Sr ₆ P ₅ BO ₂₀ : Eu, Sr ₅ (P0 ₄ ) ₃ CI: Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ CI: Eu ²⁺ , Pr ³⁺

Sr ₅ (PO ₄ ) ₃ Cl: Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ CI: Sb ³⁺ , Sr ₂ P ₂ O ₇ : Eu ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Eu ²⁺ Sr ₅ (P0 ₄₎ ₃ F: Mn ^2+, Sr ₅ (P0 ₄₎ ₃ F: Sb ^3+, Sr ₅ (P0 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⁺ (AI) , SrS: Ce ³⁺ SrS: Eu ²⁺ , SrS: Mn ² \ SrS: Cu ⁺ , Na, SrSO ₄ : Bi, SrS0 ₄ : Ce ³⁺ , SrS0 ₄ : Eu ²⁺ SrS0 ₄ : Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ O ₁₀ Cl ₆ : Eu ²⁺ , Sr ₂ Si0 ₄ : Eu ²⁺ , SrTiO ₃ : Pr ³⁺

SrTiO ₃ : Pr ³⁺ , Al ³⁺ , Sr ₃ W0 ₆ : U, SrY ₂ O ₃ : Eu ³⁺ , Th0 ₂ : Eu ³⁺ , Th0 ₂ : Pr ³⁺ , ThO ₂ : Tb ³⁺ YAI ₃ B ₄ O _12: Bi ^3+, YAI 0 ₃ B ₄ _12: Ce ^3+, YAI ₃ B ₄ Oi _2: Ce ^3+, Mn, YAI ₃ B ₄ O _12: Ce ^3+, Tb ³⁺ YAI ₃ B ₄ Oi ₂ : Eu ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ Oi ₂ : Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAIO ₃ : Ce ³⁺ Y ₃ AI ₅ 0i ₂ : Ce ³⁺ , Y ₃ Al ₅ O ₁₂ : Cr ³⁺ , YAIO ₃ : Eu ³⁺ ,

YsAlsO ^ ^{4 *} Imn, YAlO _3: Sm ^3+, YAI0 _3: Tb ^3+, Y3AI ₅ 0 _2: Tb ^3+, yaso _4: Eu ³⁺

YB0 ₃ : Ce ³⁺ , YBO ₃ : Eu ³⁺ , YF ₃ : Er ³⁺ , Yb ³⁺ , YF ₃ : Mn ²⁺ , YF ₃ : Mn ²⁺ , Th ⁴⁺ YF ₃ : Tm ³⁺ , Yb ³⁺ , (Y, Gd) B0 ₃ : Eu, (Y, Gd) B0 ₃ : Tb, (Y, Gd) ₂ O ₃ : Eu ³⁺ Yi.34 Gdo _.6 o0 ₃ (Eu, Pr), Y ₂ O _3: Bi ^3+, YOBr: Eu ^3+, Y ₂ O _3: Ce, Y ₂ 0 _3: Er ³⁺ Y ₂ 0 _3: Eu ³⁺ (YOE), Y ₂ 0 _3: Ce ^3+, Tb ³⁺ , YOCl: Ce ³⁺ , YOCl: Eu ³⁺ , YOF: Eu ³⁺ YOF: Tb ³⁺ , Y ₂ O ₃ : Ho ³⁺ , Y ₂ O ₂ S: Eu ³⁺ , Y ₂ O ₂ S : Pr ^3+, Y ₂ 0 ₂ S: Tb ^3+, Y ₂ O _3: Tb ³⁺

YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO ₄ : Mn ²⁺ , Th ⁴⁺ , YPO ₄ : V ⁵⁺ Y (P, V) O ₄ : Eu, Y ₂ Si0 _5: Ce ^3+, YTa0 _4, YTa0 _4: Nb ^5+, YV0 _4: Dy ^3+, YVO _4: Eu ³⁺ ZnAl ₂ 0 _4: Mn ^2+, ZnB ₂ O _4: Mn ²⁺ ZnBa ₂ S _3: Mn ^2+, (Zn, Be) ₂ Si0 _4: Mn ²⁺ Zn _0.4 Cd ₀ .6s: Ag, ZnO, Cdo _{_.6.} S: Ag, (Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ ZnGa ₂ O ₄ , ZnGa ₂ O ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ Ge0 ₄ : Mn ²⁺ , (Zn, Mg) F ₂ : Mn ²⁺

ZnMg ₂ (PO ₄ ) ₂ : Mn ²⁺ , (Zn, Mg) ₃ (PO ₄ ) ₂ : Mn ²⁺ , ZnO: Al ³⁺ , Ga ³⁺ , ZnO: Bi ³⁺ , ZnO: Ga ³⁺ ZnO : Ga, ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag ⁺ , CI ^" , ZnS: Ag, Cu, CI ZnS: Ag, Ni, ZnS: Au, In, ZnS- CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25) ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , Cl, ZnS-CdS: Cu, Br , ZnS-CdS: Cu, I, ZnS: Cr ZnS: Eu ²⁺ , ZnS: Cu, ZnS: Cu ⁺ , Al ³⁺ , ZnS: Cu ⁺ , Cr, ZnS: Cu, Sn, ZnS: Eu ²⁺

ZnS: Mn ²⁺ , ZnS: Mn, Cu, ZnS: Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ³ -, Cr, ZnS: Pb ²⁺ ZnS: Pt ^+, Cr, ZnS: Pb, Cu, Zn ₃ (PO ₄₎ _2: Mn ^, Zn ₂ SiO _4: Mn ^ \ Zn ₂ SiO _4: Mn ^, As ^{ö +,} Zn2SiO _4: Mn, Sb2O2 , Zn ₂ SiO ₄ : Mn ²⁺ , P, Zn ₂ SiO ₄ : Ti ⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS-ZnTe : Mn ²⁺ , ZnSe: Cu ⁺ , CI, ZnWO ₄

Furthermore, the compound according to the invention shows particular advantages in the mixture with other phosphors of other fluorescent color or when used in LEDs together with such phosphors.

It has been found that the optimization of illumination parameters for white LEDs succeeds particularly well, especially when combining the compounds according to the invention with red-emitting phosphors.

Accordingly, in an embodiment according to the invention, it is preferred if the light source contains, in addition to the phosphor according to the invention, a red emitting phosphor.

Corresponding phosphors are known to the person skilled in the art or the person skilled in the art can select from the list given above. Suitable red emitting phosphors are often nitrides, sialones or sulfides. Examples are: 2-5-8-nitrides, such as (Ca, Sr, Ba) 2Si5N8: Eu, (Ca, Sr) 2Si5N8: Eu, (Ca, Sr) AISiN3: Eu, (Ca, Sr) S: Eu, (Ca, Sr) (S, Se): Eu, (Sr, Ba, Ca) Ga2S4: Eu and also oxynitridic compounds.

An advantage of the mixtures of oxynitrides are more homogeneous properties compared to mixtures of different substance classes; the chemical stability, the morphology, the temperature behavior, etc. of the phosphors is almost identical. This allows stable light characteristics of the phosphor converted LED and a homogeneous mixture of the phosphor components, thereby reducing the binning cost of LED construction. Suitable oxynitrides are in particular the europium-doped silico-oxynitrides. Corresponding preferred silico-oxynitrides to be used correspond in their composition largely to the compounds according to the invention, europium being used instead of cerium as dopant.

In one variant, the red-emitting oxynitrides are those of the formula

2-0.5y-x + 1.5z Eu _x Si ₅ N _{8-y +} z O _y

wherein A represents one or more elements selected from Ca, Sr, Ba, and x represents a value in the range of 0.005 to 1, and y represents a value in the range of 0.01 to 3, and z represents a value the range of 0 to 3. The manufacture and use of appropriate

Compounds are described in WO 2011/091839. Particularly preferred are phosphors of the formula [Ca, Sr] 2-o, 5y-x + i, 5z uxSi ₅ N8-y + zO _y

used.

In a further preferred embodiment of the invention, red emitting compounds of the formula

A2- c + 1,5zEUcSi5Ns-2 / 3x + zOx

used, wherein the indices used have the following meanings: A is one or more elements selected from Ca, Sr, Ba; 0.01 <c <0.2; 0 <x <1; 0 <z <3.0 and a + b + c <2 + 1, 5z. Are particularly preferred phosphors of the formula [Ca, Sr] ₂ + c i, _c 5zEu O _x used Si5N _8- 2 / 3x + _z. Corresponding compounds and manufacturing methods are in the earlier patent application with the Anmeldeaktenzeichen

EP12005188.3. Thereafter, the compounds can be obtained by a process comprising mixing a europium-doped alkaline earth metal silicon nitride or europium-doped alkaline earth metal silicooxynitride and an alkaline earth metal nitride, wherein the alkaline earth metal of the europium-doped alkaline earth metal silicon nitride and silicooxynitride and Alkaline earth metal nitrides may be the same or different and the mixture is calcined under non-oxidizing conditions. The europium-doped alkaline earth metal silicon nitride or silicooxynitride used in the above-mentioned process is preferably a compound of the following general formula EA _d Eu _c E _e N _f O _x , wherein for the symbols and indices used: EA is at least one alkaline earth metal, in particular selected from the group consisting of Ca, Sr and Ba; E is at least one element of the fourth main group, in particular Si; 0.80 <d <1.995; 0.005 <c <0.2; 4.0 <e <6.00; 5.00 <f <8.70; 0 <x <3.00; the following relation holds for the indices: 2d + 2c + 4e = 3f + 2x. The europium-doped alkaline earth metal silicon nitride or silicooxynitride used in step (a) may be any known in the art

Process, as described, for example, in WO 2011/091839. However, it is particularly preferred that the europium-doped alkaline earth metal silicon nitride or silicooxynitride be obtained by a step (a ') of calcining a mixture containing a europium source, a

Silicon source and an alkaline earth metal nitride under non-oxidizing

Conditions is produced. This step (a ') precedes step (a) of the above method. As Europiumquelle any conceivable europium compound can be used with which a europium-doped alkaline earth metal silicon nitride or silicooxynitride can be prepared.

Preferably europium oxide (especially EU2O3) and / or europium nitride (EuN) are used as europium source in the process according to the invention, in particular EU2O3. As silicon source can be any conceivable

Silicon compound can be used with a europium-doped

Alkaline earth metal silicon nitride or silicooxynitride can be produced.

Silicon nitride and optionally silicon oxide are preferably used in the process according to the invention as the silicon source. If a pure nitride is to be produced, the silicon source is preferably silicon nitride. If it is desired to produce an oxynitride, silicon dioxide is used in addition to silicon nitride as silicon source. An alkaline earth metal nitride is understood as meaning a compound of the formula M ₃ N ₂ in which M is, independently of one another, an alkaline earth metal ion, in each case selected from the group consisting of calcium, strontium and barium. In other words, the alkaline earth metal nitride is preferably selected from the group consisting of calcium nitride (Ca ₃ N ₂ ), strontium nitride (Sr ₃ N ₂ ), barium nitride (Ba ₃ N ₂ ), and mixtures thereof. The compounds used in step (a ') for the production of the europium-doped alkaline earth metal silicon nitride or silicooxynitride are preferably employed in a ratio such that the atomic numbers of the alkaline earth metal, of silicon, of europium, of nitrogen and optionally of oxygen desired ratio in the alkaline earth metal silicon nitride or -Silicooxynitrid the above formula (I), (la), (Ib) or (II). In particular, a stoichiometric ratio is used, but also a slight excess of Erdalkalinitrids is possible. The weight ratio of the europium-doped alkaline earth metal silicon nitride or silicooxynitride to the alkaline earth metal nitride in step (a) of the process according to the invention is preferably in the range from 2: 1 to 20: 1 and more preferably in the range from 4: 1 to 9: 1. The process is under non-oxidizing conditions, ie under substantially or completely oxygen-free

Conditions, especially under reducing conditions.

In a variant of the invention, it is again preferred, when the phosphors are arranged on the primary light source, that the red emitting phosphor is substantially illuminated by light from the primary light source, while the yellow emitting phosphor is substantially illuminated by light which already contains the red emitting phosphor happened or was scattered by this. This can be realized by placing the red emitting phosphor between the primary light source and the yellow emitting phosphor.

The phosphors or phosphor combinations according to the invention can either be dispersed in a resin (for example epoxy or silicone resin) or, with suitable size ratios, can be arranged directly on the primary light source or can be arranged remotely therefrom, 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 can be found, for example, in 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 between the phosphor and the primary light source is realized by a photoconductive arrangement. This makes it possible that the primary light source is installed in a central location and this means

light-conducting devices, such as photoconductive fibers, is optically coupled to the phosphor. In this way, the

Lighting requirements adapted lights only consisting of one or different phosphors, which may be arranged to form a luminescent screen, and a light guide, which is coupled to the primary light source realize. In this way it is possible to place a strong primary light source at a convenient location for the electrical installation and to install without further electrical wiring, but only by laying fiber optics at any location lights of phosphors, which are coupled to the light guide.

Further subjects of the invention are a lighting unit, in particular for the backlight of display devices, thereby

in that it contains at least one light source according to the invention, as well as a display device, in particular

Liquid crystal display device (LC display), with a

Backlight, characterized in that it contains at least one lighting unit according to the invention.

When used in LEDs, the particle size of the phosphors according to the invention is usually between 50 nm and 30 μm, preferably between 1 μm and 20 μm. For use in LEDs, the phosphors can also be converted into any external forms, 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 molding containing the phosphors of the invention. Production and use of corresponding moldings is familiar to the person skilled in the art from numerous publications.

All variants of the invention described herein may be combined with each other as long as the respective embodiments are not mutually exclusive. In particular, starting from the teaching of this document in the course of routine optimization, it is an obvious process to combine different variants described here in order to arrive at a specific, particularly preferred embodiment. The following examples are intended to illustrate the present invention and in particular show the result of such exemplary combinations of the described variants of the invention. However, they are by no means to be considered limiting, but rather are intended to encourage generalization. Any compounds or components that can be used in the formulations are either known and commercially available or can be synthesized by known methods. The temperatures given in the examples always apply in ° 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%. Percentages are always to be seen in the given context. Examples

Example 1: Preparation of different compositions of compounds of the formula I according to the invention

Example 1: Synthesis of Mgi.oCao ^ BaojaCeo ^ Nao ^ SisN .ezOo.s

In a glove box are 0.67 mmol lithium nitride Li ₃ N, 2.00 mmol Cernitride CeN, 79.17 mmol silicon nitride Si ₃ N ₄ and 16.67 mmol magnesium nitride Mg ₃ N ₂ , 3.33 mmol calcium nitride Ca ₃ N ₂ and 12 mmol Ba ₃ N ₂ and 12.50 mmol silicon dioxide Si0 ₂ mixed and then homogenized by means of mortars in agate mortar. The mixture thus obtained is transferred to a boron nitride annealing dish and transferred under inert conditions in a high-temperature furnace. The annealing of the material takes place for 8 h at 1600 ° C while supplying a N ₂ / H ₂ gas mixture. The annealed sample is then crushed, sieved with a nylon sieve <36 m and characterized crystallographically and spectroscopically.

The powder diagram of the product is shown in FIG. The resulting product shows the fluorescence spectrum according to FIG

Excitation spectrum according to FIG. 3.

Example 1 b:

Analogously, the following compounds are prepared:

Product starting materials

Mgo, ₃ Cao, 62Ba ₁ , oCeo, o4Lio, o4Si5N _7i6 70o, 5Mg ₃ N ₂ , Ca ₃ N ₂ , Ba ₃ N ₂ , CeN,

Li ₃ N, Si ₃ N ₄ , SiO ₂

Mg-i, i ₂ Cao, ₄ Bao, ₄ oCeo, o4Nao, o4Si5N ₇ , 670o, 5 Mg ₃ N ₂ , Ca ₃ N ₂ , Ba ₃ N ₂ , CeN,

NaNO ₃ , Si ₃ N ₄ , SiO ₂ Mgo, 8Ca ₀ , ₄ Mg ₃ N ₂ , Ca ₃ N ₂ , Ba ₃ N ₂ , CeN,

MgO, 8Cao, Bao, 475Ceo, o5Si5N7,50o, 5 Mg ₃ N _2, Ca ₃ N _2> Ba ₃ N _2,

M o, 79Cao, 39 Bao, 465Euo, o3Ceo, o5Si5N750o, 5Mg ₃ N ₂ , Ca ₃ N ₂₎ Ba ₃ N ₂ ,

(See the fluorescence spectrum in Figure 4) CeN _I Si3N ₄ , Si0 ₂ , EuN

Mgo, i9Cao, 39Bai .oesEuo.coCeo.osSis ^ sOo.s Mg ₃ N ₂₎ Ca ₃ N ₂ , Ba ₃ N ₂ ,

MgO, 97Sro, 7Ceo, o4 ao, o4Si5N7, ₇₈ Oo, 22 Mg ₃ N _2, Sr ₃ N 2, CeN, Si ₃ N _4, Si0 _2,

NaN0 ₃

Cao, 59Bai, 33Ceo, o4Nao, o4Si3,8Gei 2N7670o, 5 Ba ₃ N ₂ , Ca ₃ N ₂ , CeN, Si ₃ N ₄ ,

Ge ₃ N ₄ , Si0 ₂₎ NaN0 ₃

Cao, 29Mgo, 3oBai, 33Ceo, o4 ao, o4Si3, ₈ Gei, 2N7,670o, 5 Ba ₃ N _2, Ca ₃ N _2, Mg ₃ N _2, CeN,

Si ₃ N _4, Ge ₃ N _4, S1O2, NaNO ₃

MgO, 465Cao, 79Bao, 39Euo, o3Ceo, o5Si5N7 50o, 5 Mg ₃ N _2, Ca ₃ N _2, Ba ₃ N _2,

Cao.ei Bao, 855 uo, oi Ceo.osSis ^ sOo.s Ca ₃ N ₂ , Ba ₃ N ₂ , CeN, Si ₃ N ₄ , SiO ₂ ,

EuN

Sro, 59Cao, 4 go, 93Ceo, o4Nao, o4Si4 _i8 7670o, 5Co, 2 Ca ₃ N _2, Mg ₃ N _2, Sr ₃ N 2, CeN, Si ₃ N _4,

Si0 ₂ , NaN0 ₃ , C

Sro _i 59Cao, IMGo, 83Ceo, o4Nao, o4Si4,8 7670o, 5Co, 2 Ca ₃ N _2, Mg ₃ N _2, Sr ₃ N _2, CeN, Si ₃ N _4l

Si0 ₂₎ NaN0 ₃ , C

Sro, 99Mgo, 93Ceo, o5Ko, 05Alo, 5Si4.5N7, oOi, o Mg ₃ N ₂ , Sr ₃ N ₂ , AlN, CeN, Si ₃ N ₄ ,

Si0 ₂ , KNO3

Sro _i 99Mgo, 93Ceo, 05Ko, 05Bo, 2Si4,8N73Oo, 7 Mg ₃ N _2, Sr ₃ N _2, AlN, CeN,

Sr ₀ , 3Mgo, 25Ceo, o5 ao, o5Si ₅ N5,302.7 Mg ₃ N ₂ , Sr ₃ N _2l CeN, Si ₃ N _4> SiO ₂ ,

NaNO ₃

Sro, i Bao, 25Cao, IMGo, ICEO, o5 ao, o5Si5N _5, 302.7 Mg ₃ N _2, Sr ₃ N _2, Ca ₃ N _2, Ba ₃ N _2,

CeN, Si ₃ N ₄ , Si0 ₂ , NaNO ₃

₀ mg, 3CaO, 62Sri, Oceo, o4 ao, o4Si5N _7, 670o, 5 Mg ₃ N _2, Ca ₃ N _2, Sr ₃ N _2, CeN,

Mg ₀ , 82Ca ₀ , 2 Sro, 9oCeo, o4 ao, o4Si ₅ N7670o, 5 Mg ₃ N ₂ , Ca ₃ N ₂ , Sr ₃ N ₂ , CeN,

NaN0 ₃ , Si ₃ N _4l SiO 2

MgO, 4Cao, 4 Sro, 85Ceo, o5 ao, o5Si5N _7, 50o, 5 Mg ₃ N _2, Ca ₃ N _2, Sr ₃ N _2, CeN,

NaN0 ₃ , Si ₃ N ₄ , Si0 ₂

MgO, 4Cao, 4 Sro, 875Ceo, o5Si5 _7, ₅ Oo, 5 Mg ₃ N _2, Ca ₃ N _2, Sr ₃ N _2,

CeN, Si ₃ N ₄ , SiO ₂

Mg ₀ , 2Ca ₀ , 275 Bai ^ Ceo.osSis ^ sOo.s Mg ₃ N ₂ , Ca ₃ N ₂ , Ba ₃ N ₂ ,

CeN, Si ₃ N ₄ , Si0 ₂

Cao, 5 Sro, 2 Bai, 2Ceo, o5 ao, o5Si5N ₇ , 670o, 5 Ba ₃ N ₂ , Ca ₃ N ₂₎ Sr ₃ N ₂ , CeN,

NaN0 ₃ , Si ₃ N _4l Si0 ₂

The corresponding fluorescence spectra show emission bands in the yellow wavelength range. The following emission maxima (peak wavelengths) may be mentioned by way of example:

Cao.s Sr ₀ , 2 Bai, 2Ceo, o5 ao, o5Si5N ₇ , 670o, 5: peak wavelength: 552 nm

Mgi, ₁₂ Cao, Bao 4, 4oCeo, o4 ao, o4Si5N7, ₆ 70o, 5: peak wavelength 571 nm

Cao.eiBao.sss uo.oiCeo.osSis ^ .sOo.s: peak wavelength 595 nm

Example 1c:

(Sr, Ba) i, 70 Ceo ₎ ioLio ₎ ioSi5N _{7) 8} Oo, 2

0.434 g of CeO ₂ (2.52 mmol), 0.029 g of Li ₃ N (0.84 mmol), 3.500 g of Ba ₃ N ₂ (7.95 mmol), 5.552 g of Si ₃ N ₄ (39.58 mmol), 0.376 g of Si0 ₂ (6.25 mmol) and 2.313 g of Sr ₃ N ₂ (7.95 mmol) are weighed together in a glovebox and in

Mix the hand mortar until a homogeneous mixture is obtained.

The mixture is transferred to a boat made of boron nitride and placed in a tube furnace centered on a support plate made of molybdenum foil and 6 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (60 l / min N ₂ + 25 l / min H ₂ ) annealed ,

Example 1d:

1.1721 g of CeO 2 (10 mmol), 0.116 g of Li ₃ N (3.333 mmol), 28.008 g of Ba ₃ N ₂ (63.336 mmol), 22.660 g of Si ₃ N ₄ (158.300 mmol) and 1, 502 g of SiO ₂ (25.000 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained.

The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (60 l / min N ₂ + 20 l / min H ₂ ) annealed ,

The phosphor thus obtained is mixed in a glove box with 20 weight percent strontium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for one hour in 1-molar hydrochloric acid, then filtered off and dried

Example 1e:

(Sr, Ba) i _{; 8} 2 Ce ₀ , o2Lio, o2 Euo ^ Sis ^ eOo ^

0.086 g of CeO ₂ (0.50 mmol), 0.006 g of Li ₃ N (0.17 mmol), 0.352 g of Eu ₂ O ₃ (1 mmol), 3.500 g of Ba ₃ N ₂ (7.95 mmol), 6.077 g of Si ₃ N ₄ (43.33 mmol), 0.376 g SiO ₂ (6.25 mmol) and 2.313 g Sr ₃ N ₂ (7.95 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed , The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

Example 2: Coating of the phosphors

Example 2a: Coating of the Phosphors According to the Invention with SiO ₂ 50 g of one of the phosphors according to the invention described above are suspended in 1 liter of ethanol in a 2 L reactor with ground cover, heating mantle and reflux condenser. For this purpose, a solution of 17 g of ammonia water (25 wt .-% NH ₃ ) in 70 ml of water and 100 ml of ethanol. Under

Stirring at 65 ° C, a solution of 48 g of tetraethyl orthosilicate (TEOS) in 48 g of anhydrous ethanol slowly (about 1, 5 ml / min) was added dropwise. To

After completion of the addition, the suspension is stirred for a further 1.5 h, brought to room temperature and filtered off. The residue is washed with ethanol and dried at 150 ° C to 200 ° C.

Example 2b: Coating of the phosphors according to the invention with Al ₂ O ₃

In a glass reactor with heating mantle 50 g of one of the previously

suspended phosphors according to the invention suspended in 950 g of ethanol. 600 g of an ethanolic solution of 98.7 g of AICI ₃ * 6H ₂ O per kg of solution are added over 3 hours to the suspension while stirring at 80 ° C. The pH is kept constant at 6.5 by addition of sodium hydroxide solution. After the end of the addition is stirred for 1 h at 80 ° C, then cooled to room temperature, the phosphor filtered off, washed with ethanol and dried.

Example 2c: Coating of the Phosphors According to the Invention with B ₂ O ₃

In a glass reactor with heating mantle 50 g of one of the previously

described phosphors according to the invention in 1000 ml of water

suspended. The suspension is heated to 60 ° C and treated while stirring with 4.994 g of boric acid H3BO3 (80 mmol). The suspension is cooled with stirring to room temperature and then stirred for 1 h. This is followed by aspiration of the suspension and drying in a drying oven. After drying, the calcination of the material takes place at 500 ° C under a nitrogen atmosphere.

Example 2d: Coating of the Phosphors According to the Invention with BN In a glass reactor with heating mantle 50 g of one of the previously

suspended phosphors according to the invention suspended in 1000 ml of water. The suspension is heated to 60 ° C and treated while stirring with 4.994 g of boric acid H3BO3 (80 mmol). The suspension is cooled with stirring to room temperature and then stirred for 1 h. This is followed by aspiration of the suspension and drying in a drying oven. After drying, the calcination of the material takes place at 1000 ° C under a nitrogen-ammonia atmosphere.

Example 2e: Coating of the Phosphors According to the Invention with Zr0 ₂

In a glass reactor with heating mantle 50 g of one of the previously

suspended phosphors according to the invention suspended in 1000 ml of water. The suspension is heated to 60 ° C and adjusted to pH 3.0. Subsequently, the slow dosage of 10 g of a 30 takes place

percent by weight ZrOC solution with stirring. After the dosage is stirred for 1 h, then filtered with suction and with deionized water

washed. After drying, the calcination of the material takes place at 600 ° C under a nitrogen atmosphere.

Example 2f: Coating of the phosphors according to the invention with MgO

In a glass reactor with heating mantle 50 g of one of the previously

suspended phosphors according to the invention suspended in 1000 ml of water. The suspension is heated to 25 ° C and 19.750 g

Ammonium hydrogen carbonate (250 mmol) was added. There is slow addition of 100 ml of a 15 weight percent magnesium chloride solution. After the dosage is stirred for 1 h, then filtered with suction and washed with deionized water. After drying, the calcination of the material takes place at 1000 ° C under a nitrogen-hydrogen atmosphere.

Example 3: LED application of the phosphors

Various concentrations of the phosphors prepared according to Example 1 and the phosphors coated in Example 2 are prepared in the silicone resin OE 6550 from Dow Corning by adding 5 ml of the components A and 5 ml of the components B of the silicone are mixed with identical amounts of the phosphor, so that after combining the two

Dispersions A and B are present by homogenization with a speed mixer the following silicone phosphor mixture ratios:

5% by weight phosphor,

10% by weight phosphor,

15 wt .-% phosphor and

30% by weight of phosphor.

These mixtures are each transferred to a dispenser from Essemtek and filled into empty LED 3528 packages from Mimaki Electronics. After curing of the silicone at 150 ° C for 1 h, the LEDs

photometrically characterized by means of a structure consisting of

Components from the company Instrument Systems: spectrometer CAS 140 and integration sphere ISP 250. For the measurement, the LEDs are contacted with a controllable current source from Keithley at room temperature with a current of 20 mA. The brightness (in lumens of the converted LED / mW of optical power of the blue LED chip) versus color point CIE x of the converted LED is plotted as a function of the phosphorus use concentration in the silicone (5, 10, 15 and 30% by weight).

The lumen equivalent is a photometric quantity known in the art with the unit Im / W, which describes how large the photometric luminous flux in lumens of a light source at a given radiometric

Radiation power with the unit watt, is. The higher the lumen equivalent, the more efficient a light source is.

The lumen is a photometrical photometric quantity which is familiar to the person skilled in the art and describes the luminous flux of a light source, which is a measure of the total visible radiation emitted by a radiation source. The larger the luminous flux, the brighter the light source appears to be

Observer. CIE x and CIE y stand for the coordinates in the CIE standard color diagram familiar to the person skilled in the art (here standard observer 1931), with which the color of a light source is described.

Description of the figures

FIG. 1: Powder X-ray diffractogram of Example 1, measured on a Transmission Powder X-Ray diffractometer StadiP 611 KL from the company Stoe & Cie. GmbH, focusing on Cu-Ka1 radiation, germanium [111]

Primary beam monochromator, linear PSD detector.

Figure 2: Fluorescence spectrum of the product of Example 1, taken with an Edinburgh Instruments spectrometer FS920 at a

Excitation wavelength of 450 nm (peak wavelength: 560 nm). In fluorescence measurement, the excitation monochromator is placed on the

Set the excitation wavelength and arranged after the sample detector monochromator in 1 nm increments between 467 and 850 nm

scanned, whereby the light intensity passing through the detector monochromator is measured.

FIG. 3: Excitation spectrum of the product from example 1, recorded with an Edinburgh Instruments spectrometer FS920. In the

Excitation measurement, the excitation monochromator is scanned in 1 nm increments between 250 nm and 500 nm, while the fluorescence light of the sample is detected constantly at a wavelength of 560 nm.

4 shows the fluorescence spectrum of the product Mg _0.79 Ca _0, 39

Bao, 465Euo, o3Ceo _, o5Si5 _7i5 0o, 5 (from example 1b) - taken with one

Edinburgh Instruments Spectrometer FS920 at an excitation wavelength of 450 nm. In fluorescence measurement, the excitation monochromator is set to the excitation wavelength and that after the sample

arranged detector monochromator in 1 nm increments between 475 and 850 nm.

Claims

claims

A compound containing an anionic skeleton structure, dopants and cations, wherein

a. the anionic skeleton structure is characterized by coordination tetrahedra GL ₄ , where G is silicon which may be partially replaced by C, Ge, B, Al or In and L is N and O, with the proviso that N is at least 60 atomic% of L,

b. the cations are selected from the alkaline earth metals, with the proviso that strontium and barium together make up less than 75 atomic% of the cations,

c. trivalent cerium or a mixture of trivalent cerium and divalent europium is present as dopant,

d. the charge equalization of the cerium doping i) via a corresponding replacement of alkaline earth cations by alkali cations and / or ii) via a corresponding increase in the nitrogen content and / or iii) a corresponding reduction of the alkaline earth cations.

A compound according to claim 1, characterized in that the alkaline earth metal cations are strontium, magnesium, calcium and / or barium, with calcium and magnesium together making up 25 atomic% or more of the alkaline earth metal cations and in the same or an alternative embodiment Calcium and magnesium together in the range of 30 at.% To 80 at.% Of the

Make up alkaline earth metal cations.

3. A compound according to claim 1 and / or 2, characterized in that G is more than 80 atomic% of silicon or G more than 90 atomic% is silicon. Compound according to one or more of the preceding claims, characterized in that silicon is partially replaced by C or Ge.

Compound according to one or more of claims 1 to 3, characterized in that G is formed by silicon.

Compound according to one or more of the preceding claims, characterized in that it is a compound of the formula Ia,

A2-0.5y-x + 1, 5z o, 5xCeo, 5xG5N8-y + zOy (| _a )

is, where

A is one or more elements selected from Ca, Sr, Ba, Mg,

M is one or more elements selected from Li, Na, K,

y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

Compound according to one or more of the preceding claims, characterized in that it is a compound of the formula Ib,

A2-0.5y-0.75x + 1.SzCeo.SxGsNs-y + zOy (ib)

is, where

A is one or more elements selected from Ca, Sr, Ba, Mg,

M is one or more elements selected from Li, Na, K,

y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

Compound according to one or more of the preceding claims, characterized in that the phosphor is a compound of the formula Ic, _A2-0, 5y + 1,5zCeo, 5xG5N8 + 0.5x ₊ y-zO _y (Ic)

is, where

A is one or more elements selected from Ca, Sr, Ba, Mg,

M is one or more elements selected from Li, Na, K,

y is a value in the range of 0.01 to 3 and

z stands for a value in the range of 0 to 3.

9. A compound according to one or more of claims 6 to 8, characterized in that x stands for a value from the range of 0.01 to 0.8, alternatively from the range 0.02 to 0.7 and further alternatively from the range 0.05 to 0.6.

10. A compound according to one or more of claims 6 to 9, characterized in that y stands for a value from the range of 0.1 to 2.5, preferably from the range 0.2 to 2 and particularly preferably from the range 0, 22 to 1, 8.

11. A compound according to one or more of the preceding claims, characterized in that present in the dopant europium and the cations contain a proportion of barium.

12. A compound according to one or more of the preceding claims, characterized in that the compound is in admixture with a silicon and oxygen-containing compound.

13. A process for preparing a compound according to one or more of claims 1 to 12, characterized in that in a step a) suitable starting materials selected from binary nitrides, halides and oxides or corresponding reactive forms are mixed thereto and the mixture in a step b) under non-oxidizing

Conditions is thermally treated.

14. Use of a compound according to one or more of claims 1 to 12 as a phosphor.

15. Light source with at least one primary light source, characterized

in that the light source contains at least one compound according to one or more of claims 1 to 12.

16. Light source according to claim 15, characterized in that the

Light source contains a red emitting phosphor.

17. Lighting unit, in particular for the backlight of

Display devices, characterized in that it comprises at least one light source according to one or more of claims 15 to 16.

18. Display device, in particular a liquid crystal display device (LC display), with a backlight, characterized in that it contains at least one illumination unit according to claim 17.

19. Use of a compound according to one or more of claims 1 to 12 for the partial or complete conversion of the blue or near UV emission of a primary light source, preferably a light-emitting diode or a laser in light of the yellow

Spectral range.