WO2017092849A1

WO2017092849A1 - Mn-activated phosphors

Info

Publication number: WO2017092849A1
Application number: PCT/EP2016/001938
Authority: WO
Inventors: Holger Winkler; Thomas Juestel; Claudia SUESSEMILCH; Matthias Mueller
Original assignee: Merck Patent Gmbh
Priority date: 2015-12-01
Filing date: 2016-11-18
Publication date: 2017-06-08
Also published as: TW201728745A; DE102015015355A1

Abstract

The present invention relates to Mn-activated garnet phosphors, a method for the production thereof and the use thereof as conversion phosphors. The present invention also relates to an emission-converting material comprising at least the conversion phosphor according to the invention, and to the use thereof in light sources, in particular pc-LEDs (phosphor-converted light-emitting devices). The invention further relates to light sources, in particular pc-LEDs, and lighting units, which contain a primary light source and the conversion phosphor according to the invention or the emission-converting material.

Description

Mn-activated phosphors

The present invention relates to Mn ⁺ -activated garnet phosphors, a process for their preparation and their use as

Conversion phosphors or in light sources, in particular in phosphorus-converted light-emitting devices, such as pc-LEDs (phosphor converted light emitting devices). The present invention further relates to an emission-converting material comprising the conversion phosphor according to the invention, and to a light source which contains the conversion phosphor 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 conversion phosphor according to the invention or the invention

Contains emission-converting material. The Mn ⁺ -activated garnet phosphors according to the invention are particularly suitable for producing warm-white light in solid-state light sources.

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.

To obtain white emitting inorganic LEDs (light emitting diodes) through additive color mixing, there are basically three different approaches: The RGB LEDs (red + green + blue LEDs), where white light is generated by mixing the light of three different emitting in the red, green and blue spectral light emitting diodes.

The systems UV LED + RGB phosphor, in which a UV emitting semiconductor (primary light source) emits the light to the environment in which three different phosphors (conversion phosphors) are excited to emit in the red, green and blue spectral range. 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 have the advantage of being able to produce white light with only one primary light source and, in the simplest case, only one conversion phosphor. The best known of these systems consists of an indium-aluminum-gallium-nitride chip as a primary light source emitting light in the blue spectral region, and a cerium-doped yttrium-aluminum garnet (YAG: Ce) as a conversion phosphor, which is excited in the blue region and emit light in the yellow spectral range. However, improvements in the color rendering index as well as the stability of the color temperature are desirable. Also, other garnet phosphors of the general formula (Y, Gd, Lu, Tb) 3 (Al, Ga, Sc) 50i 2: Ce are known for this use. Garnet phosphors are special because of their high stability to air and moisture

Interest.

The binary-complementary systems therefore require a yellow converter when using a blue-emitting semiconductor as the primary light source. fluorescent light to reflect white light. Alternatively, green and red emitting conversion phosphors can be used. Alternatively, if a semiconductor emitting in the violet spectral region or in the near UV spectrum is used as the primary light source, then either an RGB phosphor mixture or a dichroic mixture must be used

Mixture of two conversion phosphors, which emit complementary light, used to obtain white light. In the

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 can be provided. Another advantage of a dichromatic phosphor mixture is the lower spectral interaction and the associated higher "package gain".

Therefore, in particular inorganic fluorescent compounds which can be excited in the ultraviolet and / or blue spectral range are becoming increasingly important today

Conversion luminescent material for light sources, in particular for pc LEDs for producing warm white light.

A major disadvantage of using a primary light source with a broadband emitting Ce ³⁺ -doped garnet phosphor or an LED with a dichroic spectrum (blue + yellow-orange) is their dependence of the color reproduction of the color temperature. In addition, low color temperatures (T _c <5000 K) can not be achieved with sufficiently high color rendering (CRI> 80) due to the absence of dark red spectral components.

There is therefore a constant need for new conversion phosphors which can be excited in the ultraviolet or blue spectral range and emit light in the visible range, in particular in the red spectral range. Priority objectives are therefore the extension of the

Product spectrum, improving the color rendering of white LEDs and the realization of 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 efficiency and a high Lumen equivalent are provided. A number of suitable red-emitting phosphors, such as (Ca, Sr) S: Eu, (Ca.Sr.Ba ^ SisNeiEu and (Ca, Sr) AISiN3: Eu or mixtures of these phosphors have already been proposed for this purpose in a large number of patent applications. One

Disadvantage of these previously used red emitting phosphors is their relatively low stability, which is partly due to the sensitivity to hydrolysis of the sulfidic or nitridic host lattice and partly due to the redoxability of the Eu ²⁺ activator. In addition, the lumen equivalent of 200 to 270 lm / W is not as high as that of Eu ³⁺ phosphors with 280 to 360 Im W due to the broad emission band.

As alternatives to the sulfidic and nitridic phosphors, garnet phosphors have been proposed, which are characterized by a lower

Distinguish hydrolysis sensitivity.

For example, JP 2009/079094 discloses garnet phosphors which are co-doped with Mn ^{2+ in} addition to the Ce ³⁺ doping. Charge compensation takes place via the simultaneous incorporation of silicon instead of aluminum in the host lattice.

CN 101694862 A describes lithium-containing fluorescent phosphors of the chemical formula: Li _a (Gdi _-x Yx) 3Al5 + aOi2 + 2a: TR with 0 <a <1, 0; 0.1 <x <0.5; and TR = Ce, Pr, Eu, Dy, Tb, Sm, Mn, Ti or Fe, which are used in LEDs to produce warm white light.

From WO 2012/045393 A1 are Mn ⁴⁺ -akti fourth phosphors of the general formula Lu3-x-zA _x Al5-y-zSc _y Oi2: Mn _z Ca _z (with A = Y, Gd or Tb; 0 <x < 2.90, 0 <y <0.50, and 0.005 <z <0.05). Furthermore, methods for producing the Mn ⁴⁺ -activated fourth phosphors and their use as conversion phosphors in lamps are described.

WO 2014/177247 A1 shows garnet phosphors of the general formula M3- _x Ce _x (Al5-yz-wGazScw) Mn _y Oi2-yHaly (where M = Y, Gd, Lu and / or Tb; Hai = F, Cl, Br and / or I; 0 <x <0.3; 0 <y <0.2; 0 <z <1, 0; and 0 <w <1, 0). These have Ce ³⁺ and Mn ²⁺ co-doped garnet phosphors have Emission bands in the green or yellow / orange spectral range between 520 and 600 nm.

A disadvantage of the known garnet phosphors described above over the Mn ⁴⁺ -activated garnets of the present invention is that LEDs with high color rendering at low

Color temperatures (CCT <4000 K) can not be realized because the red spectral component is missing. Object of the present invention is therefore to phosphors

develop, which have a red luminescence and are particularly suitable for use in high-power pc LEDs for generating warm white light. This allows the person skilled in the art a greater choice

suitable materials for the production of white emitting devices. A further object of the present invention is to provide red phosphors which have a higher proportion of the emission in the red spectral region than the phosphors known from the prior art, or which have an emission spectrum with an emission maximum shifted to the longer wavelength range in comparison to conventional phosphors , This allows warm white pc LEDs with high color rendering at low

Color temperatures (CCT <4000 K) can be realized. Another object of the present invention is to provide red phosphors that are well known in the art

Make phosphors easier and more efficient to synthesize. Further, it is an object of the present invention to provide red phosphors which have low sensitivity to hydrolysis and low redox stability. Surprisingly, it was found that the tasks of

present invention by providing a Mn ⁴⁺ -activated phosphor can be solved. The Mn ⁴⁺ -activated phosphors of

present invention are garnet phosphors doped with Mn ⁺ and an alkali metal selected from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals. The

Surprisingly, inventors have found that suitable Y, Gd, Dy- and / or Lu-containing garnet phosphors having an emission maximum in the red spectral range, high photoluminescent quantum energy and low sensitivity to hydrolysis and Redoxlabilität be obtained if, in addition to the Mn ⁺ doping an alkali metal selected from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals, used as co-dopants. The incorporation of the monovalent alkali metal M ² takes place on the lattice sites of the trivalent Y, Gd, Dy and / or Lu. The doping with alkali metals allows a simple and efficient synthesis, since alkali metals are good in the

Have garnet structure installed.

The present invention thus relates to a compound of the following general formula (1),

(M 3-x / 2M ² × / ₂ ) (Al 5 -x- _y Ga _y ) M nx O ₂ (1) where the following applies to the symbols and indices used:

M ¹ is selected from the group consisting of Y, Gd, Dy and Lu and mixtures of these metals;

M ² is selected from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals;

0 <x <3.00; and

0 <y <1, 00.

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

Metal atom (M ¹ ) ³⁺ . M ² is a singly charged metal atom (M ² ) ⁺ . Al and Ga are in each case present as triply charged metal atoms Al ³⁺ and Ga ³⁺ and Mn is present as a fourfold charged metal atom Mn ⁴⁺ , while oxygen in the form of O ^{2 "} compensates for the positive charges in the compound.

The Mn ⁴⁺ -activated phosphors according to the invention are

Garnet phosphors selected with Mn ⁴⁺ and an alkali metal (M ² ) ⁺ from the group consisting of Li, Na, K and Rb and mixtures of two or more of these metals are doped. In the general formula (1), two Mn ⁴⁺ ions replace two Al ³⁺ ions and one (M ² ) ⁺ ion (M ¹ ) ³⁺ ion in the garnet crystal lattice.

The compounds according to the invention are obtained by the use of (M ² ) 2CÜ 3 for co-doping, where M ^{2 is} Li, Na, K or Rb and a mixture of two or more of these metals.

All of the Mn ⁺ and (M ² ) ⁺ co-doped garnet phosphors described here have emission bands in the red spectral range between 600 and 750 nm and have a high photoluminescence quantum yield.

The compounds according to the invention are usually in the ultraviolet and / or blue spectral range from about 250 to about 550 nm,

preferably from about 300 to about 400 nm, excitable and usually emit with an emission maximum in the red spectral range of about 600 to about 750 nm, thereby covering the red spectral range.

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, and blue light denotes light of which

Emission maximum between 400 and 459 nm, as cyan

Such a light whose emission maximum lies between 460 and 505 nm, as green light, whose emission maximum lies between 506 and 545 nm, as yellow light, whose emission maximum lies between 546 and 565 nm, as orange light, of which

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 MY, Lu or a mixture of Y and Lu. In a more preferred embodiment, M ^{1 is} Y or Lu. In a particularly preferred embodiment, M ^{1 is} Lu. The compound of the invention preferably contains Al or a combination of Al with up to 20 atom% of Ga.

In a preferred embodiment of the invention, for the index x in the general formula (1): 0 <x 2.00, more preferably 0 <x -i 1, 00, more preferably 0 <x <0.50, more preferably 0 <x <0.10, and most preferably 0 <x 0.05.

For the index y in the general formula (1), preferably:

0 <y <, 0.50. Particularly preferred is y = 0.

Preferably, M ^{2 is} selected from the group consisting of Li, Na and K and mixtures of two or more of these metals.

In a particularly preferred embodiment of the invention, several of the above-mentioned preferences apply simultaneously, regardless of whether they are preferred, particularly preferred, or more potent

preferred and / or most preferred features.

Particular preference is therefore given to compounds of the general formula (1) in which the following applies:

M ¹ is selected from the group consisting of Y, Lu and mixtures of these metals;

M ² is selected from the group consisting of Li, Na and K and mixtures of two or more of these metals;

0 <x <0.50, preferably 0 <x <0.10, more preferably 0 <x <0.05; and

0 <y <0.50, preferably y = 0.

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 (1), comprising the following steps: a) Preparation of a solution containing M ¹ , M ² , Al, Mn and

optionally Ga;

b) adding citric acid or tartaric acid;

c) drying the solution; and

d) calcining the resulting solid at elevated temperature.

The solution in step a) is prepared by dissolving salts which contain M ¹ , M ² , Al, Mn and optionally Ga in an aqueous medium. The salts in step a) can be added either successively in any order or simultaneously. The salts can be added either as solids or as solutions. The addition of the citric or tartaric acid in step b) takes place after the addition of all the salts in step a). The use of citric acid in step b) is preferred.

In the process for producing a compound according to the

general formula (1), the corresponding oxide (M ¹ ) 2O3 is preferably used in step a) as salt for the ion (M ¹ ) ³⁺ . The oxide is preferably dissolved in an aqueous acid such as nitric acid.

Furthermore, the ion (M ² ) ⁺ in step a) is preferably in the form of

corresponding carbonate (M ² ) 2CO3 used. It is also possible to use other water-soluble M ² salts, for example M ² halides selected from M ² F, M Cl, M ² Br and M ² I.

Suitable for Al in step a) are various salts, such as, for example, nitrate (Al (NO 3) 3), acetate (Al (OAc) 3) or other water-soluble Al salts. Preference is given to the nitrate salts. If the compound according to the invention contains Ga, this becomes

Element in step a) is preferably used in the form of the nitrate (Ga (NO 3) 3), acetate (Ga (OAc) 3) or oxalate (Ga 2 (C 2 O-i) 3).

Mn is preferably used in step a) in the form of water-soluble manganese salts, for example Mn halides selected from MnF 2, MnCb, MBr 2 and Mn, manganese acetate (ηη (ΟΑ) or manganese oxalate (MnC 2 O-r 2 H 2 O)) of manganese oxalate

(MnC ₂ O ₄ -2H ₂ O).

The solution in step a) is preferably an acidic solution. Preferably, in step a) first (M) 2O3 is dissolved in an acid, preferably in nitric acid, more preferably in dilute nitric acid. In parallel, the other salts are dissolved in demineralized water and then the previously dissolved (M) 2O3 is added. It follows the addition of

Citric acid or tartaric acid, preferably citric acid, in step b).

The dissolution of the starting compounds can be carried out at room temperature or elevated temperature. Preferably, the release of the

Starting compounds with heating at 50 to 120 ° C, more preferably at 80 to 100 ° C.

The drying of the mixture in step c) is preferably carried out at elevated temperature, more preferably in a temperature range of 70 to 170 ° C, more preferably in a temperature range of 110 to 150 ° C. After drying in step c), a precursor compound is obtained which already contains all the phosphor present in the invention

Contains metals in the corresponding stoichiometric ratio.

As a result, a uniform and complete doping of the

Phosphor with Mn ⁺ and M ² ensured. The precursor compound is then converted into the phosphor of the invention by calcination in step d).

The calcining of the solid in step d) of the process according to the invention is preferably carried out in two steps. The first calcination step is carried out in air or under oxidizing conditions. Preferred here is a reaction time of 0.5 to 10 h, more preferably from 1 to 5 h, most preferably from 2 to 4 h, and a temperature in the range of 800 to 1300 ° C, particularly preferably from 900 to 1 100 ° C, most preferably from 950 to 1050 ° C.

In a preferred embodiment of the invention, the precalcined product from the first calcination step is cooled and comminuted, for example, crushed, before being subjected to the second calcination step.

The second calcination step is preferably carried out in air or under oxidizing conditions. Preference is given here to a reaction time of from 1 to 1.5 h, particularly preferably from 2 to 10 h, very particularly preferably from 3 to 5 h, and a temperature in the range from 1400 to 1800 ° C., more preferably from 1500 to 1700 ° C., most preferably between 1550 and 1650 ° C.

The calcining can be carried out, for example, so that the resulting mixtures are introduced in a high-temperature furnace, for example in a chamber furnace. As a reaction vessel, for example, a corundum crucible with lid is suitable.

It is preferred if the compounds according to the invention are comminuted after the second calcination step, for example by mortars. In a further embodiment, the inventive

Compounds are coated. Suitable for this purpose are all the coating methods known to the person skilled in the art according to 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. In this case, the coating, for example by fluidized bed process or be carried out wet-chemically. 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. On the one hand, the aim of the coating can be a higher stability of the phosphors, 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 compound of the invention as a phosphor or conversion luminescent material, in particular for the partial or complete conversion of ultraviolet and / or blue light of a light emitting diode in light with a longer wavelength.

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

A further subject of the present invention is therefore an emission-converting material comprising a compound according to 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 "conversion luminescent substance" as defined above It may also be preferred that the emission-converting material according to the invention contains, in addition to the compound according to the invention

Conversion phosphors contains. 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 which emit light with mutually 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 an 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 according to the invention extends over a wide range, ranging from about 250 to about 550 nm, preferably from about 300 to about 400 nm. Usually, the maximum of the excitation curve is between 325 and 375 nm.

Another object of the present invention is a light source containing at least one primary light source and at least one compound of the invention. The maximum emission of the primary light source is usually in the range of about 250 to about 550 nm, preferably in the range of about 300 to about 400 nm. Particularly preferred is a range between 325 and 375 nm, wherein the primary radiation partially or completely by the inventive

Phosphor is converted into longer-wave radiation.

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 IniGajAlkN, where 0 <i, 0 <j, 0 <k, and i + j + k = 1 is.

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 invention

Light source is the primary light source is a source that shows 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 suitable phosphors which are familiar to the person skilled in the art. Corresponding phosphors which are suitable in principle for mixtures are, for example:

Ba ₂ Si0 ₄ : Eu ²⁺ , BaSi ₂ N ₂ O ₂ : Eu, BaSi ₂ O 5: Pb ²⁺ , Ba ₃ Si 60i ₂ N ₂ : Eu,

Ba _x Sri _-x F ₂ : Eu ²⁺ (where 0 <x <1), BaSrMgSi ₂ 0 ₇ : Eu ²⁺ , BaTiP ₂ 0 ₇ ,

(Ba, Ti) ₂ P ₂ O 7: Ti, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ Si0 ₄ : Mn ²⁺ , Bi4Ge ₃ Oi ₂ , CaAl ₂ 0 ₄ : Ce ³⁺ , CaLa ₄ 0 ₇ : Ce ³⁺ , CaAl ₂ O ₄ : Eu ²⁺ , CaAl ₂ O ₄ : Mn ²⁺ , CaAl ₄ 07: Pb ²⁺ , Mn ²⁺ ,

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

Ca ₃ AI ₂ _{SI30) 2:} Eu ^2+, CA2B ₅ O ₉ Br: Eu ^2+, Ca ₂ B ₅ 0 ₉ CI: Eu ^2+, Ca ₂ B ₅ 0 ₉ CI: Pb ^2+, CaB ₂ 0 ₄ : Mn ^2+, Ca ₂ B ₂ 0 _5: Mn ^2+, CaB ₂ 0 _4: Pb ^2+, CaB ₂ P ₂ O _9: Eu ^2+,

Ca ₅ B ₂ SiOi ₀ : Eu ³⁺ , Ca ₀ .5Bao. ₅ Ali ₂ Oi ₉ : Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (P0) ₃ Cl: Eu ²⁺ , CaBr ₂ : Eu ²⁺ in Si0 ₂ , CaCl ₂ : Eu ²⁺ in Si0 _2l CaCl ₂ : Eu ⁺ , Mn ²⁺ in Si0 ₂ , CaF ₂ : Ce ³⁺ , CaF ₂ : Ce ³⁺ , Mn ²⁺ , CaF ₂ : Ce ³⁺ , Tb ³⁺ , CaF ₂ : Eu ²⁺ , CaF ₂ : Mn ²⁺ , CaGa ₂ O ₄ : Mn ²⁺ , CaGa ₄ O ₇ : Mn ²⁺ , CaGa ₂ S: Ce ³⁺ , CaGa ₂ S ₄ : Eu ²⁺ ,

CaGa ₂ S ₄ : Mn ²⁺ , CaGa ₂ S: Pb ²⁺ , CaGeO ₃ : Mn ²⁺ , Cal ₂ : Eu ²⁺ in SiO ₂ , Cal ₂ : Eu ²⁺ , Mn ²⁺ in SiO _2l CaLaB0 ₄ : Eu ³⁺ , CaLaB ₃ 0 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 0 _6: Eu ^2+, Ca ₃ MgSi ₂ 0 _8: Eu ²⁺ , Ca ₂ MgSi ₂ O ₇ : Eu ⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Mn ²⁺ ,

Ca ₂ MgSi ₂ O: 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 ⁺ , Ca ₂ P ₂ 0 ₇ : Ce ³⁺ , α-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , β-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , Ca ₅ (PO ₄ ) ₃ CI: Eu ²⁺ , Ca ₅ ( P0 ₄ ) ₃ Cl: Mn ²⁺ , Ca ₅ (PO) ₃ Cl: Sb ³⁺ , Ca ₅ (P0) ₃ Cl: Sn ²⁺ , β-Ca ₃ (PO) ₂ : Eu ²⁺ , Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F: Mn ²⁺ ,

Ca ₅ (PO) ₃ F: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ F: Sn ⁺ , α-Ca ₃ (PO) ₂ : Eu ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Eu ²⁺ , Ca ₂ P ₂ O: Eu ²⁺ , Ca ₂ P ₂ O ₇ : Eu ⁺ , Mn ²⁺ , CaP ₂ 0 ₆ : Mn ²⁺ , a-Ca ₃ (P0) ₂ : Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Sn ⁺ , β-Ca ₂ P ₂ O ₇ : Sn, Mn, α-Ca ₃ (PO) ₂ : Tr, CaS: Bi ³⁺ ,

CaS: Bi ³⁺ , Na, CaS: Ce ³⁺ , CaS: Eu ⁺ , CaS: Cu ⁺ , Na ⁺ , CaS: La ³⁺ , CaS: Mn ²⁺ , CaSO 2: Bi, CaSO ₄ : Ce ³⁺ , CaSO ₄ : Ce ³⁺ , Mn ²⁺ , CaSO ₄ : Eu ²⁺ , CaSO 2: Eu ²⁺ , Mn ²⁺ , CaSO ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , CI, CaS : Pb ²⁺ , Mn ²⁺ , CaS r ^ Pb ^ .Cl, 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, CaSc204: Ce, Ca 3 (Sc, Mg) 2Si30i2: _Ce> CASI0 _3: Ce ^_3+> Ca ₃ Si0 ₄ Cl 2: Eu ^2+,

Ca ₃ SiO 4 Cl ₂ : Pb ²⁺ , CaSiO ₃ : Eu ⁺ , CaSiO ₃ : Mn ²⁺ , Pb, CaSiO ₃ : Pb ²⁺ ,

CaSiO ₃ : Pb ⁺ , Mn ²⁺ , CaSiO ₃ : Ti ⁴⁺ , CaSr 2 (PO ₄ ) ₂ : Bi ³⁺ ,

β- (Ca, Sr) 3 (PO 4) ₂ : Sn ²⁺ Mn ⁺ , CaTio. ₉ Alo.iO3: Bi ³⁺ , CaTi0 ₃ : Eu ³⁺ , CaTi0 ₃ : Pr ³⁺ , Ca ₅ (V04) 3CI, CaW0 _4l CaW0 ₄ : Pb ²⁺ , CaW0 ₄ : W, CasWOeiU, CaYAI0 ₄ : Eu ³⁺ , CaYB0 ₄ : Bi ³⁺ , CaYBO ₄ : Eu ³⁺ , CaYBo.80 ₃ .7: Eu ³⁺ , CaY ₂ ZrO ₆ : Eu ³⁺ ,

(Ca, Zn, Mg) 3 (PO 4) 2: Sn, (Ce, Mg) BaAlnOi ₈ : Ce, (Ce, Mg) SrAlnOi ₈ : Ce,

CeMgAlnOi ₉ : Ce: Tb, Cd 2 B ₆ On: Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: In, CdS: In,

CdS: ln, Te, CdS: Te, CdW0 ₄ , CsF, CsI, CsI: Na ⁺ , CsI: TI,

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

GdNb0: Bi ^3+, Gd ₂ 02S: Eu ^3+, Gd ₂ 0 ₂ Pr ^3+, Gd202S: Pr, Ce, F, Gd ₂ 0 ₂ S: Tb ^3+, Gd ₂ Si0 _5: Ce ^3+, KAIiiOi ₇ : TI ⁺ , KGanOi ₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ Oio: Eu, KMgF ₃ : Eu ²⁺ , KMgF ₃ : Mn ²⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , LaAl ₃ B40i ₂ : Eu ³⁺ , LaAIB ₂ O ₆ : Eu ³⁺ , LaAIO ₃ : Eu ³⁺ , LaAlO ₃ : Sm ³⁺ , LaAsO ₄ : Eu ³⁺ , LaBr ₃ : Ce ³⁺ , LaB0 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 0 ₃ : Eu ³⁺ , La ₂ 0 ₃ : Pr ³⁺ , La ₂ O ₂ S: Tb ³⁺ , LaP0 ₄ : Ce ³⁺ , LaP0 ₄ : Eu ³⁺ ,

LaSi0 ₃ Cl: Ce ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , Tb ³⁺ , LaV0 ₄ : Eu ³⁺ , La 2W ₃ Oi 2: Eu ³⁺ ,

LiAIF ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAlO ₂ : Fe ³⁺ , LiAlO ₂ : Mn ²⁺ , LiAl ₅ O ₈ : Mn ²⁺ ,

Li2CaP207: Ce ^3+, Mn ^2+, LiCeBa Si4Oi4 _4: Mn ^2+, LiCeSrBa ₃ Si40i _4: Mn ^2+,

LilnO ₂ : Eu ³⁺ , LilnO ₂ : Sm ³⁺ , LiLaO ₂ : Eu ³⁺ , LuAlO ₃ : Ce ³⁺ , (Lu, Gd) ₂ SiO ₅ : Ce ³⁺ , Lu ₂ SiO ₅ : Ce ³⁺ , Lu ₂ Si ₂ O 3: Ce ³⁺ , LuTaO ₄ : Nb ⁵⁺ , Lui _-x YxAlO ₃ : Ce ³⁺ (where 0 <x <1), (Lu, Y) 3 (Al, Ga, Sc) 50i 2: Ce, MgAl204: Mn ²⁺ , MgSrAli ₀ Oi: Ce, MgB ₂ O ₄ : Mn ²⁺ , MgBa ₂ (P0 ₄ ) 2: Sn ²⁺ , MgBa ₂ (PO 4) ₂ : U, MgBaP ₂ 0 ₇ : Eu ⁺ , MgBaP ₂ 07: 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) Ge 0 ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) O ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ 0 ₄ : Mn ²⁺ , Mg ₈ Ge ₂ OiiF ₂ Mn ⁺ , MgS: Eu ²⁺ , MgSiO ₃ : Mn ²⁺ , Mg ₂ Si0 ₄ : Mn ²⁺ ,

Mg ₃ Si0 ₃ F ₄ : Ti ⁴⁺ , MgSO ₄ : Eu ²⁺ , MgS0 ₄ : Pb ⁺ , MgSrBa ₂ Si ₂ O 7: Eu ²⁺ ,

MgSrP ₂ 0 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 ₄ , MgYB0 ₄ : Eu ³⁺ ,

Na ₃ Ce (PO ₄ ) 2: Tb ³⁺ , Nai.23 Ko.42Eu ₀ . i2TiSi4On: Eu ³⁺ ,

Nai.23Ko. 2Euo.i2TiSi50i3-xH2O: Eu ³⁺ , Nai.29Ko. 6Ero.o ₈ TiSi4On: 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, SrAli20i ₉ : Ce ³⁺ , Mn ⁺ , SrAl ₂ 04: Eu ²⁺ , SrAI ₄ 0 ₇ : Eu ³⁺ ,

SrAli ₂ Oi _9: Eu ^2+, SrAI ₂ S _4: Eu ^2+, SR2b ₅ 0 ₉ CI: Eu ^2+, SrB40 _7: Eu ²⁺ (F, Cl, Br), SrB ₄ 0 ₇ : Pb ²⁺ , SrB ₄ 0 ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ 0i ₃ : Sm ²⁺ ,

Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ : Eu ²⁺ , (8Γ, Β 3) 38ιΌ5: Ευ, (8Γ, θ 3) 8ί2Ν2θ ₂ : Ευ, Sr (CI, Br, I) ₂ : Eu ²⁺ in S1O 2, SrCl ₂ : Eu ²⁺ in S1O 2, Sr ₅ Cl (PO ₄ ) 3: Eu, SrwFxB ₄ O 6.5: u ²⁺ ,

SrwFxB _y O _z : Eu ²⁺ , Sm ²⁺ _> SrF ₂ : Eu ²⁺ , SrGai ₂ Oi ₉ : Mn ²⁺ , SrGa ₂ S: Ce ³⁺ ,

SrGa ₂ S ₄ : Eu ²⁺ , SrGa ₂ S ₄ : Pb ⁺ , Srln ₂ 0 ₄ : Pr ³⁺ , Al ³⁺ , (Sr, Mg) 3 (PO ₄ ) 2: Sn, SrMgSi ₂ O ₆ : Eu ²⁺ Sr2MgSi207: Eu ^+, Sr3MgSi208: 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 0 ₃ : Pb ²⁺ , Mn ²⁺ , a-SrO-3B ₂ 0 ₃ : Sm ²⁺ , Sr 6 P 5 B 0 ₂ o: Eu ₎ Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ₁ Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Pr ³⁺ , Sr ₅ (PO ₄ ) 3 Cl: Mn ²⁺ , Sr5 (P0) 3 Cl: Sb ^3+, Sr2P20 _7: Eu ^2+, Sr-ß ₃ (P0) _2: Eu ^2+, Sr ₅ (P0 ₄₎ 3F: Mn ^2+, Sr ₅ (P0 ₄₎ 3F : Sb ³⁺ , Sr ₅ (Pp) 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) 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: Ce ³⁺ , SrSO: Eu ²⁺ , SrS 0: Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ OioCl 6: Eu ²⁺ , Sr ₂ SiO ₄ : Eu ²⁺ , SrTiO ₃ : Pr ³⁺ ,

SrTi0 ₃ : Pr ³⁺ , Al ³⁺ , SrY20 ₃ : Eu ³⁺ , Th0 ₂ : Eu ³⁺ , Th0 ₂ : Pr ³⁺ , Th0 ₂ : Tb ³⁺ ,

Β ₃ Β4θΐ2: Βί ³⁺ , YAl ₃ B ₄ Oi 2: Ce ³⁺ , YAl ₃ B ₄ 0i 2: Ce ³⁺ , Mn, YAl ₃ B ₄ Oi ₂ : Ce ³⁺ , Tb ³⁺ , YAl ₃ B Oi ₂ Eu ³⁺ , YAl ₃ B ₄ O ₂ : Eu ³⁺ , Cr ³⁺ , YAl ₃ B40i 2: Th ⁺ , Ce ³⁺ _I Mn ²⁺ ,

YAI0 _3: Ce ^3+, Y3AI ₅ 0i _2: Ce ^3+, Y3AI ₅ O _2: Cr ^3+, YAlO _3: Eu ^3+, Y3AI ₅ O _2: Eu ^3r, Y4AI ₂ 0 _9: Eu ^3+, Y3AI ₅ Oi ₂ : Mn ⁴⁺ , YAlO ₃ : Sm ³⁺ , YAlO ₃ : Tb ³⁺ , Y ₃ Al ₅ Oi 2: Tb ³⁺ , YAsO ₄ : Eu ³⁺ , YBOs: Ce ³⁺ , YB0 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 0 ₃ : Eu ³⁺ , Yi. ₃ Gdo.6o0 ₃ (Eu, Pr), Y ₂ O ₃ : Bi ³⁺ , YOBr: Eu ³⁺ , Y ₂ 0 ₃ : Ce, Y ₂ 0 ₃ : Er ³⁺ , Y ₂ 0 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 0 ₃ : Ho ³⁺ , Y ₂ 0 ₂ S: Eu ³⁺ , Y ₂ O ₂ S: Pr ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ 0 ₃ : Tb ³⁺ , YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO: Mn ²⁺ , Th ⁴⁺ , YPO: V ⁵⁺ , Y (P, V) O ₄ : Eu, Y ₂ SiO ₅ : Ce ³⁺ , YTaO _4l YTaO ₄ : Nb ⁵⁺ , YVO: Dy ³⁺ , YVO: Eu ³⁺ , ZnAl ₂ O ₄ : Mn ²⁺ , ZnB ₂ O ₄ : Mn ⁺ , ZnBa ₂ S ₃ : Mn ²⁺ , (Zn, Be) ₂ Si0 ₄ : Mn ²⁺ ,

Zn ₀ .4Cdo.6S: Ag, Zn ₀ .6Cd ₀ .4S: Ag, (Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ 0 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 (P0 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 ⁺ , CI, ZnS-CdS: Cu, Br, ZnS-CdS: Cu, I, ZnS: C | -, 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 , C | -, ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , C | -, ZnS: Pb, Cu, Zn ₃ (P0 ₄ ) ₂ : Mn ²⁺ ,

Zn ₂ Si0: Mn ⁺ , Zn ₂ SiO: Mn ⁺ , As ⁵⁺ , Zn ₂ SiO: Mn, Sb ₂ O ₂ , Zn ₂ SiO: 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 .

In this case, the compound according to the invention shows 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 shown that the optimization of illumination parameters for white LEDs succeeds particularly well when the inventive compounds are combined with green-emitting phosphors.

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 suitable green emitting phosphors are included

(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 02: Eu, (Lu, Y) 3 (Al, Ga , Sc) 5Oi ₂ : Ce, β-SiAION: Eu, CaSc ₂ O ₄ : Ce, CaSc ₂ O: Ce, Mg, Ba 3 Si 6 O ₂ N ₂ : Eu and Ca 3 (Sc, Mg) ₂ Si 3 O ₂ : Ce. Particularly preferred are Ba ₃ Si ₆ Oi ₂ N ₂ : Eu and Ca ₃ (Sc, Mg) ₂ Si ₃ Oi ₂ : 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 phosphor 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 placed directly on the primary light source, or spaced therefrom, 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 J. 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 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.

Further subjects of the invention are a lighting unit, in particular for the backlight of display devices, characterized in that it contains at least one light source according to the invention, and a display device, in particular 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 μm for use in LEDs, preferably between 1 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. 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 according to the invention can be prepared more simply and more efficiently than the garnet phosphors known from the prior art.

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

3) 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.

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

All variants of the invention described here can be combined with one another, as long as the respective embodiments are not contradictory. exclude each other. In particular, starting from the teachings of this document in the context of routine optimization, it is an obvious process to combine just different variants 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 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. All compounds or components 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 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 ° 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. Reflectance spectra were measured with a fluorescence spectrometer from Edinburgh Instruments Ltd. certainly. The samples were placed in a BaS04 coated Ulbricht sphere and measured. Reflectance spectra were recorded in a range of 250 to 800 nm. The white standard used was BaS0 ₄ (Alfa Aesar 99.998%). A 450 W

Xe lamp served as an 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. As a source of inspiration was a

450 W Xe lamp used.

Example 1: Preparation of Lu2.9875 ao, oi25AI ₄ , 975Mno, o250i2

For the synthesis of 6 mmol (5.1036 g) of Lu 2.9875 Na, Oi 25 Al 4.975 Mno, O 250 I 2, 8.9625 mmol (3.5665 g) of LU 2 O 3 are dissolved in hot dilute HNO 3. In parallel, 0.0375 mmol (0.0040 g) of Na ₂ CO ₃ , 29.8500 mmol (11, 1977 g) Al (NO ₃ ) 3-9H ₂ O and 0.1500 mmol (0.0268) ΜηO _{2 are} successively added 0 ₄ · 2Η ₂ Ο dissolved in demineralized water while heating. Subsequently, the previously dissolved LU2O3 and 96.0000 mmol (20.1735 g) of citric acid

(C6H8O7 H2O) was added. The solution is then stirred for 2 h and then evaporated at 130 ° C in a drying oven. The resulting foam is mortared and calcined for 3 h at 1000 ° C and finally for 4 h at 1600 ° C in air. Figures 1, 3, 5, 7, and 9 show the associated powder X-ray diffractogram and excitation, emission and reflection spectra of Lu2,98 5Nao, oi25Al4,975Mno, o250i ₂ .

Example 2: Synthesis of Υ2.9875 ο, οΐ25ΑΙ _{4) 9} 75 ηο, ο25θΐ2

For the synthesis of 8 mmol (4.7496 g) Y2,9875Ko, oi25Al4,9 5Mno, o250i2 1 1, 9500 mmol (2.6984 g) Y2O3 dissolved in hot dilute HNO _3.

In parallel, successively, 0.0500 mmol (0.0069 g) of K 2 CO 3, 39.8000 mmol (14.9303 g) of Al (NO ₃ ) 3-9H ₂ O and 0.2000 mmol (0.0358) of MnC ₂ O ₄ - 2H ₂ 0 dissolved under heating in demineralized water. Subsequently, the previously dissolved Y2O3 and 128.0000 mmol (26.8980 g) of citric acid (06ΗβΟ ₇ · Η2θ) is added. The solution is then stirred for 2 h and then evaporated at 130 ° C in a drying oven. The resulting foam is crushed and held for 3 h at 1000 ° C and finally for 4 h Calcined at 1600 ° C in air. Figures 2, 4, 6, 8, and 10 show the associated powder X-ray diffractogram and excitation, emission and reflectance spectra of Y2.9875Ko, oi25AU, 975Mno, o250i2.

Example 3: Production and measurement of LEDs using the phosphors

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

A mass of mLS (in g) of the phosphor listed in the respective LED example is weighed and mixed with nrtsiiikon (in g) of an optically transparent silicone and then homogeneously mixed in a planetary centrifugal mixer, so that the phosphor concentration in the total mass o_s (in % By weight). The resulting silicone-phosphor mixture is applied by means of an automatic dispenser on the chip of a blue semiconductor LED and cured with heat. The reference LED listed in the present examples for LED characterization was filled with pure silicone without phosphor. The blue semiconductor LEDs used have a

Emission wavelength of 450nm 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 phosphors and other materials used in each example and the color coordinates of the resulting LEDs according to the general rule described above are summarized in Table 1. The associated LED spectra are shown in FIGS. 11 and 12. Parameter Reference LED A LED B

LED

with phosphor from Example 1: with phosphor from Example 2:

LU2,9875Nao, 0125AU, 975Mno, 0250l2 Υ2.9875Κθ, 0125Αΐ4.975ΜΠθ, 025θΐ2 rriLs / g - 5.54 5.58

m silicone 1 4,46 4,42

CLS /Gew.- - 55.4 55.8

%

CIE 1931 x 0.151 0.188 0.180

CIE 1931 y 0.027 0.046 0.043

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

Description of the figures

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

Lu2,9875Nao, oi25Al4,975Mno, o250i2 (Example 1) (above) with the

Reference diffraction diagram for LU3AI5O12 (04-001-9996) (below).

Figure 2: powder X-ray diffractogram for Cu-K _a radiation of

Y2.9875Ko, oi25AU, 975Mno, o250i2 (Example 2) (above) with the

Reference diffraction diagram for Y3AI5O12 (04-017-6068) (below).

Figure 3: Excitation spectrum of Lu2,98 5Nao, oi25Al4,9 5Mno, o250i2

(Example 1) (A _Em = 668 nm).

FIG. 4: excitation spectrum of

Y2,9875Ko, oi25AI _4, 975Mno, o250i2 (Example 2) (ÄEm = 672 nm).

Figure 5: Emission spectrum of Lu2,9875Nao, o-i25Al4,975Mno, o25Oi2

(Example 1) (λ _Εχ = 330 nm).

Figure 6: Emission spectrum of Y2.9875Ko, oi25Al4.975Mno, o250i2

(Example 2) (λ _Εχ = 330 nm).

Figure 7: Reflectance spectrum of Lu2,9875Nao, oi25Al4,975Mno, o25Oi2

(Example 1) with BaSO4 as white standard. Figure 8: Reflectance spectrum of Y2.9875Ko, oi25AU, 975Mno, o25Oi2

(Example 2) with BaSÜ4 as white standard.

Figure 9: Emission spectra of Lu2,9875Nao, oi25Al4,975Mno, o250i2

(Example 1) (λεχ = 330 nm) at T = 100 to 500 K and sigmoidal curve fitting of the emission integral.

Figure 10: emission spectra of Υ2,9β75Κο, οΐ25Αΐ4,975Μηο, ο25θΐ2 (Example 2) (λ _Ε χ = 330 nm) at T = 100 to 500 K and sigmoidal curve fitting of the emission integral.

FIG. 11: Spectrum of the LED A containing

LU2,9875Nao, 0125Al4,975 no, 0250l2.

FIG. 12: Spectrum of the LED B containing Υ2.9875Κ ₀ .οΐ25ΑΙ ₄ , 975Μηο, ο25θΐ2.

Claims

claims

Compound of the general formula (1),

(M ¹ 3-x / ² M ² x / 2) (Al 5-x-y Ga y) M n _x Ol 2 (1) where the following applies to the symbols and indices used:

0 <x <3.00; and

0 <y <1, 00.

A compound according to claim 1, characterized in that M ^{1 is} selected from the group consisting of Y and Lu and

Mixtures of these metals.

Compound according to claim 2, characterized in that M ^{1 is} Y or Lu.

Compound according to one or more of claims 1 to 3, characterized in that the following applies: 0 <x -Ξ 2.00, more preferably

0 <x <1.00, more preferably 0 <x -S 0.50, more preferably 0 <x <0.10, and most preferably 0 <x <0.05.

Compound according to one or more of Claims 1 to 4, characterized in that the following applies: 0 <y <0.50, preferably y = 0. Compound according to one or more of claims 1 to 5, characterized in that M ^{2 is} selected from the group consisting of Li, Na and K and mixtures of two or more of these metals.

Compound according to Claim 1, characterized in that the following applies to the symbols and indices used:

M is selected from the group consisting of Y, Lu and

Mixtures of these metals;

0 <x <0.50, preferably 0 <x -S 0.10, more preferably

0 <x <0.05; and

0 <y <0.50, preferably y = 0.

A compound according to one or more of claims 1 to 7, characterized in that the compound is coated on the surface with another compound.

Process for the preparation of a compound according to one or more of Claims 1 to 8, comprising the steps: a) Preparation of a solution comprising M ¹ , M ² , Al, Mn and

optionally Ga;

b) adding citric acid or tartaric acid;

c) drying the solution; and

d) calcining the resulting solid at elevated temperature.

Use of a compound according to one or more of

Claims 1 to 8 as a phosphor or conversion luminescent material for the partial or complete conversion of ultraviolet and / or blue light into light having a longer wavelength.

11. An emission-converting material comprising a compound according to one or more of claims 1 to 8 and optionally one or more further conversion phosphors.

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

at least one compound according to one or more of claims 1 to 8 or an emission-converting material according to claim 11.

13. Lighting unit containing at least one light source

Claim 12.