EP2872592A1

EP2872592A1 - Process for production of phosphors

Info

Publication number: EP2872592A1
Application number: EP13729920.2A
Authority: EP
Inventors: Tim Vosgroene; Holger Winkler; Ralf Petry; Andreas Benker; Christof Hampel
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2012-07-13
Filing date: 2013-06-14
Publication date: 2015-05-20
Also published as: CN104428395A; KR20150034782A; WO2014008970A1; US20150203748A1; TWI602903B; TW201406926A; US9580649B2; JP2015529701A; CN104428395B

Abstract

The present invention relates to a process for production of a europium-doped alkaline earth metal siliconitride or alkaline earth metal silicooxynitride having an increased emission efficiency. The present invention further relates to europium-doped alkaline earth metal siliconitrides and alkaline earth metal silicooxynitrides which are obtainable according to the production process according to the invention, and also to the use of the europium-doped alkaline earth metal siliconitrides and alkaline earth metal silicooxynitrides according to the invention as conversion phosphors. The present invention also further relates to a light-emitting device which contains a europium-doped alkaline earth metal siliconitride or alkaline earth metal silicooxynitride according to the invention.

Description

Process for the production of phosphors

The present invention relates to a process for producing a europium-doped alkaline earth metal silicon nitride or silicooxynitride with increased emission efficiency. Another object of the present invention relates to europium-doped alkaline earth metal siliconitrides or silicooxynitrides, which are obtainable according to the manufacturing method of the invention, and to the use of the europium-doped alkaline earth metal siliconitrides or silicooxynitrides according to the invention as conversion phosphors. A further subject matter of the present invention relates to a light-emitting device which contains a europium-doped alkaline earth metal silicon nitride or silicooxynitride according to the invention.

Inorganic fluorescent powders excitable in the blue and / or UV spectral range are becoming increasingly important as conversion phosphors for phosphor converted LEDs, in short pc LEDs. Meanwhile, many conversion phosphor systems are known, such as alkaline earth orthosilicates, thiogallates, garnets and nitrides each doped with Ce ³⁺ or Eu ²⁺ . In particular, the latter Nitridleuchtstoffe, z. M ₂ Si ₅ N ₈ : Eu (M = Ca, Sr and / or Ba) or

MAISiN ₃ : Eu (M = Ca and / or Sr) are currently the subject of intense research because these materials have emission wavelengths above 600 nm and are therefore important for the production of warm white pc LEDs with color temperatures <4000 K.

In the following, the currently known processes for the preparation of M ₂ Si ₅ N ₈ : Eu are briefly summarized, where M stands for an alkaline earth metal:

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

(Schnick et al., Journal of Physics and Chemistry of Solids (2000),

61 (12), 2001-2006)

(2) (2-x) M ₃ N ₂ + 3x EuN + 5 Si ₃ N 3 M _2-x Eu _x Si ₅ N ₈ + 0.5x N ₂

(Hintzen et al., Journal of Alloys and Compounds (2006), 417 (1-2), 273-279) (3) (2-x) MO + 1, 666 Si ₃ N ₄ + 0.5x Eu ₂ O ₃ + (2 + 0.5x) C + 1.5 N ₂ ^

M _2-x Eu _x Si ₅ N ₈ + (2 + 0.5x) CO

(Piao et al., Applied Physics Letters 2006, 88, 161908) (4) 2 Si ₃ N ₄ + 2 (2-x) MCO 3 + x / 2 Eu ₂ O ₃ -> M ₂ -xEu _x Si ₅ N 8 + M ₂ SiO ₄ + CO ₂ (Xie et al., Chemistry of Materials, 2006, 18, 5578)

(5) (2-x) M + x Eu + 5 SiCl ₄ + 28 NH ₃ M _2- xEu _x Si ₅ N ₈ + 20 NH ₄ Cl + 2 H ₂ (Jansen et al., WO 2010/029184 A1 ). Silicooxynitrides are included, for example, by stoichiometric mixing of SiO ₂ , M ₃ N ₂ , S 13 N 4 and EuN followed by calcining

Temperatures of about 1600 ° C accessible (eg, according to WO 2011/091839).

Of the above methods for the preparation of silicon nitrides, in particular, the method (2) is suitable, since the corresponding starting materials are commercially available, in the synthesis of no secondary phases and the efficiency of the resulting materials is highest. In this process, a second calcining step is often connected, which increases the efficiency of the material even more.

In a variation of the above process (2), the underlying alkaline earth metal nitride can be used in an excess of up to 30 mol% to the stoichiometric amount given in equation (2). The superstoichiometric use of the alkaline earth metal nitride leads to an increased radiation-induced emission efficiency of the resulting conversion phosphor.

In addition, it has also been found that the excess of alkaline earth metal nitride used can be chosen to be so high that theoretically a different nitride phase is formed. Substituting the respective reactants according to the reaction equation (ii) below, it is not the material SrSiN ₂ which is also known, but Sr ₂ Si ₅ N ₈ , which is produced according to equation (i) by default (the europium compound necessary for doping with europium became Simplification omitted): 2/3 Sr ₃ N ₂ + 5/3 Si ₃ N ₄ Sr ₂ Si ₅ N ₈ (')

1/3 Sr ₃ N ₂ + 1/3 Si ₃ N ₄ > SrSiN ₂ ())

-> 0.2 Sr ₂ Si ₅ N ₈ + 0.2 Sr ₃ N ₂

According to equation (ii), however, only the strontium compound can be represented. The corresponding Ba ₂ Si ₅ N ₈ , however, can not be represented in a phase-pure manner analogous to reaction equation (ii), but only according to reaction equation (i).

Furthermore, it has been found that in a superstoichiometric use of the alkaline earth metal nitride in a modified by the method (2) reaction, a second calcining step has no effect on the efficiency of the material so illustrated.

Since alkaline earth metal nitrides are very expensive, the disadvantage of a method in which these are used more than stoichiometrically, is obvious. To conserve resources, it would therefore be desirable to have a method available in which a smaller amount of alkaline earth metal nitride is needed. The disadvantage of a process in which the Erdakalimetall-nitride is stoichiometrically or only in slight excess is used, however, as described above, the lower radiation-induced emission efficiency of the material obtained.

It was therefore the object of the present invention to provide a method with which the radiation-induced emission efficiency of

Europium-doped alkaline earth metal siliconitrides or silicooxynitrides can be increased without having to use an extreme excess of alkaline earth metal nitride for the synthesis. Another

The object of the present invention is also to provide a process for the production of europium-doped alkaline earth metal siliconitrides or silicooxynitrides with increased radiation-induced emission efficiency, with which the barium compounds and not only the

Strontium compounds are available. Another object of the present invention is to provide a method with which the emission wavelength of a europium-doped alkaline earth metal silicon nitride or silicooxynitrides can be shifted to larger or smaller wavelengths.

In a first aspect of the present invention, there is provided a method for increasing radiation-induced emission efficiency and / or a method for shifting the emission wavelength of a europium-doped alkaline earth metal silicon nitride or a europium-doped alkaline earth silicooxynitride, comprising the steps of: (a) producing a mixture of a europium-doped alkaline earth metal silicon nitride or europium-doped alkaline earth metal silico-oxynitride and an alkaline earth metal nitride, wherein the alkaline earth metal of the europium-doped alkaline earth metal silicon nitrile or silicooxynitride and the alkaline earth metal nitride are the same or different could be; and

(b) calcining the mixture under non-oxidizing conditions.

Europium-doped alkaline earth metal siliconitrides or silicooxynitrides are known to the person skilled in the art as conversion phosphors, and the person skilled in the art knows which compounds fall into these classes of materials. In particular, these are compounds which, apart from the dopant, essentially consist of the elements alkaline earth metal, in particular Ca, Sr and / or Ba, silicon, nitrogen and in the case of oxynitrides oxygen. These may also contain SiO ₂ and / or Si ₃ N ₄ , which may each be present in amorphous and / or crystalline form. It should be pointed out that aluminosiliconitrides which additionally contain aluminum are not understood to be siliconitrides or silicooxynitrides in the context of the present application. The term "conversion luminescent material" is understood in the present application to mean a material which absorbs radiation in a specific wavelength range of the electromagnetic spectrum, preferably in the blue or in the UV spectral range, and in another wavelength range of the electromagnetic wavelength

Spectrum, preferably in the red, orange, yellow or green spectral range, in particular in the red spectral range, emitted visible light. In this context, the term "radiation-induced

"Emission efficiency", ie the conversion phosphor absorbs radiation in a certain wavelength range and emits radiation in another wavelength range with a certain efficiency.The increase of the emission efficiency is measured in the increase of the emitted light intensity. that one conversion luminescent material emits light at a different wavelength compared to another or a similar conversion luminescent material, that is, shifts to a smaller or larger wavelength, ie it shifts the emission maximum.

The europium-doped alkaline earth metal silicon nitride or silicooxynitride used in the above-mentioned process is preferably a compound represented by the following general formula (I):

EA _d Eu _c e _e NfO _x · m SiO ₂ · n Si ₃ N ₄ formula (I) in which the following applies to the symbols and indices used:

EA is at least one alkaline earth metal, in particular selected from

Group consisting of Ca, Sr and Ba;

E is at least one element of the fourth main group, in particular Si; 0.80 <d <1, 995;

0.005 <c <0.2;

4.0 <e <6.00;

5.00 <f <8.70;

0 <x <3.00;

0 <m <2.50;

0 <n <0.50; where the following relationship applies to the indexes:

2d + 2c + 4e = 3f + 2x.

In the compounds of the formula (I), m = 0 and n = 0 are preferred. Preferred europium-doped alkaline earth metal or siliconitrides -Silicooxy- nitrides are also the compounds of the following formulas (Ia) and (Ib), Ba2 _-a - _b - _{c +} _{i, 5z} Sr _a Ca _b Eu _c Si5N _8- 2 / 3x _{+ z} O _x · m Si0 ₂ · n Si ₃ N ₄ formula (Ia) where the indices used have the following meanings:

0 <a <2;

0 <b <2;

0.01 <c <0.2, preferably 0.02 <c <0, 1;

0 <x <1, preferably 0 <x <0.6;

0 <z <3.0, preferably 0 <z <1, 0, more preferably z = 0;

and a + b + c <2 + 1.5z;

0 <m <2.50, preferably 0 <m <1.00, more preferably m = 0;

0 <n <0.50, preferably n = 0; Baa _a - _b - _c _{+ x} i os. _δ Sr _a Ca _b Eu _c SisNe- _x + _z O _x · m SiO ₂ · n Si ₃ N ₄ Formula (Ib) where the indices used have the following meanings:

0 <a <2;

0 <b <2;

0.01 <c <0.2, preferably 0.02 <c <0.1;

0 <x <1, preferably 0 <x <0.6;

0 <z <3.0, preferably 0 <z <1, 0, more preferably z = 0;

0 <m <2.50, preferably 0 <m <1.00, more preferably m = 0;

0 <n <0.50, preferably n = 0. Another suitable alkaline earth metal silicon nitride which can be used in the above-mentioned process is a compound of the following general formula (II)

Bai _-a- bc raCabEucSi ₇ Nio · m · n S1O2 S13N4 formula (II) wherein the indices used have the following meanings: 0 <a <1;

0 <b <1; 0.01 <c <0.2, preferably 0.02 <c <0.1; and

a + b + c <1;

0 <m <2.50, preferably 0 <m <1.00, more preferably m = 0;

0 <n <0.50, preferably n = 0.

In the compounds of the formula (I), (Ia), (Ib) and (II), m is preferably 0 or n = 0, more preferably m = 0 and n = 0.

Particularly preferably, in the compounds of the formulas (Ia), (Ib) and (II), the abovementioned preferences occur simultaneously.

The europium-doped alkaline earth metal silicon nitride or silicooxynitride used in step (a) can be prepared by any method known in the art, for example as described above under processes (1) to (5) or in WO 2011/091839 , However, it is particularly preferred that the europium-doped alkaline earth metal silicon nitride or silicooxynitride be prepared by a step (a ') comprising calcining a mixture containing a europium source, a silicon source and an alkaline earth metal nitride under non-oxidizing conditions. This step (a ') precedes step (a) of the above method.

As europium source in step (a '), any conceivable europium compound can be used with which a europium-doped alkaline earth metal silicon nitride or silicooxynitride can be prepared. Europium oxide (especially Eu ₂ O ₃ ) and / or europium nitride (EuN), in particular Eu ₂ O _3, are preferably used as europium source in the process according to the invention.

As silicon source in step (a ¹ ), any imaginable silicon compound can be used with which a europium-doped alkaline earth metal silicon nitride or silicooxynitride can be produced. Silicon nitride and optionally silicon oxide are preferably used in the process according to the invention as the silicon source. If a pure nitride is to be produced, the silicon source is preferably silicon nitride. Is the Production of an oxynitride is desired, so silicon dioxide is used in addition to silicon nitride as silicon source.

An alkaline earth metal nitride is understood as meaning a compound of the formula M ₃ N ₂ in which M is independently an alkaline earth metal ion in each occurrence, in particular selected from the group consisting of calcium, strontium and barium. In other words, the alkaline earth metal nitride is preferably selected from the group consisting of calcium nitride (Ca ₃ N ₂ ), strontium nitride (Sr ₃ N ₂ ), barium nitride (Ba ₃ N ₂ ) and their

Mixtures exists.

The compounds used in step (a ') for the preparation of

Europium-doped alkaline earth metal silicon nitride or silicooxynitride are preferably used in a ratio to one another such that the atomic number of the alkaline earth metal, of silicon, of europium, of nitrogen and optionally of oxygen is the desired

Ratio in the alkaline earth metal silicon nitride or silicooxynitride of the above formula (I), (la), (Ib) or (II). In particular, a stoichiometric ratio is used, but also a slight excess of alkaline earth nitride is possible.

The weight ratio of the europium-doped alkaline earth metal silicon nitride or silicooxynitride to the alkaline earth metal nitride in step (a) of the process according to the invention is preferably in the range from 2: 1 to 20: 1 and more preferably in the range from 4: 1 to 9: 1.

The process is carried out under non-oxidizing conditions, i. H. under largely or completely oxygen-free conditions, in particular under reducing conditions.

When the inventive method for shifting the emission wavelength of the europium-doped alkaline earth metal silicon nitride or

Silicooxynitride, it is preferred that in step (a) the alkaline earth metal in the alkaline earth metal nitride be different from the alkaline earth metal in the europium-doped alkaline earth metal silicon nitride or silicooxynitride. If, for example, barium is used as the alkaline earth metal in the alkaline earth metal silicon nitride or silicooxynitride in step (a), it is preferred that strontium be used as the alkaline earth metal in the alkaline earth metal nitride. In this way, the method according to the invention leads to a europium-doped alkaline earth metal silicon nitride or silicooxynitride, which shows a red-shifted emission compared to the europium-doped barium silicon nitride or silicooxynitride, which was used as starting material. Conversely, in the europium-doped alkaline earth metal silicon nitride or

Silicooxynitride of step (a) using strontium as the alkaline earth metal and barium as the alkaline earth metal in alkaline earth metal nitride, this results in a europium-doped alkaline earth metal silicon nitride or silicooxynitride compared to strontium silicon nitride or silicooxynitride, respectively Edukt was used, a blue shifted emission shows.

A further embodiment of the present invention relates to a process for producing a post-treated europium-doped alkaline earth metal silicon nitride or a post-treated europium-doped silicooxynitride, comprising the following steps:

(i) Synthesis of a europium-doped alkaline earth metal silicon nitride or

-Silicooxynitrids; and

(ii) calcining a mixture containing that obtained in step (i)

Europium-doped alkaline earth metal silicon nitride or silicooxynitride and an alkaline earth metal nitride under non-oxidizing conditions.

The synthesis in process step (i) is preferably carried out by

Calcining a mixture containing at least one europium source, at least one silicon source and at least one alkaline earth metal nitride under non-oxidizing conditions. Calcining the mixture of this europium-doped alkaline earth metal silicon nitride or silicooxynitride with an alkaline earth metal nitride in step (ii) gives the aftertreated europium-doped alkaline earth metal silicon nitride or silicooxynitride. The term "post-treated" in the context of the present invention therefore relates to a europium-doped alkaline earth metal silicon nitride or Silicooxynitride which has been calcined with an alkaline earth metal nitride under non-oxidizing conditions.

The aftertreated europium-doped alkaline earth metal silicon nitride or silico-oxynitride prepared in the process of this embodiment according to the invention is also defined as described above. All preferred variants given above are also preferred according to the invention here.

The step (i) is preferably carried out identically to the step (a ') described above. All definitions and preferred variants to

Step (a ') mentioned above, also apply according to the invention for the step

(») ^■

The product obtained in step (i) is preferably a europium-doped alkaline earth metal silicon nitride or silicooxynitride, as defined above. Preference is thus given to compounds of the formula (I), (Ia), (Ib) and (II). The difference between the europium-doped alkaline earth metal silicon nitride or silicooxynitride obtained in step (i) and the aftertreated europium-doped alkaline earth metal silicon nitride or silicooxynitride prepared in the process of the second embodiment can not be determined from the empirical formula when the alkaline earth metal of europium -doped alkaline earth metal silicon nitride or silicooxynitride and the alkaline earth metal nitride are the same, so that both compounds are preferably a compound of general formula (I), (la), (Ib) or (II). If the alkaline earth metal of the europium-doped alkaline earth metal silicon nitride or silicooxynitride differs from the alkaline earth metal of the alkaline earth metal nitride, then the content of the alkaline earth metals of the europium-doped alkaline earth metal silicon nitride or

Silicooxynitride from that of the post-treated europium-doped alkaline earth metal silicon nitride or silicooxynitride. If, for example, a barium silicon nitride or silicooxynitride is subsequently treated with strontium nitride, a barium strontium silicon nitride or silicooxynitride is obtained after the aftertreatment. The essential difference that can be discerned, however, is not in the given structural formula (I) or (II), but is mainly found in the radiation-induced emission efficiency. Is used as Alkaline earth metal nitride used in step (i) another alkaline earth metal nitride than in step (ii), then the difference of the europium-doped alkaline earth metal silicon nitrile or silicooxynitride from step (i) to the aftertreated obtained after step (ii) Europium-doped alkaline earth metal silicon nitride or silicooxynitride in that the emission maximum of the radiation-induced emission is shifted.

The ratio by weight of europium-doped alkaline earth metal silicon nitride or silicooxynitride from step (i) to the alkaline earth metal nitride in step (ii) is preferably in the range from 2: 1 to 20: 1, and more preferably in Range from 4: 1 to 9: 1.

All mixtures prepared in the process according to the invention are preferably prepared by processing the starting compounds into a homogeneous mixture. In other words, the starting compounds are used in powder form and processed together, for example by a mortar, to a homogeneous mixture.

All steps of calcining, such as steps (a '), (b), (i) and (ii) are preferably carried out under non-oxidizing conditions. Non-oxidizing conditions are understood to be any conceivable non-oxidizing atmospheres, in particular substantially oxygen-free atmospheres, ie an atmosphere whose maximum oxygen content is <100 ppm, in particular <10 ppm, vacuum not being suitable as non-oxidizing atmosphere in the present case , A non-oxidizing atmosphere can be generated, for example, by the use of inert gas, in particular nitrogen or argon. A preferred non-oxidizing atmosphere is a reducing atmosphere. The reducing atmosphere is defined as containing at least one reducing gas. Which gases have a reducing effect is known to the person skilled in the art. Examples of suitable reducing gases are hydrogen, carbon monoxide, ammonia or ethylene, more preferably hydrogen, which gases may also be mixed with other non-oxidizing gases. The reducing atmosphere is particularly preferred by a mixture of nitrogen and Hydrogen produced, preferably in the ratio H ₂ : N ₂ from 10: 50 to 33: 30, each based on the volume.

The steps of calcination (a '), (b), (i) and (ii) are each independently preferably at a temperature in the range of 1200 ° C to 2000 ° C, more preferably 1400 ° C to 1800 ° C and on most preferably carried out 1500 ° C to 1700 ° C. In this case, the period of calcination is independently of each other preferably 2 to 14 hours, more preferably 4 to 12 hours, and most preferably 6 to 10 hours.

The calcining is preferably carried out in each case such that the resulting mixtures are introduced, for example, in a vessel made of boron nitride in a high-temperature furnace. The high-temperature furnace is preferably a tube furnace containing a carrier plate of molybdenum foil.

After calcination in step (b) or step (ii), the compounds obtained are preferably treated with acid to wash away unreacted alkaline earth metal nitride. Hydrochloric acid is preferably used as the acid. Here, the resulting powder is preferably suspended for 0.5 to 3 hours, more preferably 0.5 to 1.5 hours in 0.5 molar to 2 molar hydrochloric acid, more preferably about 1 molar hydrochloric acid, then filtered off and filtered at a temperature of Range dried from 80 to 150 ° C.

In a further embodiment of the invention, after the calcination and the work-up, which can be carried out by acid treatment as described above, a further calcination step is connected again. This preferably takes place in a temperature range from 200 to 400.degree. C., more preferably from 250 to 350.degree. This further calcination step is preferably carried out under a reducing atmosphere. The duration of this calcination step is usually between 15 minutes and 10 hours, preferably between 30 minutes and 2 hours.

In yet a further embodiment, the compounds obtained by one of the above-mentioned inventive methods will be coated. Suitable for this purpose are all coating methods, as 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. The coating can be carried out, for example, by fluidized bed processes. Further suitable coating methods are known from JP 04-304290, WO 91/10715, WO 99/27033, US 2007/0298250, WO 2009/065480 and WO 2010/075908.

The present invention further relates to a post-treated europium-doped alkaline earth metal silicon nitride or silicooxynitride, which is obtainable according to one of the methods according to the invention. The compound produced by the process according to the invention differs from compounds of the same or similar composition prepared according to the prior art in that it has a higher emission efficiency. Due to the complex structure of the compound of the invention, the compound of the invention can not be clearly characterized by structural features. However, it is clearly distinguishable from compounds known in the art by having a higher radiation-induced emission efficiency and possibly a color shift of the emission maximum compared to corresponding materials in which no further calcination step was carried out with an alkaline earth metal nitride.

An alkaline earth metal silicooxynitride of the above formula (Ia) is novel and is therefore a further subject of the present invention. This compound is an essential starting material in the process according to the invention of the first embodiment. This compound corresponds, depending on the exact execution of the process and depending on the educts used, further the reaction product after the post-treatment step.

The invention therefore furthermore relates to a compound of the formula (Ia)

Ba2 _-a -bc ₊ _i, _b 5zSraCa EucSi5N _8- 2 / 3x ₊ zox m · SiO ₂ · n Si ₃ N ₄ formula (la) where the indices used have the following meanings: 0 <a <2;

0 <b <2;

0.01 <c <0.2, preferably 0.02 <c <0.1;

0 <x <1, preferably 0.03 <x <0.8, more preferably 0.1 <x <0.6; 0 <z <3.0, preferably 0 <z <1, 0, more preferably z = 0;

0 <m <2.50, preferably 0 <m <1.00, more preferably m = 0;

0 <n <0.50, preferably n = 0;

and a + b + c <2 + 1.5z.

In the compounds of the formula (Ia), preference is given to m = 0 or n = 0, more preferably m = 0 and n = 0.

In the compounds of the formula (Ia), the abovementioned preferences are particularly preferably present simultaneously, that is to say they are preferably compounds for which the following applies:

0 <a <2;

0 <b <2;

0.02 <c <0.1;

0.03 <x <0.8;

0 <z <1.0;

0 <m <1.00;

n = 0;

and a + b + c <2 + 1.5z.

Particularly preferred are compounds for which:

0 <a <2;

0 <b <2;

0.02 <c <0.1;

0.1 <x <0.6;

z = 0;

m = 0;

n = 0;

and a + b + c <2 + 1.5z. Another object of the present invention is the use of the aftertreated europium-doped alkaline earth metal silicon nitride or silicooxynitride or the compound of the abovementioned formula (Ia) as a phosphor, in particular as a conversion luminescent substance.

A further subject of the present invention is an emission-converting material comprising the aftertreated europium-doped alkaline earth metal silicon nitride or silicooxynitride according to the invention or the compound of the formula (Ia). The emission-converting material may consist of the europium-doped alkaline earth metal silicon nitride or silicooxynitride or of the compound of the formula (Ia) according to the invention and would in this case be equated with the term "conversion luminescent substance" as defined above.

It is also possible that the emission-converting material according to the invention contains, in addition to the compound according to the invention, further conversion phosphors. In this case, the emission-converting material according to the invention contains a mixture of at least two conversion phosphors, one of which is an aftertreated europium-doped alkaline earth metal silicon nitride according to the invention or

Silicooxynitride or a compound of formula (la). It is particularly preferred that the at least two conversion phosphors are phosphors which emit light of different wavelengths which are complementary to one another. Is it in the aftertreated europium-doped alkaline earth metal silicon nitride or

Silicooxynitride or the compound of formula (Ia) to a red

emitting phosphor, it is preferably used in combination with a green or yellow emitting phosphor or with a cyan or blue emitting phosphor. Alternatively, the red-emitting conversion phosphor according to the invention can also be used in combination with (a) blue-emitting and green-emitting conversion phosphor (s). Alternatively, the red-emitting conversion phosphor according to the invention can also be used in combination with (a) green-emitting conversion luminescent substance (s). It may therefore be preferred that the conversion phosphor according to the invention in Combination with one or more further conversion phosphors is used in the emission-converting material according to the invention, which together then preferably emit white light. In the context of this application, blue light is defined as light whose emission maximum lies between 400 and 459 nm, cyan light whose emission maximum is between 460 and 505 nm, green light whose emission maximum lies between 506 and 545 nm , as yellow light such, 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 670 nm. The aftertreated europium-doped alkaline earth metal silicon nitride or silicooxynitride according to the invention or the compound of the formula (Ia) is preferably a red-emitting conversion luminescent substance. As a further conversion luminescent substance that can be used together with the compound according to the invention, it is generally possible to use any possible conversion luminescent substance. Suitable examples are: Ba ₂ Si0 ₄ : Eu ²⁺ , BaSi ₂ O ₅ : Pb ²⁺ , Ba _x Sr ₁ -x F ₂ : Eu ²⁺ ,

BaSrMgSi ₂ 0 ₇ : Eu ²⁺ , BaTiP ₂ O ₇ , (Ba, Ti) ₂ P ₂ O ₇ : Ti, Ba ₃ W0 ₆ : U,

BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ Si0 ₄ : Mn ²⁺ , Bi ₄ Ge ₃ O ₁₂ , CaAl ₂ 0 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 ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ 0 _2: Eu ^2+, Ca ₂ B ₅ O ₉ Br: Eu ^2+, Ca ₂ B ₅ O ₉ Cl: Eu ^2+, Ca ₂ B ₅ 0 ₉ CI: Pb ^2+, CaB ₂ 0 ₄ : Mn ²⁺ , Ca ₂ B ₂ O ₅ : Mn ²⁺ ,

CaB ₂ O ₄ : Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ²⁺ , Ca ₅ B ₂ SiO ₂ ₀ : Eu ³⁺ ,

Cao. ₅ Bao.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⁺ , CaF ₂ : Eu ²⁺ , CaF ₂ : Mn ²⁺ , CaF ₂ : U, CaGa ₂ O ₄ : Mn ²⁺ ,

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

CaGa ₂ S ₄ : Pb ²⁺ , CaGeO ₃ : Mn ²⁺ , Cal ₂ : Eu ²⁺ in SiO ₂ , Cal ₂ : Eu ²⁺ , Mn ²⁺ in

Si0 ₂ , CaLaBO ₄ : Eu ³⁺ , CaLaB ₃ 0 ₇ : Ce ³⁺ , Mn ²⁺ , Ca ₂ La ₂ BO ₆ . _5: Pb ^2+, Ca ₂ MgSi ₂ O _7> Ca ₂ MgSi ₂ 0 _7: Ce ^3+, CaMgSi ₂ O _6: Eu ^2+, Ca ₃ MgSi ₂ 0 _8: Eu ^2+, Ca ₂ GSi 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 P2O _7: Ce ^3+, a-Ca ₃ (P0 ₄₎ 2: Ce ^3+, beta-Ca ₃ (P0 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 (P0 ₄₎ 3 Cl: Sn ²⁺ ₍

beta-Ca3 (PO4) 2: Eu ^2+, Mn ^2+, Ca ₅ (P0 ₄₎ ₃ F: Mn ^2+, Ca _s (PO ₄₎ ₃ F: Sb ^3+, Ca _s (PO4) ₃ F: Sn ^2+, a-Ca ₃ (PO ₄₎ _2: Eu ^2+, beta-Ca ₃ (PO4) _2: Eu ^2+, Ca ₂ P ₂ 0 _7: Eu ^2+, Ca ₂ P ₂ O _7: Eu ₁ ²⁺ Mn ^_2+> CaP ₂ O _6: Mn ^2+, a-Ca ₃ (PO ₄₎ 2: Pb ^2+, a-Ca ₃ (P0 ₄₎ _2: Sn ^2+, beta-Ca ₃ (PO ₄ ) 2: Sn ²⁺ , β-Ca ₂ PO 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 ₄ : Eu ²⁺ , CaSO ₄ : Eu ²⁺ , Mn ²⁺ , CaSO ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , CI, CaS: Pb ²⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , CI, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ , CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , CI, CaS: Y ³⁺ ,

CaS: Yb ²⁺ , CaS: Yb ²⁺ , CI, CaSiO ₃ : Ce ³⁺ , Ca ₃ Si0 ₄ Cl ₂ : Eu ²⁺ , Ca ₃ Si0 ₄ Cl ₂ : Pb ²⁺ ,

CaSiO ₃ : Eu ²⁺ , CaSiOaiMn ^ .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⁺ , CaTio.gAlo.iOsiBi ^{3 *} ,

CaTi0 ₃ : Eu ³⁺ , CaTi0 ₃ : Pr ³⁺ , Ca ₅ (V0 ₄ ) ₃ Cl, CaWO ₄ , CaW0 ₄ : Pb ²⁺ , CaWO ₄ : W, Ca ₃ W0 ₆ : U, CaYAI0 ₄ : Eu ^{3 +} , CaYBO ₄ : Bi ³⁺ , CaYB0 ₄ : Eu ³⁺ , CaYBo. ₈ 0 ₃ .7: Eu ³⁺ , CaY ₂ ZrO ₆ : Eu ³⁺ , (Ca, Zn, Mg) 3 (PO ₄ ) ₂ : Sn _I CeF ₃ , (Ce, Mg) BaAl Oie: Ce,

(Ce, Mg) SrAlnOi ₈ : Ce, CeMgAl Oi ₉ : Ce: Tb, Cd ^ eO iMn ² *, CdS: Ag ⁺ , Cr, CdS: In, CdS: In, CdS: In, Te, CdS: Te, CdW0 ₄ , CsF, CsI, CsI: Na ⁺ , CshTI, (ErCl ₃ ) o. ₂ 5 (BaCl ₂ ) o.75, GaN: Zn, Gd ₃ Ga ₅ O ₁₂ : Cr ³⁺ , Gd ₃ Ga ₅ O ₁₂ : Cr, Ce,

GdNb0 ₄ : Bi ³⁺ , Gd ₂ 0 ₂ S: Eu ³⁺ , Gd ₂ 0 ₂ Pr ³⁺ , Gd ₂ 0 ₂ S: Pr, Ce, F, Gd ₂ 0 ₂ S: Tb ³⁺ , Gd ₂ Si0 ₅ : Ce ³⁺ , KAIn 0 ₁₇ : TI ⁺ , KGa 0 ₇ : Mn ² \ K ₂ La ₂ Ti ₃ O ₁₀ : Eu, KMgF ₃ : Eu ²⁺ , KMgF ₃ : Mn ²⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , LaAl ₃ B ₄ 0i 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⁺ , LaBO ₃ : Eu ³⁺ , (La, Ce, Tb) PO ₄ : Ce: Tb, LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³⁺ , LaOBr: Tm ³⁺ , 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 CI: Ce ³⁺ , LaSiO ₃ CI: 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⁺ , LiAlO ₂ : Fe ³⁺ , LiAlO ₂ : Mn ²⁺ , LiAl ₅ O ₈ : Mn ²⁺ ,

Li ₂ CaP ₂ O ₇ : Ce ³⁺ , Mn ²⁺ , LiCeBa ₄ Si ₄ O ₄ : Mn ²⁺ , LiCeSrBa ₃ Si ₄ O ₁₄ : Mn ²⁺ ,

LilnO _2: Eu ^3+, LilnO _2: Sm ^3+, LiLa0 _2: Eu ^3+, LuAIO _3: Ce ^3+, (Lu, Gd) ₂ Si0 _5: Ce ^3+, Lu ₂ Si0 _5: Ce ^3+, Lu ₂ Si ₂ O ₇ : Ce ³⁺ , LuTaO ₄ : Nb ⁵⁺ , Lu _1- xY _x AlO ₃ : Ce ³⁺ , MgAl ₂ O ₄ : Mn ²⁺ , gSrAl ₁₀ O ₁₇ : Ce, MgB ₂ O. _4: Mn ^2+, MgBa ₂ (P0 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 (P0 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 0 ₁₉ : Tb ³⁺ , Mg ₄ (F) GeO ₆ : Mn ²⁺ ,

Mg ₄ (F) (Ge, Sn) 0 ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ 0 ₄ : Mn ⁺ , Mg ₈ Ge ₂ O ₁ iF ₂ : Mn ⁴⁺ , MgS: Eu ²⁺ , MgSiO ₃ : Mn ²⁺ , Mg ₂ SiO ₄ : Mn ²⁺ , Mg ₃ Si0 ₃ F ₄ : Ti ⁴⁺ , MgSO ₄ : Eu ²⁺ , MgS0 ₄ : Pb ²⁺ , 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 Oe: Eu ²⁺ , Mn ²⁺ , Mg ₂ Sr (SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ti0 ₄ : Mn ⁴ \ MgW0 ₄ ,

gYB0 ₄ : Eu ³⁺ , Na ₃ Ce (P0 ₄ ) ₂ : Tb ³⁺ , NalrTI, Na ^ Ko ^ Euo. ^ TiSUO ^ Eu ³ *, Nai ₂ 3Ko. ₄₂ Euo.i ₂ TiSi5O ₁₃ xH ₂ 0: Eu ³⁺ , Na _{1 29} Ko. ₄ 6Ero.o8TiSi ₄ Oii: Eu ³⁺ ,

Na ₂ Mg ₃ A! ₂ Si ₂ Oi ₀ : Tb ₁ Na (Mg _2-x Mn _x ) LiSi ₄ O ₁₀ F ₂ : Mn, NaYF ₄ : Er ³⁺ , Yb ³⁺ ,

NaY0 ₂ : Eu ³ \ P46 (70%) + P47 (30%), SrAl ₁₂ 0 ₁₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ : Eu ²⁺ , SrAl ₄ 0 ₇ : Eu ³⁺ , SrAli ₂ O ₁₉ : Eu ²⁺ , SrAl ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ O ₉ Cl: Eu ²⁺ ,

SrB407: Eu ²⁺ (F, CI, Br), SrB ₄ 0 ₇ : Pb ²⁺ , SrB ₄ 0 ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ 0i ₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O _{4-z / 2} : Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ : Eu ²⁺ , 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 F _x B _y O _z : Eu ²⁺ , Sm ²⁺ , SrF ₂ : Eu ²⁺ , SrGai ₂ O ₁₉ : 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 (P0 ₄₎ _2: Sn, SrMgSi ₂ O _6: Eu ^2+, Sr ₂ MgSi ₂ 0 _7: Eu ^2+, Sr ₃ MgSi ₂ O _8: Eu ² \ SrMoO _4: U, SrO -3B ₂ O ₃ : Eu ²⁺ , CI, β-SrO-3B ₂ 0 ₃ : Pb ²⁺ , β-SrO-3B ₂ O ₃ : Pb ² Mn ²⁺ , a-SrO 3B ₂ 0 ₃ : Sm ²⁺ , Sr ₆ P ₅ BO ₂ o: Eu,

Sr ₅ (PO ₄₎ ₃ Cl: Eu ^+, Sr ₅ (P0 ₄₎ ₃ Cl: Eu ^2+, Pr ^3+, Sr ₅ (PO ₄₎ ₃ Cl: Mn ^2+, Sr ₅ (PO ₄₎ ₃ CI : Sb ^3+, Sr ₂ P ₂ O _7: Eu ^2+, Sr-ß ₃ (P0 ₄₎ _2: Eu ^2+, Sr ₅ (PO ₄₎ ₃ F: Mn ^2+, Sr ₅ (P0 ₄₎ ₃ F: Sb ³⁺ ,

Sr ₅ (PO ₄₎ ₃ F: Sb ^3+, Mn ^2+, Sr ₅ (P0 ₄₎ ₃ F: Sn ^2+, Sr ₂ P ₂ 0 _7: Sn ^2+, ß-Sr ₃ (PO ₄₎ ₂ Sn ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Sn ²⁺ , Mn ²⁺ (Al), SrS: Ce ³⁺ , SrS: Eu ⁺ , SrS: Mn ²⁺ , SrS: Cu ⁺ , Na, SrS0 ₄ : Bi, SrS0 ₄ : Ce ³⁺ , SrS0 ₄ : Eu ² \ SrSO ₄ : Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ O ₁₀ Cl ₆ : Eu ²⁺ ₍ Sr ₂ SiO ₄ : Eu ²⁺ , SrTiO ₃ : Pr ³⁺ , SrTiOs r ^ .AI ³ *, Sr ₃ W0 ₆ : U, SrY ₂ O ₃ : Eu ³⁺ , Th0 ₂ : Eu ³⁺ , ThO ₂ : Pr ³⁺ , Th0 ₂ : Tb ³⁺ , YAl ₃ B ₄ O ₁₂ : Bi ³⁺ , YAl ₃ B ₄ Oi ₂ : Ce ³⁺ ,

YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , Mn, YAl ₃ B ₄ 0 ₂ : Ce ³⁺ , Tb ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ ,

YAI ₃ B ₄ O _12: Eu ^3+, Cr ³⁺ _I YAI ₃ B ₄ Oi _2: Th ^4+, Ce ^3+, Mn ^2+, YAlO _3: Ce ^3+, YaAlsO ^ ICE ³ * ₅ O Y3AI _12: Cr ^3+, YAI0 _3: Eu ^3+, Y3AI ₅ O _2: Eu ^3r,

YAI0 _3: Sm ^3+, YAI0 _3: Tb ^3+, Y3AI ₅ 0i _2: 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) B0 ₃ : Eu, (Y, Gd) B0 ₃ : Tb, (Y, Gd) ₂ O ₃ : Eu ³⁺ , Y _{1 34} Gd _0.6 oO ₃ (Eu, Pr), Y ₂ O ₃ : Bi ³⁺ , YOBr: Eu ³⁺ , Y ₂ 0 ₃ : Ce, Y ₂ O ₃ : Er ³⁺ , Y ₂ O ₃ : Eu ³⁺ (YOE), Y ₂ O ₃ : Ce ³⁺ , Tb ³⁺ , YOCl: Ce ³⁺ ,

YOCI: Eu ^3+, YOF: Eu ^3+, YOF: Tb ^3+, Y ₂ O _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 O _3: Tb ^3+, YPO _4: Ce ^3+, YPO _4: Ce ^3+, Tb ^3+, YPO _4: Eu ^3+,

YPO ₄ : Mn ²⁺ , Th ⁺ , YPO ₄ : V ⁵ \ Y (P, V) 0 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 Si0 _4: Mn ^2+, Zn _0th ₄ Cd ₀ .6S: Ag, Zn _0.6 Cdo _.4 S: Ag, (Zn, Cd) S: Ag, CI,

(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 (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 ⁺ , Cr, 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 ⁺ , Cl ^" , ZnS: Cu, Sn, ZnS: Eu ²⁺ , ZnS: Mn ²⁺ , ZnS: Mn, Cu, ZnS : Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ³ -, Cr, ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , Cl ^" , ZnS: Pb, Cu, Zn ₃ (P0 ₄ ) ₂ : Mn ^2+, Zn ₂ Si0 _4: Mn ^2+, Zn ₂ SiO _4: Mn ^2+, As ^5+, Zn ₂ SiO _4: Mn, Zn ₂ Si0 ₄ SB20 _2l: 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 or ZnWO ₄ .

Another object of the present invention is the use of the emission-converting material according to the invention in a light source. Particularly preferably, the light source is an LED, in particular a phosphor-converted LED, in short pc-LED. In this case, it is particularly preferred that the emission-converting material comprises, in addition to the conversion luminescent material according to the invention, at least one further conversion luminescent material, in particular such that the light source emits white light or light with a specific color point (color-on-demand principle). "Color-on-demand principle" means the realization of light of a particular color point with a pc-LED using one or more conversion phosphors.

Another object of the present invention is thus a light source comprising a primary light source and the emission-converting material.

Again, it is particularly preferred that the emission-converting material in addition to the conversion phosphor according to the invention comprises at least one further conversion luminescent material, so that the light source preferably emits white light or light with a specific color point.

The light source according to the invention is preferably a pc-LED. A pc-LED usually contains a primary light source and an emission converting material. The emission-converting invention

For this purpose, material can either be dispersed in a resin (for example epoxy or silicone resin) or, with suitable size ratios, directly on the Primary light source or from this, depending on the application, be located remotely (the latter arrangement also includes the "Remote Phosphorus Technology" with a). The primary light source may be a semiconductor chip, a luminescent light source such as ZnO, a so-called transparent conducting oxide, a ZnSe or SiC based device, an organic light emitting layer based device (OLED), or a plasma or discharge source, most preferably semiconductor chip. The person skilled in possible forms of such primary light sources are known.

If the primary light source is a semiconductor chip, it is preferably a luminescent indium-aluminum-gallium nitride (InAIGaN), as known in the art. Also suitable are lasers as a light source.

The emission-converting material according to the invention can be converted for use in light sources, in particular pc LEDs, into any external forms such as spherical particles, platelets and structured materials and ceramics. These forms are under the term

"Shaped body" summarized. Consequently, the moldings are emission-converting moldings.

Another subject of the invention is a lighting unit which contains at least one light source according to the invention. Such lighting units are mainly used in display devices, in particular liquid crystal display devices (LC display) with a backlight. Therefore, such a display device is the subject of the present invention.

In the illumination unit according to the invention, the optical

Coupling between the emission-converting material and the primary light source (in particular semiconductor chips), preferably by a light-conducting arrangement. This makes it possible that at a central Location the primary light source is installed and this is optically coupled by means of light-conducting devices, such as photoconductive fibers, to the emission-converting material. In this way, the illumination requirements adapted lights consisting of one or more different conversion phosphors, which may be arranged to a fluorescent screen, and a light guide, which is coupled to the primary light source realize. This makes it possible to place a strong primary light source in a convenient location for the electrical installation and to install without further electrical wiring, only by laying fiber optics at any location, lights of emission-converting materials, which are coupled to the light guide.

The following examples and figures are intended to illustrate the present invention. However, they are by no means to be considered limiting. Description of the figures

Figure 1: emission spectra of variously prepared nitride phosphors. The curve marked 1 shows the emission spectrum of a phosphor prepared according to Comparative Example 1A), which by stoichiometric composition of

Reaction mixture was prepared. The curve marked 2 shows the emission spectrum of a phosphor prepared according to Comparative Example 1 B), which was prepared with an excess of strontium nitride in a single annealing step. Figure 2: emission spectra of variously prepared nitride phosphors. The curve marked 2 shows an emission spectrum of a phosphor prepared according to Comparative Example 1 B), which was prepared with an excess of strontium nitride in a single annealing step. The curve marked 3 shows an emission spectrum of a phosphor according to the invention produced according to Example 1C), which is characterized by stoichiometric representation of the phosphor in the first annealing step and subsequent recalcination of the phosphor was made with the addition of 20 wt .-% strontium nitride.

FIG. 3: Emission spectrum of nitride phosphors produced in various ways. The curve marked 4 shows an emission spectrum of a phosphor prepared according to Comparative Example 2A), which was produced by stoichiometric representation with a single annealing step. The curve marked 5 shows an emission spectrum of a phosphor prepared according to Comparative Example 2B), which was prepared with an excess of barium nitride in an annealing step.

Figure 4: emission spectra of variously prepared nitride phosphors. The curve labeled 4 shows an emission spectrum of a phosphor prepared according to Comparative Example 2A), which was produced by using a stoichiometric mixture in a single annealing step. The curve marked with 6 shows an emission spectrum of a phosphor prepared according to Example 2C), which was prepared by a stoichiometric mixture in a first annealing step followed by Nachkalzination of the phosphor with the addition of 20 wt .-% barium nitride.

Figure 5: emission spectra of variously produced nitride phosphors. The curve marked 6 shows an emission spectrum of a phosphor prepared according to Example 2C), which is characterized by a stoichiometric mixture in the first annealing step with subsequent recalcination of the phosphor with the addition of

20 wt .-% barium nitride was prepared. The curve marked with 7 shows an emission spectrum of a phosphor prepared according to Example 2D), which was prepared by a stoichiometric mixture in the first annealing step and subsequent recalcination of the phosphor with the addition of 20 wt .-% strontium nitride. Figures 6 to 14: emission spectra and results of the LEDs according to Examples 13 to 21, wherein Figure 6 refers to Example 13, Figure 7 to Example 14, etc.

Figure 15: Emission aspects and results of the LEDs according to Example 22A) containing the phosphor according to Example 8A) according to the prior art and Example 22B) containing the phosphor according to Example 8C) according to the present invention.

Examples:

General regulation for measuring the emission

Powder emission spectra are measured by the following general procedure: A phosphor powder bed having a depth of 5 mm, the surface of which has been smoothed out with a glass plate, becomes the integration sphere of a Edinburgh fluorescence spectrometer

Instruments FL 920 irradiated with a xenon lamp as an excitation light source at a wavelength of 450 nm and the intensity of the emitted fluorescence radiation in a range of 465 nm to 800 nm in 1 nm steps measured.

Example 1 :

A) Comparative Example: Preparation of Sr ₂ Si _{5 7)} 6660o, 5: Eu (stoichiometric composition)

3.625 g (12.4 mmol) of strontium nitride, 4.438 g (31 mmol) of silicon nitride, 0.451 g (7.5 mmol) of silica and 0.448 g (3.0 mmol) of europium nitride are weighed together in a glove box and mixed in the hand mortar, until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

B) Comparative Example: Representation of Sr ₂ Si ₅ N _7> 666O ₀ , 5: Eu

Use of a Sr ₃ N ₂ excess

9.452 g (32.333 mmol) of strontium nitride, 4.438 g (31 mmol) of silicon nitride, 0.451 g (7.5 mmol) of silica and 0.498 g (3.0 mmol) of europium nitride are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

C) Preparation of Sr ₂ Si ₅ N ₇ , 6660o, 5: Eu (stoichiometric composition) and postcalzination with addition of Sr ₃ N ₂

The phosphor thus obtained is dissolved in a glove box containing 20% by weight.

Strontium nitride mixed and mixed until a homogeneous

Mixture arises. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess strontium nitride, the phosphor thus obtained is suspended in 1 molar hydrochloric acid for 1 h, then filtered off and dried.

Example 2

A) Comparative example: Preparation of Ba ₂ Si ₅ N ₈ : Eu (stoichiometric composition)

7.223 g (16.333 mmol) of barium nitride, 5.964 g (41.666 mmol) of silicon nitride and 0.166 g (1, 0 mmol) of europium nitride are placed in a glovebox

weighed together and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen /

Hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed. B) Comparative example: Preparation of Ba ₂ Si ₅ N ₈ : Eu using a Ba ₃ N ₂ excess

14.269 g (32.333 mmol) of barium nitride, 4.772 g (33.333 mmol) of silicon nitride and 0.166 g (1, 0 mmol) of europium nitride are placed in a glove box

weighed together and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed. C) Preparation of Ba ₂ Si ₅ N ₈ : Eu (stoichiometric composition) and post-calcination with the addition of Ba ₃ N ₂

weighed together and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

The phosphor thus obtained is mixed in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess barium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. D) Preparation of Ba ₂ Si ₅ N ₈ : Eu (stoichiometric composition) and post-calcination with the addition of Sr ₃ N ₂

weighed together and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , The phosphor thus obtained is dissolved in a glove box containing 20% by weight.

Strontium nitride mixed and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess barium nitride, the phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 3

A) Comparative Example: Synthesis of (Sr, Ba) i, 9oEuo, ioSi5 ₇ , 670o, 5

(Stoichiometric)

0.443 g Eu ₂ 0 ₃ (1.26 mmol), 3.500 g Ba ₃ N ₂ (7.95 mmol), 5.552 g Si ₃ N ₄ (39.58 mmol), 0.376 g Si0 ₂ (6.25 mmol) and 2.313 g of Sr ₃ N ₂ (7.95 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

B) Comparative Example: Synthesis of (Sr, Ba) i, ₀ 9oEu, _{ioSi5N> 67} Oo, 5

(Excess)

0.443 g Eu ₂ O ₃ (1.26 mmol), 4.900 g Ba ₃ N ₂ (10.13 mmol), 5.552 g Si ₃ N ₄ (39.58 mmol), 0.376 g Si0 ₂ (6.25 mmol) and 3,233 g of Sr ₃ N ₂ (10.13 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , To remove excess barium and strontium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid,

then filtered off and dried.

C) Synthesis of (Sr, Ba) i, 9oEuo, ioSi5N ₇ , ₆₇ Oo, 5 - postcalzination

1.761 g of Eu ₂ O ₃ (5 mmol), 28.008 g of Ba ₃ N ₂ (63.336 mmol), 22.660 g of Si ₃ N ₄ (158.300 mmol) and 1, 502 g of SiO ₂ (25.000 mmol) are combined in a glove box weighed and mixed in a hand mortar until, until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

Strontium nitride mixed and mixed until a homogeneous

Mixture arises. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess barium nitride, the phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

D) Synthesis of (Sr, Ba) i, 9oEuo, ioSi5N _7> 6 ₇ Oo, 5 - recalcination

1, 761 g Eu ₂ O ₃ (5 mmol), 18.421 g Sr ₃ N ₂ (63.336 mmol), 22.660 g Si ₃ N ₄ (158.300 mmol) and 1, 502 g SiO ₂ (25.000 mmol) are in a

Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

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

E) Synthesis of (Sr, Ba) i, 9oEuo, ioSi5N ₇ , ₆ 70o, 5 - stoichiometric

Composition and subsequent post calcination

0.443 g Eu ₂ O ₃ (1.26 mmol), 3.500 g Ba ₃ N ₂ (7.95 mmol), 5.552 g Si ₃ N ₄

(39.58 mmol), 0.376 g SiO ₂ (6.25 mmol) and 2.313 g Sr ₃ N ₂ (7.95 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and centered in a tube furnace placed on a support plate made of molybdenum foil and annealed at 1600 ° C for 8 h under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ).

The phosphor thus obtained is mixed in a glove box with 20 wt .-% of a 1: 1 mixture of strontium nitride / barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess barium and strontium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid,

then filtered off and dried.

F) (Sr, Ca, Ba) i, 92euo, o8Si5 ₇ , ₆₇ 0o, 5 - recalcination

50 g of phosphor, described in Examples 3A) - 3E), is added in a glove box with 20 wt .-% calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 4

A) Comparative Example: (Sr, Ca) i, 92euo, o8Si5 ₇ , ₆ 70o, 5-stoichiometric composition

2.115 g Eu ₂ O ₃ (6.00 mmol), 16.370 g (56.00 mmol) Sr ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol), 5.930 g Ca ₃ N ₂ (40.00 mmol ) and 2.253 g (37.50 mmol) of Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

B) Comparative Example - surplus

2.115 g Eu ₂ O ₃ (6.00 mmol), 23.560 g (81.00 mmol) Sr ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) _, 10.674 g Ca ₃ N ₂ (72.00 mmol ) and 2.253 g (37.50 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The Mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

C) (Sr, Ca) i, 92euo, o8Si5N7,670o, 5 - stoichiometric composition and subsequent postcalzination

2.115 g Eu ₂ O ₃ (6.00 mmol), 16.370 g (56.00 mmol) Sr ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) _, 5.930 g Ca ₃ N ₂ (40.00 mmol ) and 2.253 g (37.50 mmol) of Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

60 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% of a mixture of 8.810 g of strontium and 3.190 g of calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess calcium and strontium nitride, the resulting phosphor is heated for 1 h

Suspended 1 molar hydrochloric acid, then filtered off and dried.

D) - postcalzination

2.115 g Eu ₂ O ₃ (6.00 mmol), 27.924 g (96.00 mmol) Sr ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) _, and 2.253 g (37.50 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

60 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess strontium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. E) (Sr.Ca ^ Euo.osSis ^ Oo.s - postcalzination

2.115 g Eu ₂ O ₃ (6.00 mmol), 14.232 g (96.00 mmol) Ca ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol), and 2.253 g (37.50 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

50 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% strontium nitride and mixed until a homogeneous

Mixture arises. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess strontium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

F) (Sr, Ca, Ba) i, 92euo, o8Si5 _7.67 0o, 5 - recalcination

50 g of phosphor, described in Examples 4A) - 4E) is added in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 5

A) Comparative Example: (Ca, Ba) i, ₉ 2euo, o8SisN ₇ , 670o, 5-stoichiometric composition

2.115 g Eu ₂ O ₃ (6.00 mmol), 17.600 g (40.00 mmol) Ba ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol), 8.302 g Ca ₃ N ₂ (56.00 mmol ) and 2.253 g (37.50 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube oven centrally placed on a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

B) Comparative Example - surplus

2.115 g Eu ₂ O ₃ (6.00 mmol), 27.940 g (63.50 mmol) Ba ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, 10.791 g Ca ₃ N ₂ (72.79 mmol ) and 2.253 g (37.50 mmol) of Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and in a

Tube furnace centrally placed on a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

C) (Ca, Ba) i, 92Euo, o8Si5N _{7> 67} 0o, 5 - stoichiometric composition and subsequent post - calcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 17.600 g (40.00 mmol) Ba ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) _, 8.302 g Ca ₃ N ₂ (56.00 mmol ) and 2.253 g (37.50 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and in a

Tube furnace centered on a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

60 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% of a mixture of 9.680 g of barium nitride and 2.320 g of calcium nitride and mixed until a homogeneous mixture is formed.

This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess calcium and strontium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

D) (Ca, Ba) i, 92Eu _0> o8Si5 _{7> 67} 0o, 5 - recalcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 42.240 g (96.00 mmol) Ba ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, and 2.253 g (37.50 mmol) SiO ₂ be in a glove box weighed together and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

80 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess barium nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

E) (Sr, Ca) i, 92Eu ₀ , o8Si5N ₇ , 67 o, 5 - postcalcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 14.232 g (96.00 mmol) Ca ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) and 2.253 g (37.50 mmol) SiO ₂ weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

50 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess calcium nitride, the phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

F) (Sr, Ca, Ba) i, 92euo, o8Si _{5 7)} 670o, 5 - recalcination

50 g of phosphor, described in Examples 5A) - 5E) is added in a glove box with 20 wt .-% strontium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. to

Removal of excess nitride, the phosphor thus obtained is suspended for 1 h in 1-molar hydrochloric acid, then filtered off and dried. Example 6

A) Comparative Example: (Sr, Ca, stoichiometric composition

2.115 g Eu ₂ O ₃ (6.00 mmol), 8.144 g (28.00 mmol) Sr ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, 5.930 g Ca ₃ N ₂ (40.00 mmol ), 12.320 g (28.00 mmol) of Ba ₃ N ₂ and 2.253 g (37.50 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

B) Comparative Example: (Sr, Ca, Ba) i, ₉ 2euo, o8Si5 ₇ , 670o, 5 - excess

2.115 g Eu ₂ O ₃ (6.00 mmol), 12.217 g (42.00 mmol) Sr ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, 8.895 g Ca ₃ N ₂ (60.00 mmol ), 18.480 g (42.00 mmol) of Ba ₃ N ₂ and 2.253 g (37.50 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen peroxide atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

C) (Sr, Ba, Ca) i, ₉ 2Euo, o8Si5N _{7> 67} Oo, 5 - stoichiometric composition and subsequent post - calcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 8.144 g (28.00 mmol) Sr ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, 5.930 g Ca ₃ N ₂ (40.00 mmol ), 12.320 g (28.00 mmol) Ba3N2 and 2.253 g (37.50 mmol) Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

60 g of the phosphor thus obtained are applied in a glove box containing about 20% by weight of a mixture of 3.054 g of strontium nitride and 2.313 g of calcium chloride. nitrite and 4,620 g of barium nitride are added and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is heated for 1 h

Suspended 1 molar hydrochloric acid, then filtered off and dried.

D) (Sr, Ca, Ba) i, 92Eu ₀ , o8Si5N _7.67 0o, 5 - recalcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 14.232 g (96.00 mmol) Ca ₃ N ₂ , 33.998 g Si ₃ N ₄ (242.35 mmol) and 2.253 g (37.50 mmol) SiO ₂ weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture turns into a boat

Boron nitride transferred and placed in a tube furnace centered on a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

50 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 4,000 g strontium and 6,000 g barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

E) (Sr, Ca, Ba) i, 92euo, o8Si5N ₇ , ₆₇ 0o, 5 - recalcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 27.924 g (96.00 mmol) Sr ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol) _, and 2.253 g (37.50 mmol) Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

5Ό g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 8,200 g of barium nitrate and 1, 800 g of calcium nitride and mixed until a homogeneous mixture is formed. This is followed by recalcination, which are conditions identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. F) (Sr, Ca, Ba) i, 92euo, o8Si5N _7i6 70o, 5 - recalcination

2.115 g Eu ₂ O ₃ (6.00 mmol), 42.240 g (96.00 mmol) Ba ₃ N ₂ , 33.989 g Si ₃ N ₄ (242.35 mmol), and 2.253 g (37.50 mmol) Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

80 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 12,000 g Strontiumnitrird and 4,000 g of calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 7:

A) Comparative Example (Ba) i, 87Euo, o3Si5N ₇ , ₈ 0 _0> 2

0.599 g of Eu ₂ O ₃ (1.70 mmol), 32.811 g of Ba ₃ N ₂ (74.57 mmol), 26.589 g of Si ₃ N ₄ (189.6 mmol) are weighed together in a glovebox and mixed in a hand mortar, until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

B) (Ba) _> 87Euo _I o3Si ₅ N7 _> 80o ₎ 2

0.599 g of Eu ₂ O ₃ (1.70 mmol), 32.811 g of Ba ₃ N ₂ (74.57 mmol), 26.589 g of Si ₃ N ₄ (189.6 mmol) are weighed together in a glovebox and mixed in a hand mortar, until a homogeneous mixture is formed. The phosphor thus obtained is mixed in a glove box with 20 wt.% Barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the phosphor thus obtained is suspended for a further 1 hour in 1 molar hydrochloric acid, then filtered off and dried.

C) (Ba) i, 87euo, o3Si ₅ N7 _; 80o 2

0.599 g of Eu ₂ O ₃ (1.70 mmol), 38.133 g of Ba ₃ N ₂ (86.67 mmol), 26.589 g of Si ₃ N ₄ (189.6 mmol) are weighed together in a glove box and mixed in a hand mortar, until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , To remove excess nitride, the phosphor thus obtained is suspended for a further 1 hour in 1-molar hydrochloric acid and then filtered off and dried.

0.199 g Eu ₂ O _s (0.565 mmol), 10.985 g Ba ₃ N ₂ (24.97 mmol), 8.143 g Si ₃ N ₄ (58.10 mmol) and 0.817 g Si0 ₂ (13.60 mmol) are in Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen /

Hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid and then filtered off and dried.

E) (Ba eaEuo.oaSisN ^y jOo.a

0.199 g of Eu ₂ O ₃ (0.565 mmol), 10.985 g of Ba ₃ N ₂ (24.97 mmol), 8.143 g of Si ₃ N ₄ (58.10 mmol) and 0.817 g of SiO ₂ (13.60 mmol) are added in a Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The phosphor thus obtained is mixed in a glove box with 20 weight percent barium nitride and mixed until a homogeneous mixture is formed. Subsequently, a recalcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for one hour in 1-molar hydrochloric acid, then filtered off and dried.

0.199 g of Eu ₂ O ₃ (0.565 mmol), 13.200 g of Ba ₃ N ₂ (30.00 mmol), 8.143 g of Si ₃ N ₄ (58.10 mmol) and 0.817 g of SiO ₂ (13.60 mmol) are added in a Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , The phosphor thus obtained was suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. G) (Ba) i, 87Euo, o3Si ₅ N7, ₈ Oo, 2

0.199 g Eu ₂ 0 ₃ (0.565 mmol), 10.985 g Ba ₃ N ₂ (24.97 mmol), 8.881 g Si ₃ N ₄ (64.33 mmol) and 0.817 g SiO ₂ (13.60 mmol) are in a Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and in a tube furnace centered on a support plate

Molybdenum foil and 8 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

0.199 g Eu ₂ 0 ₃ (0.565 mmol), 10.985 g Ba ₃ N ₂ (24.97 mmol), 8.881 g Si ₃ N ₄ (64.33 mmol) and 0.817 g SiO ₂ (13.60 mmol) are in a Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The phosphor thus obtained is mixed in a glove box with 20 weight percent barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

0.199 g of Eu ₂ O ₃ (0.565 mmol), 13.200 g of Ba ₃ N ₂ (30.00 mmol), 8.881 g of Si ₃ N ₄ (64.33 mmol) and 0.817 g of Si0 ₂ (13.60 mmol) are in Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 8: A) Comparative Example (Sr, Ba) i _I 77Euo, o8Si5N _7> 7Oo _> 3

0.531 g Eu ₂ O ₃ (1, 51 mmol), 4,200 g Ba ₃ N ₂ (9.54 mmol), 6.718 g Si ₃ N ₄ (47.90 mmol), 0.451 g Si0 ₂ (7.50 mmol) and 2,775 g of Sr ₃ N ₂ (9.54 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed ,

B) (Sr, Ba) i ₍ 82Euo, o8Si _{5 7} , 80o, 2

0.443 g Eu ₂ O ₃ (1.26 mmol), 3.500 g Ba ₃ N ₂ (7.95 mmol), 6.077 g Si ₃ N ₄ (43.33 mmol), 0.376 g SiO ₂ (6.25 mmol) and 2.313 g of Sr ₃ N ₂ (7.95 mmol) are weighed together in a glovebox and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed , The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. C) (Sr.BaJuTEuo.oeSisN / jOo.a

1, 761 g Eu ₂ 0 ₃ (5 mmol), 28.008 g Ba ₃ N ₂ (63.336 mmol), 22.660 g of Si ₃ N ₄ (158.300 mmol) and 1, 502 g of SiO ₂ (25,000 mmol) are in a

Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed ,

Strontium nitride mixed and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, which takes place at 1625 ° C for 8 h under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ). The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. D) (Sr, Ba) i _; 77Euo, o8Si ₅ N7,70 _0> 3

1, 761 g Eu ₂ 0 ₃ (5 mmol), 18.421 g Sr ₃ N ₂ (63.336 mmol), 22.660 g Si ₃ N ₄ (158.300 mmol) and 1, 502 g SiO ₂ (25.000 mmol) are combined in a glovebox weighed and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed ,

The phosphor thus obtained is mixed in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

0.443 g Eu ₂ 0 ₃ (1.26 mmol), 4.900 g Ba ₃ N ₂ (10.13 mmol), 5.552 g Si ₃ N ₄ (39.58 mmol), 0.376 g Si0 ₂ (6.25 mmol) and 3,233 g of Sr ₃ N ₂ (10.13 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 20 l / min H ₂ ) annealed. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

F) (Sr, Ba) i, 82Euo, o8Si5N7.80 _0> 2

1.761 g of Eu ₂ O ₃ (5 mmol), 18.421 g of Sr ₃ N ₂ (63.336 mmol), 23.840 g of Si ₃ N ₄ (170.00 mmol) and 1.502 g of SiO ₂ (25.000 mmol) are added in a Weigh the glove box together and mix in a hand mortar until a homogeneous mixture is obtained. The mixture turns into a boat

Boron nitride transferred and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed.

The phosphor thus obtained is mixed in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

G) (Sr.BaJij Euo.osSisN jOo.a

1.330 g of Eu ₂ O ₃ (3.78 mmol), 10.494 g of Ba ₃ N ₂ (23.85 mmol), 6.937 g of Si ₃ N ₄ (23.85 mmol), 1.127 g of SiO ₂ (18, 75 mmol) and 16.652 g of Sr ₃ N ₂ (118.74 mmol) are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (60 l / min N ₂ + 15 l / min H ₂ ) annealed ,

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

Example 9:

A) Comparative Example (Ca, Ba) i, 83Euo, o7Si5N _7> 80o, 2

1.309 g Eu ₂ O ₃ (3.72 mmol), 18.979 g (43.13 mmol) Ba ₃ N ₂ , 21, 074 g Si ₃ N ₄ (150.33 mmol) _, 2.471 g Ca ₃ N ₂ (16 , 67 mmol) and 1.399 g (23.3 mmol) of Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and in a

Tube furnace centered on a support plate made of molybdenum foil and 8 hours at 1650 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed.

1.309 g Eu ₂ O ₃ (3.72 mmol), 26.312 g (59.80 mmol) Ba ₃ N ₂ , 21, 074 g Si ₃ N ₄ (150.33 mmol) and 1.399 g (23.3 mmol) Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed.

60 g of the phosphor thus obtained is mixed in a glove box with 5 wt.% Calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for one hour in 1-molar hydrochloric acid, then filtered off and dried.

C) (Ca, Ba) i, 83Euo _> o7Si ₅ N7 _> 80o, 2

21, 309 g Eu ₂ O ₃ (3.72 mmol), 26.312 g (59.80 mmol) Ba ₃ N ₂ , 21, 074 g Si ₃ N ₄ (150.33 mmol) and 1.399 g (23.3 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and in a tube furnace centered on a support plate Molybdenum foil placed and annealed at 1625 ° C for 8 h under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ).

80 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% of a proportionate mixture of relative proportion of 80% barium nitrite and 20% calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

D) (Ca, Ba) i, 83Euo, o7Si5N7.80 _0> 2

21, 309 g Eu ₂ O ₃ (3.72 mmol), 26.312 g (59.80 mmol) Ba ₃ N ₂₎ 21, 074 g Si ₃ N ₄ (150.33 mmol) and 1.399 g (23.3 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1625 ° C under a nitrogen hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed.

80 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% of a proportionate mixture of relative proportion of 90% barium nitride and 10% calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

E) (Ba.Ca eaEuo.oTSisN / .eOo.a

1.309 g Eu ₂ O ₃ (3.72 mmol), 8.865 g (59.80 mmol) Ca ₃ N ₂ , 21, 074 g Si ₃ N ₄ (150.33 mmol) and 1.399 g (23.3 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 8 h at 1650 ° C under a nitrogen hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed. 50 g of the phosphor thus obtained is mixed in a glove box with 20 wt .-% barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

F) (Ca, Ba) i, 83Euo, o7Si5N7,80 o.2

1.309 g Eu ₂ O ₃ (3.72 mmol), 20.534 g (46.67 mmol) Ba ₃ N ₂ , 2.965 g Ca ₃ N ₂ (20.00 mmol), 21, 074 g Si ₃ N ₄ (150 , 33 mmol) and 1.399 g (23.3 mmol) of Si0 ₂ are weighed together in a glovebox and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and in a

Tube furnace centered on a support plate made of molybdenum foil and 8 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (70 l / min N ₂ + 10 l / min H ₂ ) annealed. The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 10:

A) Comparative Example (Sr, Ca, Ba) i, ₀ 83Eu, o7Si5N _7, 80o, 2

0.757g Eu ₂ O ₃ (2.15mmol), 1.939g (6.67mmol) Sr ₃ N ₂ , 8.125g (18.47mmol) Ba ₃ N ₂ , 1.483g (10.00mmol ) Ca ₃ N ₂ , 13.183 g of Si ₃ N ₄ (94.00 mmol), and 0.601 g (10.00 mmol) of Si0 ₂ are weighed together in a glovebox and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

B) (Sr, Ba, Ca eaEuo.ozSis ^ Oo ^

0.757g Eu ₂ O ₃ (2.15mmol), 1.939g (6.67mmol) Sr ₃ N ₂ , 8.125g (18.47mmol) Ba ₃ N ₂ , 1.483g (10.00mmol ) Ca ₃ N ₂ , 13.183 g Si ₃ N ₄ (94.00 mmol), and 0.601 g (10.00 mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous

Mixture arises. The mixture is transferred to a boat made of boron nitride and in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

60 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 1, 940 g of strontium and 1, 460 g of calcium nitride and 8,600 g of barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

C) (Sr, Ca, Ba eaEuo.o SisNy.eOca

0.757 g of Eu ₂ O ₃ (2.15 mmol), 2.133 g (7.33 mmol) of Sr ₃ N ₂ , 8.800 g (20.00 mmol) of Ba ₃ N ₂ , 1. 631 g (1.00 mmol) Ca ₃ N ₂ , 13.183 g of Si ₃ N (94.00 mmol) _, and 0.601 g (10.00 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1625 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed , The phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

D) (Sr, Ca, Ba) i, ₈₃ Euo, o7Si5 _{7> 8} 0o, 2

0.757g Eu ₂ O ₃ (2.15mmol), 15.459g (35.13mmol) Ba ₃ N ₂ , 13.183g Si ₃ N ₄ (94.00mmol) _, and 0.601g (10.00mmol) SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

80 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 0.000 g strontium nitride and 6,000 g calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. For removal of excess nitride the phosphor thus obtained is suspended for a further 1 h in 1 molar hydrochloric acid, then filtered off and dried.

0.757 g of Eu ₂ O ₃ (2.15 mmol), 5.209 g (35.13 mmol) of Ca ₃ N ₂ , 13.183 g of Si ₃ N ₄ (94.00 mmol) _, and 0.601 g (10.00 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 h at 1600 ° C under a nitrogen / hydrogen atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

50 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 4,000 g strontium nitride and 6,000 g barium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the phosphor thus obtained is suspended for a further 1 h in 1 molar hydrochloric acid, then filtered off and dried.

F) (Sr, Ca, Ba) i, 83euo, o7Si ₅ N ₇ , 80o, 2

0.757 g of Eu ₂ O ₃ (2.15 mmol), 10.219 g (35.13 mmol) of Sr ₃ N ₂ , 13.183 g of Si ₃ N ₄ (94.00 mmol) _, and 0.601 g (10.00 mmol) of SiO ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is obtained. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 h at 1625 ° C under a nitrogen / water, ₅ -material atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed.

50 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 8,200 g of barium nitride and 1, 800 g of calcium nitride and mixed until a homogeneous mixture is formed. This is followed by a renewed calcination, the conditions are identical i0 to the first annealing step. To remove excess nitride, the resulting phosphor is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried. G) (Sr, Ca, Ba) i _> 83Euo, o7Si ₅ N7 _> 80o _> 2

0.757 g Eu ₂ O ₃ (2.15 mmol), 2.133 g (7.33 mmol) Sr ₃ N ₂ , 8.800 g (20.00 mmol) Ba ₃ N ₂ , 1, 156 g (7.80 mmol) Ca ₃ N ₂ , 13.183 g of Si ₃ N ₄ (94.00 mmol) _, and 0.601 g (10.00 mmol) of Si0 ₂ are weighed together in a glove box and mixed in a hand mortar until a homogeneous mixture is formed. The mixture is transferred to a boat made of boron nitride and placed in a tube furnace in the middle of a support plate made of molybdenum foil and 6 hours at 1600 ° C under a nitrogen / hydrogen peroxide atmosphere (50 l / min N ₂ + 20 l / min H ₂ ) annealed ,

80 g of the phosphor thus obtained is mixed in a glove box with about 20 wt .-% of a mixture of 10,000 g barium nitride, 2,000 g Strontiumnitrird and 4,000 g calcium nitride and mixed until a homogeneous mixture. This is followed by a renewed calcination, the conditions are identical to the first annealing step. To remove excess nitride, the phosphor thus obtained is suspended for 1 h in 1 molar hydrochloric acid, then filtered off and dried.

Example 11: Coating of the phosphors

A) coating of the phosphors according to the invention with Si0 ₂

50 g of one of the phosphors according to the invention described above are suspended in 1 liter of ethanol in a 2 L reactor with ground cover, heating mantle and reflux condenser. For this purpose, a solution of 17 g of ammonia water (25 wt .-% NH ₃ ) in 70 ml of water and 100 ml of ethanol. With stirring, a solution of 48 g of tetraethyl orthosilicate (TEOS) in 48 g of anhydrous ethanol slowly (about 1, 5 ml / min) was added dropwise at 65 ° C. After completion of the addition, the suspension is stirred for a further 1.5 h, brought to room temperature and filtered off. The residue is washed with ethanol and dried at 150 ° C to 200 ° C.

B) Coating of the phosphors according to the invention with Al ₂ O ₃

In a glass reactor with a heating jacket, 50 g of one of the phosphors according to the invention described above are suspended in 950 g of ethanol. 600 g of an ethanolic solution of 98.7 g of AICI ₃ ^* 6H ₂ O per kg of solution are stirred into the suspension at 80 ° C. over 3 hours added. The pH is kept constant at 6.5 by addition of sodium hydroxide solution. After the end of the addition is stirred for 1 h at 80 ° C, then cooled to room temperature, the phosphor filtered off, washed with ethanol and dried.

C) coating of the phosphors according to the invention with B ₂ 0 ₃

In a glass reactor with a heating jacket, 50 g of one of the phosphors according to the invention described above are suspended in 1000 ml of water. The suspension is heated to 60 ° C and treated while stirring with 4.994 g of boric acid H ₃ BO ₃ (80 mmol). The suspension is cooled with stirring to room temperature and then stirred for 1 h.

This is followed by aspiration of the suspension and drying in a drying oven. After drying, the calcination of the material takes place at 500 ° C under a nitrogen atmosphere.

D) coating of the phosphors according to the invention with BN

In a glass reactor with a heating jacket, 50 g of one of the phosphors according to the invention described above are suspended in 1000 ml of water. The suspension is heated to 60 ° C and treated while stirring with 4.994 g of boric acid H3BO3 (80 mmol). The suspension is cooled with stirring to room temperature and then stirred for 1 h. This is followed by aspiration of the suspension and drying in a drying oven. After drying, the calcination of the material takes place at 1000 ° C under a nitrogen-ammonia atmosphere.

E) coating of the phosphors according to the invention with Zr0 ₂

In a glass reactor with a heating jacket, 50 g of one of the phosphors according to the invention described above are suspended in 1000 ml of water. The suspension is heated to 60 ° C and adjusted to pH 3.0. Subsequently, the slow dosage of 10 g of a 30 weight percent ZrOC solution is carried out with stirring. After successful

The mixture is stirred for a further 1 h, then filtered off with suction and washed with deionised water. After drying, the calcination of the material takes place at 600 ° C under a nitrogen atmosphere. F) coating of the phosphors according to the invention with MgO

In a glass reactor with a heating jacket, 50 g of one of the phosphors according to the invention described above are suspended in 1000 ml of water. The suspension is heated to 25 ° C and 19.750 g

Ammonium hydrogen carbonate (250 mmol) was added. It is slow

Add 100 ml of a 15% by weight magnesium chloride solution. After the dosage is stirred for 1 h, then filtered with suction and washed with deionized water. After drying, the calcination of the material takes place at 1000 ° C under a nitrogen-hydrogen atmosphere.

Example 12: Thermal post calcination

50 g of one of the above-described phosphors is transferred to an Alsint annealing crucible and then reductively calcined. The calcination takes place at 300 ° C under a nitrogen-hydrogen atmosphere. The hydrogen content is up to 10 percent by volume. After cooling, the phosphor according to the invention is gently briefly mortared and then sieved, and further charkatized.

Example 13: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 3000 K has:

1 g of the red phosphor described in Example 8C) with a

Maximum of the emission wavelength of 620 nm is weighed together with 8 g of a green phosphor having the composition Lu ₂ , 976Ce _0, o24Al5O ₁ 2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 14 wt.%. 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 blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 14: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 5000 K has:

1 g of the red phosphor described in Example 8C) with a

Maximum of the emission wavelength of 620 nm is weighed together with 19 g of a green phosphor having the composition Lu ₂ , 976Ce ₀ , o2 Al5Oi2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 12 wt.%. 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 blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 15: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 6500 K comprises:

1 g of the red phosphor described in Example 8G) with a

Maximum of the emission wavelength of 620 nm is weighed together with 21 g of a green phosphor having the composition Lu2,976Ce ₀ , o24Al5Oi ₂ and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 10 wt.%. The silicone-phosphor mixture obtained in this way is applied to the chip of a blue semiconductor LED with the aid of an automatic dispenser and cured while supplying heat. The blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra. EXAMPLE 16 Production of a pc-LED Using a Phosphor Produced in Accordance With the Invention A Correlated Color

Temperature (CCT) of 3000 K has:

1 g of the described in Example 6F) red phosphor with a

Maximum of the emission wavelength of 630 nm is weighed together with 12 g of a green phosphor having the composition Lu ₂ , 976Ceo _, o2 Al5O-i2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 17 wt.%. The silicone-phosphor mixture obtained in this way is applied to the chip of a blue semiconductor LED with the aid of an automatic dispenser and cured while supplying heat. The blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained becomes further calculations of characteristic properties of the LED used. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 17: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 5000 K has:

1 g of the described in Example 6F) red phosphor with a

Maximum of the emission wavelength of 630 nm is weighed together with 21 g of a green phosphor having the composition Lu2 _, 976Ce _0, o24Al5O ₁₂ and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 13.5 wt.%. 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 blue semiconductor LEDs used for LED characterization have an emission wavelength of 442 nm and are operated at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

EXAMPLE 18 Production of a PC-LED Using a Phosphor Produced According to the Invention, Using a Correlated Color

Temperature (CCT) of 6500 K comprises:

1 g of the described in Example 6F) red phosphor with a

Maximum of the emission wavelength of 630 nm is weighed together with 23 g of a green phosphor having the composition Lu _2, 976Ce _0, o24Al5O ₁₂ and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 12 wt.%. The resulting silicone-phosphor mixture is determined by means of a automatic dispenser applied to the chip of a blue semiconductor LED and cured with heat. The blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 19: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 3000 K has:

1 g of the red phosphor described in Example 5C) with a

Maximum of the emission wavelength of 650 nm is weighed together with 4.5 g of a green phosphor having the composition Lu2,976Ce _0, o24Al5Oi2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 21 wt.%. 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 blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra. Example 20: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 5000 K has:

1 g of the red phosphor described in Example 5C) with a

Maximum of the emission wavelength of 650 nm is weighed together with 7.5 g of a green phosphor having the composition Lu2,976Ce ₀ , o24Al5Oi2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 18 wt.%. 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 blue LED's used for LED characterization have an emission wavelength of 442 nm and operate at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 21: Production of a pc-LED using a phosphor prepared according to the invention, which has a Correlated Color

Temperature (CCT) of 6500 K comprises:

1 g of the red phosphor described in Example 5C) with a

Maximum of the emission wavelength of 650 nm is weighed together with 8 g of a green phosphor having the composition Lu _2, 976Ce ₀ , o2 Al ₅ Oi2 and homogeneously mixed in a planetary centrifugal mixer. Subsequently, the mixture is mixed with an optically transparent silicone and mixed, so that the phosphor concentration is 15 wt.%. 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 blue semiconductor LEDs used for the LED characterization have an emission wave- length of 442 nm and are operated at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED. These are the color point coordinates CIE x and y, the brightness in lumens and the general color rendering index Ra.

Example 22

A) Production of a pc-LED, which exclusively a red

Phosphor according to Example 8A)

0.175 g of the red phosphor described in Example 8A) is mixed with an optically transparent silicone and mixed so that the phosphor concentration is 1.75 wt.%. 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 blue semiconductor LEDs used for LED characterization have an emission wavelength of 442 nm and are operated at 350 mA current. The light-technical characterization of the LED 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 determining the wavelength-dependent spectral power density. The spectrum of light emitted by the LED thus obtained is used for further calculations of characteristic properties of the LED.

B) production of a pc-LED, which exclusively a red

Phosphor according to Example 8C)

The preparation of the pc-LED and the characterization thereof are carried out according to Example 22A), but using the red phosphor described in Example 8C). Results:

It can be seen from FIG. 1 that the phosphor produced according to comparative example 1A) has a higher emission intensity than the phosphor produced according to comparative example 1B). FIG. 2 shows that the phosphor according to the invention of Example 1C) has an even higher emission intensity than the phosphor prepared according to Comparative Example 1A). This demonstrates how phosphors with increased emission efficiency can be produced by the method according to the invention. The same applies to the comparison of the intensities in FIGS. 3 and 4 of the phosphors produced in the comparative examples 2A) and 2B) and in the inventive example 2C). The comparison of the wavelengths in FIG. 5 of the phosphors produced in examples 2C) and 2D) also shows that the emission wavelength can be shifted by the method according to the invention.

Figures 6 to 14 show that the phosphors according to the invention are very well suited for the production of white-emitting LEDs.

From Figure 15 it is apparent that the produced according to Example 8C)

phosphor according to the invention has a higher proportion of the emission intensity in the LED spectrum when used in a pc-LED despite identical phosphor concentration than the phosphor prepared according to Example 8A).

Claims

claims

1. A method for increasing the radiation-induced emission efficiency and / or for shifting the emission wavelength of a

A europium-doped alkaline earth metal silicon nitride or a europium-doped alkaline earth metal silicooxynitride, comprising the steps:

(a) preparing a mixture of a europium-doped alkaline earth metal silicon nitride or a europium-doped alkaline earth metal silicooxynitride and an alkaline earth metal nitride, wherein the alkaline earth metal of the europium-doped alkaline earth metal silicon nitride or the europium-doped alkaline earth metal Silico-oxynitrides and the alkaline earth metal nitride may be the same or different; and

(b) calcining the mixture under non-oxidizing conditions.

2. The method of claim 1, wherein in the mixture, the weight ratio of europium-doped alkaline earth metal silicon nitride or silicooxynitride to the alkaline earth metal nitride in the range of 2: 1 to 20: 1.

3. The method of claim 1 or 2, wherein the alkaline earth metal in the alkaline earth metal nitride is different from the alkaline earth metal in the alkaline earth metal silicon nitride or silicooxynitride.

4. The method according to one or more of claims 1 to 3, wherein the europium-doped alkaline earth metal silicon nitride or

Silicooxynitride is prepared by a step (a ¹ ), wherein step (a ') comprises calcining a mixture containing a europium source, a silicon source and an alkaline earth metal nitride under non-oxidizing conditions and step (a) of the method according to one or more of claims 1 to 3 precedes. A process for producing a post-treated europium-doped alkaline earth metal silicon nitride or europium-doped alkaline earth metal silicooxynitride comprising the following steps:

(i) synthesis of a europium-doped alkaline earth metal silicon nitride or a europium-doped alkaline earth metal silicooxynitride;

(ii) calcining a mixture containing the europium-doped alkaline earth metal silicon nitride or europium-doped alkaline earth metal silicooxynitride obtained in step (i) and an alkaline earth metal nitride under non-oxidizing conditions.

A method according to claim 5, characterized in that the synthesis of the europium-doped alkaline earth metal silicon nitride or the europium-doped alkaline earth metal silicooxynitride in step (i) by calcination of a mixture containing a europium source, a silicon source and an alkaline earth metal nitride under non- oxidizing conditions.

A process according to claim 5 or 6, wherein in the mixture in step (ii) the weight ratio of the europium-doped alkaline earth metal silicon nitride or silicooxynitride obtained in step (i) to the alkaline earth metal nitride ranges from 2: 1 to 20: 1.

Method according to one or more of claims 1 to 7, wherein the europium-doped alkaline earth metal silicon nitride or silicooxynitride or the post-treated europium-doped alkaline earth metal silicon nitride or silicooxynitride is a compound of general formula (I) or (II) .

EA _d EucE _e NfOx · m Si0 ₂ · n Si ₃ N ₄ (I) wherein for the symbols and indices used: EA is at least one alkaline earth metal; E is at least one element of the fourth main group, in particular Si;

0.80 <d <1.995;

0.005 <c <0.2;

4.0 <e <6.00;

5.00 <f <8.70;

0 <x <3.00;

0 <m <2.50;

0 <n <0.50;

where the following relationship applies to the indexes:

2d + 2c + 4e = 3f + 2x;

Bai _-a- _b-c Si cSraCabEu Ni ₇ ₀ · m Si0 ₂ · n Si ₃ N ₄ (II) wherein the indices used have the following meanings:

0 <a <1

0 <b <1

0.01 <c <0.2, preferably 0.02 <c <0.1;

0 <m <2.50;

0 <n <0.50; and

a + b + c <1.

The method according to one or more of claims 1 to 8, wherein the europium-doped alkaline earth metal silicon nitride or silico-oxynitride or the post-treated europium-doped alkaline earth metal silicon nitride or silicooxynitride is a compound according to the formula (Ia) or (Ib) .

Ba2 _-a - _b - _{c +} i, _5z Sr _a Ca _b Eu _c Si ₅ N _{_8-z} O 23x ₊ _x · m Si0 ₂ · n Si ₃ N ₄ (la) wherein the indices used have the following meanings:

0 <a <2; 0 <b <2;

0.01 <c <0.2, preferably 0.02 <c <0.1;

0 <x <1, preferably 0 <x <0.6;

0 <z <3.0, preferably 0 <z <1, 0, more preferably z = 0;

0 <m <2.50;

0 <n <0.50;

and a + b + c <2 + 1.5z;

Baaabco.sx + i.szSraCabEucSisNe-x + zOx.m Si0 ₂ · n Si ₃ N ₄ (Ib) where the indices used have the following meanings

exhibit:

0 <a <2;

0 <b <2;

0.01 <c <0.2, preferably 0.02 <c <0.1;

0 <x <1, preferably 0 <x <0.6;

0 <z <3.0, preferably 0 <z <1, 0, more preferably z = 0;

0 <m <2.50;

0 <n <0.50.

The method of one or more of claims 1 to 9, wherein the alkaline earth metal nitride at each occurrence is independently selected from the group consisting of calcium nitride,

Strontium nitride, barium nitride and mixtures thereof.

A process according to one or more of claims 1 to 10, wherein the calcination in steps (a ¹ ) and (b) or (i) and (ii) are each independently at a temperature in the range of 1200 to 2000 ° C is carried out. 2. The method according to one or more of claims 1 to 11, wherein the non-oxidizing conditions in step (a ') and (b) or (i) and (ii) are prepared by a reducing atmosphere, wherein the reducing atmosphere is preferred Contains hydrogen.

13. A compound obtainable by a process according to any of claims 8 to 12.

14. Compound of the formula (Ia)

Baa-ab-c + i.szSraCabEucSisNs-a / sx + zOx.m SiO ₂ n Si ₃ N ₄ formula (Ia) where the indices used have the following meanings:

0 <a <2;

0 <b <2;

0.01 <c <0.2;

0 <x <1;

0 <z <3.0;

0 <m <2.50;

0 <n <0.50;

and a + b + c <2 + 1.5z.

15. A compound according to claim 14, wherein the indices used have the following meanings:

0 <a <2;

0 <b <2;

0.02 <c <0.1;

0.03 <x <0.8, preferably 0.1 <x <0.6;

0 <z <1, 0, preferably z = 0;

0 <m <1.00, preferably m = 0;

n = 0;

and a + b + c <2 + 1.5z.

16. Use of a compound according to one or more of claims 13 to 15 as a conversion phosphor.

17. Light-emitting device containing a compound according to one or more of claims 13 to 15.