EP3538624A1

EP3538624A1 - Mn4+-activated luminescence material as conversion luminescent material for led solid state light sources

Info

Publication number: EP3538624A1
Application number: EP17780427.5A
Authority: EP
Inventors: Ralf Petry; Ingo Koehler; Mathias RAPPHAHN; Thomas Juestel; Thomas Jansen
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2016-10-12
Filing date: 2017-10-09
Publication date: 2019-09-18
Also published as: TW201821593A; CN109996856A; US20200194625A1; KR20190068580A; JP2019533629A; WO2018069195A1

Abstract

The invention relates to Mn4+-activated luminescence materials, to a method for the production thereof, and to the use thereof as luminescent materials or conversion luminescent materials in light sources. The invention further relates to an emissions-converting material containing the luminescent material according to the invention and to a light source that contains the luminescent material or the emissions-converting material according to the invention. The invention further relates to light sources, in particular LEDs, and lighting units, which contain a primary light source and the luminescence material or the emissions-converting material according to the invention. The Mn4+-activated luminescence materials according to the invention are particularly suitable for generating warm white light in LEDs.

Description

Mn-activated luminescent material

as conversion phosphor for LED solid-state light sources

Subject of the invention

The present invention relates to Mn ⁴⁺ -activated luminescent materials, a process for their preparation and their use as

Phosphors or conversion phosphors

(Conversion phosphors), especially in phosphor converted light emitting devices, such as PC LEDs (phosphor converted light emitting diodes). The present invention further relates to

emission-converting material containing the luminescent material according to the invention, as well as a light source containing the luminescent material according to the invention or the emission-converting material. Another object of the present invention is a

Lighting unit, which is a light source with the luminescent material according to the invention or the invention

Contains emission-converting material. The Mn ^{4+ -activated} luminescent materials according to the invention are particularly suitable for

Generation of warm white light in LED solid state light sources.

Background of the invention

For more than 100 years, inorganic phosphors have been developed to provide emitting screens, X-ray amplifiers, and radiation

Spectrally adapt light sources so that they meet the requirements of the respective field of application as optimally as possible and at the same time consume as little energy as possible. The nature of the excitation, i. the nature of the primary radiation source and the required

Emission spectrum of crucial importance for the selection of host lattices and activators.

Especially for fluorescent light sources for general lighting, ie 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. In principle, in order to obtain white emitting inorganic LEDs (light emitting diodes) through additive color mixing, there are basically three

different approaches:

(1) The RGB LEDs (red + green + blue LEDs), which have white light

is produced by mixing the light of three different emitting in the red, green and blue spectral light-emitting diodes.

(2) The systems UV LED + RGB phosphor, where a semiconductor emitting in the UV range (primary light source) emits the light to the environment in which three different phosphors (conversion phosphors) are excited, in the red, green and blue spectral range to emit. Alternatively, two different phosphors can be used which emit yellow or orange and blue.

(3) Complementary systems where an emitting semiconductor

(Primary light source) emits, for example, blue light, which excites one or more phosphors (conversion phosphors) to emit light in the yellow area, for example. By mixing the blue and the yellow light, white light is created. Alternatively, two or more phosphors emitting, for example, green or yellow and orange or red light may be used.

Binary complementary systems require a yellow conversion phosphor to reproduce white light when using a blue emitting semiconductor as a primary light source. Alternatively, green and red emitting conversion phosphors can be used. 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 dichromatic mixture of two conversion phosphors emitting complementary light 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 especially high lumen equivalent. Another advantage of a dichromatic phosphor mixture is the lower spectral interaction and the associated higher "package gain".

Therefore, in particular inorganic luminescent materials, which can be excited in the ultraviolet and / or blue spectral range, are becoming increasingly important today as conversion luminescent materials for light sources, in particular for pc LEDs for producing warm white light.

Thus, there is a continuing need for new luminescent materials that can be used as conversion phosphors in the ultraviolet or blue

Spectral can be excited and light in the visible range, especially in the red spectral range. The primary goals are to expand the product range, to improve the color rendering of white LEDs and to realize trichromatic LEDs. For this purpose, green, yellow and red-emitting phosphors with high absorption in the blue, violet or UV spectral range, with a high quantum yield and a high lumen equivalent must be provided.

Mn ⁴⁺ activated luminescent materials are incorporated in

Fluorescent light sources (CFL, TL, LED) and in emissive screens (cathode ray tubes) used for the conversion of non-visible radiation or high energy particles into visible light. A material that has found quite widespread use for this purpose is

Mg8Ge2O F2: Mn, whose emission maximum is around 660 nm and which is good at 160 nm or 254 nm but also in the deep blue

Stimulate spectral range. It is therefore conditional for the

Use in phosphor-converted LEDs, especially since Mn ⁴⁺ -doped phosphors can show efficient photoluminescence even at high temperatures (100 - 200 ° C).

A disadvantage of using Mn ⁴⁺ -activated phosphors in

High-power LED solid-state light sources are usually relatively small Absorption cross section in the near UV or in the blue spectral range. This finding severely restricts the ergonomic use of Mn ⁴⁺ -a scavenged phosphors as a radiation converter in near-UV or blue LEDs. In addition, LEDs with high color rendering and high lumen output require a red phosphor with one

Emission maximum in the red spectral range of 620 and 640 nm, which is only partially possible in oxidic host materials.

Therefore, the search for new Mn ⁴⁺ -a cavitated LED phosphors in many academic and industrial research laboratories, such as General Electric, continues to be highly advanced.

Thus, WO 2014/152787 A1 discloses a process for the synthesis of color-stable Mn ⁴⁺ -doped phosphors, wherein, for example

K ₂ [SiF ₆ ]: Mn ⁴⁺ , K ₂ [TiF ₆ ]: Mn ⁴⁺ or K ₂ [SnF ₆ ]: Mn ⁴⁺ are reacted as precursors in gaseous form at elevated temperature with a fluorine-containing oxidizing agent.

WO 2014/179000 A1 describes a method for producing a light-emitting device which comprises a light-emitting diode (LED) and a layered phosphor composite. Of the

The phosphor composite includes a first phosphor layer having a yellow emitting phosphor disposed over a second phosphor layer containing a manganese-doped potassium fluorosilicate (PFS). From WO 2014/179000 A1 are red emitting Mn ⁴⁺ -doped complex fluoride phosphors, such as K2 [SiF6]: Mn ⁴⁺ , K2 [TiF6]: Mn ⁴⁺ and K ₂ [SnF ₆ ]: Mn ⁴⁺ known.

WO 2008/100517 A1 relates to light emitting devices comprising a light source and a phosphor material, the phosphor material containing a complex Mn ⁴⁺ -activated fluoride phosphor including at least one of the following compounds: (A) A2 [MF5]: Mn ⁴⁺ , (B)

A ₃ [MF ₆ ]: Mn ⁴⁺ , (C) Zn ₂ [MF ₇ ]: Mn ⁴⁺ or (D) A [ln ₂ F ₇ ]: Mn ⁴⁺ with A = Li, Na, K, Rb, Cs and / or NH ₄ and M = Al, Ga and / or In. The luminescent materials known from the prior art are usually increased by reacting a precursor compound with a fluorine-containing oxidant in the gas phase

Temperature or in aqueous phase. The use of such highly corrosive fluorine-containing oxidizing agents places high demands on the apparatus and its material. As a result, the synthesis is complicated and expensive.

Another disadvantage of the previously known Mn ⁴⁺ -doped fluorides is their low stability, especially under irradiation with blue light or UV radiation. The fluorides partially release fluorine, leaving residual defects in the material itself and reducing Mn ⁴⁺ .

This will affect the life and stability of the color temperature.

Object of the invention

Object of the present invention is to provide long-term stable luminescent materials that have a luminescence in the red spectral range and are particularly suitable for use in high-power pc LEDs to produce warm white light. This will allow one skilled in the art to choose from a wider variety of suitable materials for making white emitting devices.

Object of the present invention is thus new

To provide luminescent materials that are characterized by a broad absorption cross section in the near UV to blue spectral range

have an emission maximum in the red spectral range between 620 and 640 nm and thus suitable for use as

Conversion phosphors in LEDs with high color rendering are suitable.

In addition, it is an object of the invention to provide luminescent materials with a long life, which are easily accessible by an efficient and inexpensive synthesis. Furthermore, it is an object of the present invention to improve the color rendering index and the stability of the color temperature in an LED. This can be warm white pc LEDs with high color rendering values at low color temperatures (CCT <4000 K).

Description of the invention

Surprisingly, it was found that the tasks of

present invention by Mn ⁴⁺ -activated luminescent materials on a fluoride host lattice of the form M ¹ M ² F6 (with M ¹ = Li, Na, K, Rb and / or Cs; M ² = As, Sb and / or Bi). The inventors have surprisingly found that red emitting luminescent materials with emission maxima between 620 and 640 nm, high

Quantum yield, high color rendering, high life and high stability of the color temperature can be realized by Mn ⁴⁺ ions in the fluoride host lattice M ¹ M ² F ₆ (with M ¹ = Li, Na, K, Rb and / or Cs M ² = As, Sb and / or Bi) are installed so that

Luminescent materials of the general composition M ¹ M ² F6: Mn ⁴⁺ can be obtained. In addition, the luminescent materials are accessible efficiently and inexpensively through a simple synthesis, with As ⁵⁺ , Sb ⁵⁺ and Bi ⁵⁺ in particular offering long-term stable fluorides, because the associated complex anions [M ² F 6] ^" have an extraordinary high stability.

The incorporation of the tetravalent Mn ⁴⁺ ions occurs at the lattice sites of the pentavalent M ² ions (M ² = As, Sb and / or Bi). The doping with Mn ⁴⁺ allows a simple and efficient synthesis, since the Mn ⁴⁺ ions fit well into the crystal structure of the host lattice. The charge balance is due to fluoride defects in the host lattice.

Compounds of this general composition are red-emitting Mn ⁴⁺ luminescent materials whose emission line multiplet in the red spectral region has a maximum between 620 and 640 nm and which are suitable for use as an application

Conversion phosphors in solid state radiation sources of any kind, such as LED solid state light sources or high-power LED solid state light sources claimed. The CIE1931 color coordinates All materials claimed here are x> 0.66 and y <0.33. The lumen equivalent is higher than 200 lm / W.

The present invention thus provides a compound of the following general formula (I) or (II)

where the symbols and indices used are:

M ¹ is selected from the group consisting of Li, Na, K, Rb, Cs and mixtures of two, three or more thereof;

M ² is selected from the group consisting of As, Sb, Bi and

Mixtures of two or three thereof; and

0 <x <1, 00.

In the above general formula (I), M ^{1 is} a singly charged one

Metal atom (M ¹ ) ⁺ . M ² is a five-fold charged metal atom (M ² ) ⁵⁺ . Mn is present as a fourfold charged metal atom Mn ⁴⁺ , while fluorine in the form of fluoride (F ^" ) is present in the compound.

The Mn ⁴⁺ -activated luminescent materials according to the invention are conversion materials which are doped with Mn ⁴⁺ . In the general formula (I) replaces a Mn ⁴⁺ ions, a (M ²⁾ ⁵⁺ + ion and an F ^"+ ion. The charge is thus compensated by fluoride voids in the host lattice.

The compounds of the invention are usually in

Spectral range from about 250 to about 550 nm, preferably from about 300 to about 525 nm, more preferably from about 300 to about 400 nm, or from about 400 to 525 nm, most preferably from about 425 to about 500 nm, excitable and usually emit in the red

Spectral range from about 600 to about 650 nm, the

Emission maximum in the spectral range between 620 and 640 nm, preferably between 625 and 635 nm. The invention Compounds additionally show a high photoluminescence quantum yield and have a high color rendering and high stability of the color temperature when used in an LED.

In the context of this application, UV light is defined as light whose emission maximum lies between 100 and 389 nm, when violet light denotes light whose emission maximum lies between 390 and 399 nm, blue light denotes such light, whose emission maximum is between 400 and 3800 nm 459 nm, as cyan light, whose emission maximum lies between 460 and 505 nm, as green light, whose emission maximum is between 506 and 545 nm, as yellow light, whose emission maximum lies between 546 and 565 nm, as orange Light such, whose

Emission maximum between 566 and 600 nm and is such as red light whose emission maximum is between 601 and 750 nm.

In a preferred embodiment of the invention, M ^{1 is} selected from the group consisting of Li, Na, K and mixtures of two or three thereof. In a more preferred embodiment, M ^{1 is} selected from the group consisting of Li, Na and K.

In a preferred embodiment of the invention, M ^{2 is} selected from the group consisting of As, Sb and mixtures of As and Sb, which may optionally contain Bi.

In a preferred embodiment of the invention, M ^{2 is} selected from mixtures consisting of As and Sb, As and Bi, Sb and Bi and As, Sb and Bi.

In a preferred embodiment of the invention, for the subscript x in the general formula (I): 0 <x <0.80, more preferably 0 <x <0.60, more preferably 0 <x <0.40, most preferably 0.001 <x <0.20, more preferably 0.001 <x <0.10, and most preferably 0.001 <x <0.010. In a particularly preferred embodiment of the invention, several of the above-mentioned preferred features are contemporaneous, regardless of whether they are preferred, particularly preferred, more preferred, and / or most preferred.

Particular preference is therefore given to compounds of the general formula (I) in which the following applies:

M ¹ is selected from the group consisting of Li, Na, K and

Mixtures of two or three thereof;

M ² is selected from the group consisting of As, Sb and mixtures of As and Sb, which may optionally contain Bi; and

0 <x <0.60, more preferably 0 <x <0.40, more preferably 0.001 <x <0.20, more preferably 0.001 <x <0.10, and most preferably 0.001 <x <0.010.

The compound of the invention may preferably be coated on its surface with another compound, as below

is described.

Another object of the present invention is a process for preparing a compound according to the general formula (I), comprising the following steps: a) preparation of a suspension / solution containing M ¹ , M ² and Mn in an HF solution;

b) stirring the suspension / solution; and

c) separation of the resulting solid.

The preparation of the suspension / solution in step a) is carried out by

Suspend / dissolve salts containing M ¹ , M ² , Al and Mn in an HF solution. In this case, the salts in step a) either

be added sequentially in any order or at the same time. The salts can be either as solids or as Suspensions / solutions are added. As the HF solution, a concentrated HF solution is preferably used. Preferably, concentrated aqueous HF solution (hydrofluoric acid) with 10-60 wt.% HF, more preferably 20-50 wt.% HF, and most preferably 30-40 wt.% HF, is used in the inventive production process.

In the process for the preparation of a compound according to the general formula (1) in step a) as the salt for the ions (M ¹ ) ⁺ and (M ² ) ⁵⁺ preferably fluoride compounds are used as starting compounds, such as M ¹ M ² F6, NH ₄ M ² F ₆ , M ¹ F and M ² F ₅ .

Preferred fluoride compounds M ¹ M ² F ₆ are: LiAsF ₆ , NaAsF ₆ , KAsF ₆ , RbAsF ₆ , CsAsF ₆ , LiSbF ₆ , NaSbF ₆ , KSbF ₆ , RbSbF ₆ , CsSbF ₆ , LiBiF ₆ , NaBiF ₆ , KbiF ₆ , RbBiF ₆ and CsBiF ₆ . Preferred fluoride compounds NH ₄ M ² F ₆ are: NH ₄ AsF ₆ , NH ₄ SbF ₆ and NH ₄ BiF ₆ . Preferred fluoride compounds M ¹ F are: LiF, NaF, KF, RbF and CsF. Preferred fluoride compounds M ² F are: AsF ₅ , SbF ₅ and B1F ₅ .

Mn is used in step a) preferably in the form of tetravalent manganese salts as starting compounds, such as M ¹ 2MnF6.

Preferred tetravalent manganese salts M ¹ 2MnF 6 are Li 2 MnF ₆ , Na 2 MnF ₆ , K 2 MnF ₆ , Rb 2 MnF ₆ and Cs 2 MnF ₆ .

The suspension / release of the starting compounds can at

Temperatures between 0 and 100 ° C, preferably between 20 and 90 ° C, more preferably between 40 and 80 ° C, and most preferably between 50 and 75 ° C, take place.

The stirring of the suspension / solution in step b) is preferably carried out at temperatures between 0 and 100 ° C, preferably between 20 and 90 ° C, more preferably between 40 and 80 ° C and most preferably between 50 and 75 ° C for a period of time up to 10 hours, preferably up to 6 hours, more preferably up to 4 hours, and most preferably up to 3 hours. Preferred periods for stirring the suspension / solution in step b) are 0.1 -10 h, 0.5-6 h, 1 -4 h and 2-3 h. In a preferred Embodiment, the suspension / solution is stirred in step b) at a temperature between 50 and 75 ° C for 2-3 h.

The separation of the resulting solid in step c) takes place

preferably by filtration, centrifugation or decantation, more preferably by filtration through a suction filter.

In a preferred embodiment of the present invention, step c) is followed by a further step d), in which the solid obtained in step c) is washed and dried. The washing of the solid is preferably carried out with an organic solvent until the solid is acid-free. Preferred are organic aprotic solvents such as acetone, hexane, heptane, octane, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The one used for washing

Solvent preferably has a temperature of -10 to 20 ° C.

The drying of the solid in step d) is preferably carried out under

reduced pressure. Drying may be at room temperature (20 to 25 ° C) or at an elevated temperature, such as 25 to 150 ° C. After drying in step d) the desired

Lumineszenzverbindung received.

In a further embodiment, the inventive

Luminescent materials are coated. Suitable for this purpose are all coating methods known to the person skilled in the art from the prior art and used for phosphors. 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 or wet-chemical. Suitable coating methods are known, for example, from JP 04-304290, WO 91/10715, WO 99/27033, US 2007/0298250, WO 2009/065480 and WO 2010/075908, which are hereby incorporated by reference. On the one hand, the aim of the coating can be a higher stability of the luminescent materials, for example against air or moisture. The goal can also be an improved coupling and decoupling of light by a suitable choice of the surface of the coating and the

Refractive indices of the coating material.

Yet another object of the present invention is the use of the luminescent materials according to the invention as

Phosphor or conversion luminescent material, in particular for the partial or complete conversion of UV light, violet light and / or blue light into light with a longer wavelength.

The compounds of the invention are therefore also referred to as phosphors.

Another object of the present invention is a

emission converting material comprising a compound of the invention. The emission-converting material may consist of the compound according to the invention and would in this case be equated with the term "phosphor" or "conversion luminescent substance" as defined above. It may also be preferred that the inventive emission-converting material in addition to the inventive

Compound still contains more conversion phosphors. In this case, the emission-converting material according to the invention preferably contains a mixture of at least two conversion phosphors, at least one of which is a compound according to the invention. It is particularly preferred that the at least two

Conversion phosphors are phosphors that emit light with complementary wavelengths.

If the compounds according to the invention are used in small amounts, they already give good LED qualities. The LED quality is doing with usual parameters, such as the Color

Rendering Index (CRI), the Correlated Color Temperature (CCT),

Lumen equivalents or absolute lumens or the color point in CIE x and y coordinates described.

The Color Rendering Index (CRI) is a familiar, non-standard photometric size, which the color fidelity of a artificial light source with that of sunlight or and

Comparing filament light sources (the latter two have a CRI of 100).

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

The lumen equivalent is a photometric quantity known to those 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 can be calculated from the emission spectra of the light source using methods known to those skilled in the art.

The excitability of the phosphors of the invention extends over a wide range, which is most preferably from about 250 to about 550 nm, preferably from about 300 to about 525 nm, more preferably from about 300 to about 400 nm, or from about 400 to 525 nm from about 425 to about 500 nm. A further subject of the present invention is a light source which contains at least one primary light source and at least one compound according to the invention or an emission-converting material according to the invention. The emission maximum of the primary light source is usually in the range from about 250 to about 550 nm, preferably from about 300 to about 525 nm, more preferably from about 300 to about 400 nm or from about 400 to 525 nm, most preferably from about 425 to about 500 nm, wherein the primary radiation is partially or completely converted by the phosphor according to the invention into longer-wave radiation.

In a preferred embodiment of the light source according to the invention, the primary light source comprises a luminescent indium-aluminum-gallium-nitride compound, which is preferably represented by the formula IniGajAlkN, 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 one

luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC or also on an organic light-emitting layer-based arrangement (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 Lumineszenzmatenalien invention can be used individually or as a mixture with suitable phosphors, which are familiar to the expert. Corresponding phosphors which are suitable in principle for mixtures are, for example:

Ba ₂ SiO ₄ : Eu ²⁺ , BaSi ₂ N ₂ O ₂ : Eu, BaSi ₂ O ₅ : Pb ²⁺ , Ba ₃ Si 6 O ₁₂ N ₂ : Eu,

BaxSri-xF ₂ : Eu ²⁺ (where 0 <x <1), BaSrMgSi ₂ O ₇ : Eu ²⁺ , BaTiP ₂ O ₇ ,

(Ba, Ti) ₂ P ₂ O ₇ : Ti, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ SiO ₄ : Mn ²⁺ , Bi ₄ Ge ₃ O ₁₂ , CaAl ₂ O ₄ : Ce ³⁺ , CaLa ₄ O ₇ : Ce ³⁺ , CaAl ₂ O ₄ : Eu ²⁺ , CaAl ₂ O ₄ : Mn ²⁺ , CaAl ₄ O ₇ : Pb ²⁺ , Mn ²⁺ ,

CaAl ₂ O ₄ : Tb ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ : Ce ³⁺ ,

Ca ₃ Al ₂ Si ₃ O, ₂ : Eu ²⁺ , Ca ₂ B ₅ O ₉ Br: Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl: Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl: Pb ²⁺ , CaB ₂ O ₄ : Mn ²⁺ , Ca ₂ B ₂ O ₅ : Mn ²⁺ , CaB ₂ O ₄ : Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ²⁺ ,

Ca ₅ B ₂ SiOio: Eu ³⁺ , Cao.5Ba ₀ .5Ali ₂ Oi ₉ : Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (PO ₄ ) ₃ Cl: 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⁺ , Ca F ₂ : Eu ²⁺ , CaF ₂ : Mn ²⁺ ,

CaGa ₂ O ₄ : Mn ²⁺ , CaGa ₄ O ₇ : Mn ²⁺ , CaGa ₂ S ₄ : Ce ³⁺ , CaGa ₂ S ₄ : Eu ²⁺ ,

CaGa ₂ S ₄ : Mn ²⁺ , CaGa ₂ S ₄ : Pb ²⁺ , CaGeO ₃ : Mn ²⁺ , 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 : Ce ³⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Ca ₃ MgSi ₂ O ₈ : Eu ²⁺ , Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Mn ²⁺ ,

Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , CaMoO ₄ , CaMoO ₄ : Eu ³⁺ , CaO: Bi ³⁺ , CaO: Cd ²⁺ , CaO: Cu ⁺ , CaO: Eu ³⁺ , CaO: Eu ³⁺ , Na ⁺ , CaO: Mn ²⁺ , CaO: Pb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaO: Tb ³⁺ , CaO: TI, CaO: Zn ²⁺ , Ca ₂ P ₂ O ₇ : Ce ³⁺ , α-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , β-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Eu ^{2 +} , Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F: Mn ²⁺ ,

Ca ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ F: 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⁺ , 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,

CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, CaSiO ₃ : Ce ³⁺ , Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ ,

Ca ₃ SiO ₄ Cl ₂ : Pb ²⁺ , CaSiO ₃ : Eu ²⁺ , 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, (Ce, Mg) BaAliiOi ₈ : Ce, (Ce, Mg) SrAliiOi ₈ : Ce, CeMgAliiOi ₉ : Ce: Tb, Cd ₂ B ₆ On: Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: ln, CdS: ln,

CdS: In, Te, CdS: Te, CdWO ₄ , CsF, CsI, CsI: Na ⁺ , CsI: TI,

(ErCl ₃ ) o.25 (BaCl ₂ ) o.75, GaN: Zn, Gd ₃ Ga ₅ O ₁₂ : Cr ³⁺ , Gd ₃ Ga ₅ O ₁₂ : Cr, Ce,

GdNbO ₄ : Bi ³⁺ , Gd ₂ O ₂ S: Eu ³⁺ , Gd ₂ O ₂ Pr ³⁺ , Gd ₂ O ₂ S: Pr, Ce, F, Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAInOi ₇ : TI ⁺ , KGanOi ₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ Oi ₀ : Eu, KMgF ₃ : Eu ²⁺ , KMgF ₃ : Mn ²⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , LaAl ₃ B ₄ O ₁₂ : 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⁺ , LaCI ₃ : Ce ³⁺ ,

La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³⁺ , LaOBr: Tm ³⁺ , LaOCl: Bi ³⁺ , LaOCl: Eu ³⁺ , LaOF: Eu ³⁺ , La ₂ O ₃ : Eu ³⁺ , La ₂ O ₃ : Pr ³⁺ , La ₂ O ₂ S: Tb ³⁺ , LaPO ₄ : Ce ³⁺ , LaPO ₄ : Eu ³⁺ ,

LaSiO ₃ Cl: Ce ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , Tb ³⁺ , LaVO ₄ : Eu ³⁺ , La ₂ W ₃ O ₁₂ : Eu ³⁺ ,

LiAIF ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAIO ₂ : Fe 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 Oi ₄ : Mn ²⁺ , LiCeSrBa ₃ Si ₄ Oi ₄ : Mn ²⁺ ,

LilnO ₂ : Eu ³⁺ , LilnO ₂ : Sm ³⁺ , LiLaO ₂ : Eu ³⁺ , LuAIO ₃ : Ce ³⁺ , (Lu, Gd) ₂ SiO ₅ : Ce ³⁺ , Lu ₂ SiO ₅ : Ce ³⁺ , Lu ₂ Si ₂ O ₇ : Ce ³⁺ , LuTaO ₄ : Nb ⁵⁺ , Lui _-x Y _x AIO ₃ : Ce ³⁺ (where 0 <x <1), (Lu, Y) ₃ (Al, Ga, Sc ) ₅ O ₁₂ : Ce, MgAl ₂ O ₄ : Mn ²⁺ , MgSrAh ₀ Oi ₇ : Ce, MgB ₂ O ₄ : Mn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : Sn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : U, MgBaP ₂ O ₇ : Eu ²⁺ , MgBaP ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , MgBa ₃ Si ₂ O ₈ : Eu ²⁺ , MgBa (SO ₄ ) ₂ : Eu ²⁺ , Mg ₃ Ca ₃ (PO ₄ ) ₄ : Eu ²⁺ , MgCaP ₂ O ₇ : Mn ²⁺ , Mg ₂ Ca (SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ca (SO ₄ ) ₃ : Eu ²⁺ , Mn ² , MgCeAl _n Oi ₉ : 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 OnF ₂ : Mn ⁴⁺ , MgS: Eu ²⁺ , MgSiO ₃ : Mn ²⁺ , Mg ₂ SiO ₄ : Mn ²⁺ ,

Mg ₃ SiO ₃ F ₄ : Ti ⁴⁺ , MgSO ₄ : Eu ²⁺ , MgSO ₄ : Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ : Eu ²⁺ ,

MgSrP ₂ O ₇ : Eu ²⁺ , MgSr ₅ (PO ₄ ) ₄ : Sn ²⁺ , MgSr ₃ Si ₂ O ₈ : Eu ²⁺ , Mn ²⁺ ,

Mg ₂ Sr (SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ TiO ₄ : Mn ⁴⁺ , MgWO ₄ , MgYBO ₄ : Eu ³⁺ ,

Na ₃ Ce (PO ₄ ) ₂ : Tb ³⁺ , Nai. ₂₃ K ₀ .4 ₂ Euo.i ₂ TiSi ₄ On: Eu ³⁺ ,

Nai. ₂₃ Ko. ₄₂ Euo.i ₂ TiSi5Oi ₃ xH ₂ O: Eu ³⁺ , Nai. ₂ 9Ko. ₄ 6Ero.o8TiSi ₄ On: Eu ³⁺ ,

Na ₂ Mg ₃ Al ₂ Si ₂ Oio: Tb, Na (Mg _2-x Mn _x ) LiSi ₄ OioF ₂ : Mn (where 0 <x <2),

NaYF ₄ : Er ³⁺ , Yb ³⁺ , NaYO ₂ : Eu ³⁺ , P46 (70%) + P47 (30%), β-SiAION: Eu, SrAli ₂ Oi ₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ : Eu ²⁺ , SrAl ₄ O ₇ : Eu ³⁺ ,

SrAli ₂ Oi ₉ : Eu ²⁺ , SrAl ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ O ₉ Cl: Eu ²⁺ , SrB ₄ O ₇ : Eu ²⁺ (F, Cl, Br), SrB ₄ O ₇ Pb ²⁺ , SrB ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ Oi ₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O _4- z / ₂ : Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ : Eu ²⁺ , (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ca) Si ₂ N ₂ O ₂ : Eu, Sr (CI, 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 FxByOz: Eu ²⁺ , Sm ²⁺ , SrF ₂ : Eu ²⁺ , SrGai ₂ 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 ₄ ) ₂ : Sn, Sr MgSi ₂ O ₆ : Eu ²⁺ , Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ , SrMoO ₄ : U,

SrO-3B ₂ O ₃ : Eu ²⁺ , Cl, β-SrO-3B ₂ O ₃ : Pb ²⁺ , β-SrO-3B ₂ O ₃ : Pb ²⁺ , Mn ²⁺ , a-SrO-3B ₂ O ₃ : Sm ²⁺ , Sr ₆ P 5BO ₂ o: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Pr ³⁺ Sr ₅ (PO ₄ ) ₃ CI: 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 OioCl ₆ : Eu ²⁺ , Sr ₂ SiO ₄ : Eu ²⁺ , SrTiO ₃ : Pr ³⁺ ,

SrTiO ₃ : Pr ³⁺ , Al ³⁺ , SrY ₂ O ₃ : Eu ³⁺ , ThO ₂ : Eu ³⁺ , ThO ₂ : Pr ³⁺ , ThO ₂ : Tb ³⁺ ,

YAl ₃ B ₄ O ₁₂ : Bi ³⁺ , YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , Mn, YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , Tb ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ O ₁₂ : Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ ,

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 ₁₂ : Eu ^3r , 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⁺ , Th ⁴⁺ , YF ₃ : Tm ³⁺ , Yb ³⁺ , (Y, Gd) BO ₃ : Eu, (Y, Gd) BO ₃ : Tb,

(Y, Gd) ₂ O ₃ : Eu ³⁺ , Yi. ₃₄ Gd ₀ .6oO ₃ (Eu, Pr), Y ₂ O _3: Bi ^3+, YOBr: Eu ^3+, Y ₂ O _3: Ce, Y ₂ O _3: Er ^3+, Y ₂ O _3: Eu ^{3 +} , Y ₂ O ₃ : Ce ³⁺ , Tb ³⁺ , YOCl: Ce ³⁺ , YOCl: Eu ³⁺ , YOF: Eu ³⁺ , YOF: Tb ³⁺ , Y ₂ O ₃ : Ho ³⁺ , Y ₂ O ₂ S: Eu ³⁺ , Y ₂ O ₂ S: Pr ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ O ₃ : Tb ³⁺ , YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO ₄ : Mn ²⁺ , Th ⁴⁺ , YPO ₄ : V ⁵⁺ , Y (P, V) O ₄ : Eu, Y ₂ SiO ₅ : Ce ³⁺ , YTaO ₄ , YTaO ₄ : Nb ⁵⁺ , YVO ₄ : Dy ³⁺ , YVO ₄ : Eu ³⁺ , ZnAl ₂ O ₄ : Mn ²⁺ , ZnB ₂ O ₄ : Mn ²⁺ , ZnBa ₂ S ₃ : Mn ²⁺ , (Zn, Be) ₂ SiO ₄ : Mn ²⁺ ,

Zn ₀ .4Cdo.6S: Ag, Zno. ₆ Cdo.4S: Ag, (Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ O ₄ , ZnGa ₂ O ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ GeO ₄ : Mn ²⁺ , (Zn, Mg) F ₂ : Mn ²⁺ , ZnMg ₂ (PO ₄ ) ₂ : Mn ²⁺ , (Zn, Mg) ₃ (PO ₄ ) _2: Mn ^2+, ZnO: Al ^3+, Ga ^3+, ZnO: Bi ^3+, ZnO: Ga ^3+, ZnO: Ga, ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag ⁺ , C | -, ZnS: Ag, Cu, Cl, ZnS: Ag, Ni, ZnS: Au, In, ZnS-CdS (25-75), ZnS-CdS (50-50) ZnS-CdS ( 75-25), ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , Cl, ZnS-CdS: Cu, Br, ZnS-CdS: Cu, l, ZnS: Cl ^" , ZnS: Eu ²⁺ , ZnS: Cu, ZnS: Cu ⁺ , Al ³⁺ , ZnS: Cu ⁺ , C | -, ZnS: Cu, Sn, ZnS: Eu ²⁺ , ZnS: Mn ²⁺ , ZnS: Mn, Cu, ZnS: Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ³ -, CI ^" , ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , CI ^" , ZnS: Pb, Cu, Zn ₃ (PO ₄ ) ₂ : Mn ²⁺ ,

Zn ₂ SiO ₄ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , As ⁵⁺ , Zn ₂ SiO ₄ : Mn, Sb ₂ O ₂ , Zn ₂ SiO ₄ : Mn ²⁺ , P, Zn ₂ SiO ₄ : Ti ⁴⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS-ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , Cl and ZnWO ₄ . The compounds of the invention show particular advantages in the mixture with other phosphors of other fluorescent colors or when used in LEDs together with such phosphors.

The compounds according to the invention are preferably used together with green-emitting phosphors. It has been found that, especially when the compounds according to the invention are combined with green-emitting phosphors, the optimization of

Lighting parameters for white LEDs are particularly successful.

Corresponding green-emitting phosphors are known to the person skilled in the art or the person skilled in the art can select from the list given above. Particularly useful green-emitting phosphors are (Sr, Ba) ₂ SiO _4: Eu, (Sr, Ba) 3 SiO _5: Eu, (Sr, Ca) Si ₂ N ₂ O _2: Eu, BaSi ₂ N ₂ O _2: Eu , (Lu, Y) 3 (Al, Ga, Sc) ₅ O ₁₂ : Ce, β-SiAION: Eu, CaSc ₂ O ₄ : Ce, CaSc ₂ O ₄ : Ce, Mg, Ba 3 Si 6 O ₁₂ N ₂ : Eu and Ca 3 (Sc, Mg) ₂ Si 3 O ₁₂ : Ce. Particularly preferred are Ba ₃ Si ₆ O ₁₂ N _2: Eu and Ca 3 (Sc, Mg) ₂ Si ₃ O _12: Ce.

In a further preferred embodiment of the invention, it is preferred to use the compound according to the invention as the sole phosphor. The compound of the invention shows by the broad emission spectrum with a high proportion of red even when used as a single luminescent very good results.

In yet another embodiment of the invention, it is preferred, when the phosphors are arranged on the primary light source, that the red emitting phosphor is substantially illuminated by the light of the primary light source, while the green emitting

Substance is substantially illuminated by the light that has already passed through the red emitting phosphor or was scattered by this. This can be realized by mounting the red emitting phosphor between the primary light source and the green emitting phosphor.

The phosphors or phosphor combinations according to the invention can be present as bulk material, powder material, thick or thin layer material or self-supporting material, preferably in the form of a film. Furthermore, it may be embedded in a potting material. The

Phosphors or phosphor combinations according to the invention can be used either in a resin (eg epoxy or silicone resin) as

Potting material may be dispersed, or may be disposed directly on the primary light source, or spaced apart from it, as appropriate, depending on the application (the latter arrangement also incorporates "remote phosphor technology".) The advantages of "remote phosphor technology" are Known and expert eg in the following publication: Japanese Journal of Applied Physics Vol. 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 light-conducting arrangement. This makes it possible that the primary light source is installed at a central location and this is optically coupled to the phosphor by means of light-conducting devices, such as light-conducting fibers. In this way, the lighting requirements adapted lights can only be made of one or more different phosphors, the one to

Can be arranged, 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.

In addition, the phosphor according to the invention or the emission-converting material can be used in a filament LED, as described for example in US 2014/0369036 A1.

Further subjects of the invention are a lighting unit, in particular for the backlighting of display devices, characterized in that it contains at least one light source according to the invention, and a 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 the invention.

The particle size of the phosphors according to the invention is usually between 50 nm and 30 μιτι for use in LEDs, preferably between 1 μιτι and 20 μιτι.

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. The production and

Use of corresponding shaped bodies is familiar to the person skilled in the art from numerous publications.

The compounds according to the invention have the following advantageous properties:

1) The compounds of the invention have an emission spectrum with a high proportion of red and they have a high photoluminescence quantum yield.

2) The compounds of the invention have only a small

thermal extinction on. Thus, the TQi / 2 values of the compounds according to the invention are usually in the range of more than 500 K.

3) The high temperature stability of the compounds of the invention allows the application of the material even in highly thermally stressed light sources.

4) Furthermore, the compounds of the invention are characterized by a long service life and allow high color rendering and high stability of the color temperature in an LED. This allows warm-white pc LEDs with high color rendering values at low color temperatures (CCT <4000 K) can be realized.

5) The compounds of the invention can be prepared efficiently and inexpensively via a simple synthesis.

All embodiments described herein may be combined with each other unless the respective embodiments are mutually exclusive. In particular, starting from the teachings of this document in the context of routine optimization, it is an obvious process to combine various embodiments described here in order to arrive at a concrete particularly preferred embodiment.

The following examples are intended to illustrate the present invention and, in particular, illustrate the result of such exemplary combinations of the described embodiments of the invention. However, they are by no means to be considered as limiting, but rather are intended to encourage generalization. Any compounds or components used in the preparation 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 amounts of ingredients used in the compositions always add up to a total of 100%. Percentages are always to be seen in the given context.

Examples

measurement methods

The phase formation of the samples was checked by X-ray diffractometry. For this purpose the X-ray diffractometer Miniflex II of the company Rigaku with Bragg-Brentano geometry was used. The radiation source used was an X-ray tube with Cu-Ka radiation (λ = 0.15418 nm). The tube was operated with a current of 15 mA and a voltage of 30 kV. It was measured in an angle range of 10 to 80 ° with 10 ^o -min ^{~ 1} .

The emission spectra were recorded with a fluorescence spectrometer from Edinburgh Instruments Ltd., equipped with a mirror optics for powder samples, at an excitation wavelength of 450 nm. The excitation source used was a 450 W Xe lamp. For temperature-dependent measurement of the emission, the spectrometer was equipped with a cryostat from Oxford Instruments (MicrostatN2). Nitrogen was used as the coolant. Reflection spectra were measured using a fluorescence spectrometer from the company

Edinburgh Instruments Ltd. certainly. The samples were placed in a BaSO ₄ coated Ulbricht sphere and measured. Reflectance spectra were recorded in a range of 250 to 800 nm. The white standard used was BaSO ₄ (Alfa Aesar 99.998%). A 450 W Xe lamp served as the excitation source.

The excitation spectra were recorded with a fluorescence spectrometer from Edinburgh Instruments Ltd., equipped with a mirror optics for powder samples, at 550 nm. The excitation source used was a 450 W Xe lamp.

Example 1: Preparation of NaAso, 995Mn ₀ , 005F5, 995

2.0 g of NaAsF ₆ (9.4 mmol) and 0.05 g (0.2 mmol) of foMnF ₆ are suspended in 5 ml of concentrated HF and stirred for about 2 hours at 70 ° C. Subsequently, the crude product is filtered off and washed with cold acetone several times until the material is acid-free. The obtained light yellow powder is dried in a desiccator in vacuo for 8 h. The CIE1931 color point is x = 0.688 and y = 0.312. The lumen equivalent is 231 lm / W _op t.

Example 2: Preparation of LiAso, 99sMn ₀ , oo5F5, 995

2.0 g of LiAsF ₆ (10.2 mmol) and 0.05 g (0.2 mmol) of K ₂ MnF ₆ are suspended in 5 ml of concentrated HF and stirred at 70 ° C. for about 2 hours. Subsequently, the crude product is filtered off and washed with cold acetone several times until the material is acid-free. The light yellow powder obtained is dried in a desiccator in vacuo for 8 h.

Example 3: Representation of KAso, 995Mn ₀ , oosF5,995

2.0 g of KAsF ₆ (8.8 mmol) and 0.05 g (0.2 mmol) of K ₂ MnF ₆ are suspended in 5 ml of concentrated HF and stirred at 70 ° C. for about 2 hours. Subsequently, the crude product is filtered off and washed with cold acetone several times until the material is acid-free. The light yellow powder obtained is dried in a desiccator in vacuo for 8 h.

Example 4: Preparation of NaSbo, 995Mn ₀ , oosF5,995

2.0 g of NaSbF ₆ (7.7 mmol) and 0.05 g (0.2 mmol) of K ₂ MnF ₆ are suspended in 5 ml of concentrated HF and stirred for about 2 hours at 70 ° C. Subsequently, the crude product is filtered off and washed with cold acetone several times until the material is acid-free. The light yellow powder obtained is dried in a desiccator in vacuo for 8 h.

Example 5: Preparation of LiSbo, 99sMn ₀ , oo5F5, 995

2.0 g of LiSbF ₆ (8.2 mmol) and 0.05 g (0.2 mmol) of K ₂ MnF ₆ are suspended in 5 ml of concentrated HF and stirred at 70 ° C. for about 2 hours. Subsequently, the crude product is filtered off and washed with cold acetone several times until the material is acid-free. The light yellow powder obtained is dried in a desiccator in vacuo for 8 h.

Example 6: Representation of KSbo, 995Mn ₀ , oosF5,995

2.0 g of KSbF ₆ (7.3 mmol) and 0.05 g (0.2 mmol) of K ₂ MnF ₆ are suspended in 5 ml of concentrated HF and stirred at 70 ° C. for about 2 hours. The crude product is then filtered off with suction and cold acetone washed several times until the material is acid-free. The light yellow powder obtained is dried in a desiccator in vacuo for 8 h.

Example 7: Production and Measurement of LEDs Using the Luminescent Materials

General regulation for the production and measurement of pc-LEDs:

A mass of ITILS (in g) of the luminescent material listed in the respective LED example and a mass of nriYAG: ce (in g) (available under the trade name U728 from Philips) are weighed and mixed with msiiikon (in g) of an optically transparent silicone and then homogeneously mixed in a planetary centrifugal mixer, so that the

Concentration of the luminescent material in the total mass o_s (in wt .-%) is. The resulting silicone-luminescent material mixture is applied by means of an automatic dispenser on the chip of a blue semiconductor LED and cured with heat. The listed in the present examples for the LED characterization

Reference LED was filled with pure silicone without luminescent material. The blue semiconductor LEDs used have a

Emission wavelength of 450 nm and are operated with a current of 350 mA. The light-technical characterization of the LEDs is carried out with a spectrometer from the company Instrument Systems - spectrometer CAS 140 and an associated integrating sphere ISP 250.

The LED is characterized by the determination of the

wavelength-dependent spectral power density. The spectrum thus obtained of the light emitted by the LED is used to calculate the color point coordinates CIE x and y.

The weights of the luminescent materials and other materials used in the respective example as well as the color coordinates of the LEDs obtained according to the general procedure described above are summarized in Table 1. The associated LED spectra are shown in FIG.

Table 1: Composition and properties of the manufactured LED A and LED B.

Description of the figures

Figure 1: powder X-ray diffractogram (Cu-K _a radiation) of

NaAso, 995Mno, oo5F ₅ , 995 (Example 1).

Figure 2: Reflectance spectrum of NaAso, 995Mno, oo5F ₅ , 995 (Example 1).

FIG. 3: Excitation spectrum of NaAso, 99sMno, oo5F5.995 (Example 1) (A _Em = 627 nm).

Figure 4: Emission spectrum of NaAso, 995Mno, oo5F ₅ , 995 (Example 1) (λ _Ε χ = 465 nm).

FIG. 5: spectra of LED A and LED B containing YAG: Ce and NaAsF ₆ : Mn ⁴⁺ (Example 1) for the color temperatures 2700 and 3000 K.

Claims

claims

1 . Compound of the general formula (I)

where the symbols and indices used are:

M ² is selected from the group consisting of As, Sb, Bi and

Mixtures of two or three thereof; and

0 <x <1, 00.

2. A compound according to claim 1, characterized in that M ¹

is selected from the group consisting of Li, Na, K and

Mixtures of two or three of them.

3. A compound according to claim 1 or 2, characterized in that M ^{2 is} selected from the group consisting of As, Sb and mixtures of As and Sb, which may optionally contain Bi.

4. A compound according to one or more of claims 1 to 3, characterized in that 0 <x <0.80, preferably 0 <x <0.60, more preferably 0 <x <0.40, more preferably 0.001 <x < 0.20, more preferably 0.001 <x <0.10, and most preferably 0.001 <x <0.010.

5. A compound according to claim 1, characterized in that applies to the symbols and indices used:

M ¹ is selected from the group consisting of Li, Na, K and

Mixtures of two or three thereof; M ² is selected from the group consisting of As, Sb and

Mixtures of As and Sb which may optionally contain Bi; and

0 <x <0.60, preferably 0 <x <0.40, more preferably 0.001 <x <0.20, more preferably 0.001 <x <0.10, and most preferably 0.001 <x <0.010.

6. A compound according to one or more of claims 1 to 5, characterized in that the compound is coated on the surface with another compound.

7. A process for preparing a compound according to one or more of claims 1 to 6, comprising the steps: a) preparation of a suspension / solution comprising M ¹ , M ² and Mn in an HF solution;

b) stirring the suspension / solution; and

c) separation of the resulting solid.

The process of claim 7, wherein step c) is followed by the following step: d) washing and drying the resulting solid.

9. Use of a compound according to one or more of

Claims 1 to 6 as a phosphor or conversion luminescent material for the partial or complete conversion of UV light, violet light and / or blue light in light with a longer wavelength.

10. An emission-converting material comprising a compound according to one or more of claims 1 to 6 and optionally one or more further conversion phosphors.

11. Light source, comprising at least one primary light source and

at least one compound according to one or more of claims 1 to 6 or an emission-converting material according to claim 9.

The light source of claim 1 1, wherein the primary light source comprises a luminescent indium-aluminum-gallium-nitride.

13. The light source according to claim 12, wherein the luminescent indium

Aluminum gallium nitride is a compound of the formula IniGajAlkN where 0 <i, 0 <j, 0 <k and i + j + k = 1.

14. Lighting unit, comprising at least one light source according to one or more of claims 1 1 to 13.