TW201533219A - Phosphors - Google Patents

Abstract

The present invention relates to europium-doped alkaline-earth metal silicooxynitrides, to a process for the preparation of these compounds, and to the use of the europium-doped alkaline-earth metal silicooxynitrides according to the invention as conversion phosphors. The present invention furthermore relates to a light-emitting device which comprises a europium-doped alkaline-earth metal silicooxynitride according to the invention.

Description

Phosphor

The present invention relates to cerium-doped alkaline earth metal cerium oxynitride, a process for preparing the same, and a cerium-doped alkaline earth metal cerium oxynitride according to the present invention for use as a conversion phosphor. The invention further relates to a light-emitting device comprising an erbium-doped alkaline earth metal lanthanum oxynitride according to the invention.

As a conversion phosphor of a phosphor-converted LED (abbreviated as pc-LED), an inorganic phosphor powder which can be excited in a blue and/or UV spectral region is extremely important. At the same time, many conversion phosphor systems such as alkaline earth metal orthosilicates, thiogallates, garnets, nitrides and oxynitrides are known, each of which is doped with Ce ³⁺ or Eu ²⁺ . In particular, the last mentioned nitride and oxynitride phosphors are currently the subject of intensive research because these materials exhibit red light emission with emission wavelengths greater than 600 nm, and therefore for warm white pc-LEDs with a color temperature <4000K It is vital.

However, it would be desirable to have an available phosphor that displays an emission that is further shifted into red light. Accordingly, it is an object of the present invention to provide phosphors of this type.

It has surprisingly been found that this goal is achieved if certain other elements, especially one or more of the elements Mg, Zn, Ge and/or S, are incorporated into the cerium-doped alkaline earth metal cerium oxynitride. Accordingly, the present invention is directed to compounds of this type.

The present invention relates to a compound of the following formula (1), EA _a Eu _x E _e N _f Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ (1)

Wherein the following applies to the symbols and indices used: EA represents one or more elements selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; E represents one or more elements selected from the group consisting of Si and Ge; Represents one or more elements selected from the group consisting of O and S; 0.80 a 1.995; 0.005 x 0.20; 4.00 e 6.00;5.00 f 8.70;0.01 y 3.00; where, for the indices a, x, e, f, and y: 2a + 2x + 4e = 3f + 2y; m 4.00;0 n 0.50; characterized in that the compound contains at least one of the elements Mg and/or Zn and/or Ge and/or S.

In a preferred embodiment of formula (1), the following are applied independently of each other to the index: 1.20 a 1.995; preferably 1.60 a 1.995;0.01 x 0.20; preferably 0.02 x 0.16; 4.50 e 5.50; preferably 4.80 e 5.20; specifically e=5.00; 6.00 f 8.00; preferably 6.00 f 7.90; 0.1 y 2.5; preferably 0.15 y 1.5;0 m 3.00; preferably 0 m 2.50;0 n 0.50; preferably 0 n 0.20.

In a particularly preferred embodiment, the preferences mentioned above for the index in formula (1) occur simultaneously.

Therefore, the following are better applicable to the index used: 1.20 a 1.995;0.01 x 0.20; 4.50 e 5.50; 6.00 f 8.00; 0.1 y 2.5;0 m 3.00; and 0 n 0.50.

The following are particularly preferred for the index used: 1.60 a 1.995;0.02 x 0.16; 4.80 e 5.20; specifically e=5.00; 6.00 f 7.90; 0.15 y 1.5;0 m 2.50; and 0 n 0.20.

Due to the presence of Mg and/or Zn and/or Ge and/or S in the compounds according to the invention, a red shift is achieved compared to the corresponding compound, which does not contain such elements but In addition to this, it has the same composition, and has continued to maintain good emission properties and higher emission efficiency.

If the compound according to the invention contains Mg, the proportion thereof is preferably at most 40%, preferably from 5% to 40%, of the element EA.

If the compound according to the invention contains Zn, the proportion thereof is preferably at most 40%, preferably from 5% to 40%, of the element EA.

If the compound according to the invention contains Ge, the proportion is at most 100%, preferably from 1% to 100%, particularly preferably from 2% to 20%, of the element E.

If the compound according to the invention contains S, the proportion is at most 100%, preferably from 1% to 100%, particularly preferably from 2% to 100%, of the element Y.

Preferred examples of the compound of the formula (1) are compounds of the following formula (2), formula (3) and formula (4), EA _2-x+1.5z Eu _x E ₅ N _8-2/3y+z Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ (2)

EA _{2-x-0.5y+1.5z} Eu _x E ₅ N _8-y+z Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ (3)

EA _2-x+1.5z Eu _x E ₅ N _8-y+z Y _3/2y ̇m SiO ₂ ̇n Si ₃ N ₄ (4)

Where EA, E, Y and the indices x, y, m and n have the meaning given above, and in addition: 0 z 3.0, preferably 0 z 1.0, particularly preferably z=0; characterized in that the compound contains at least one of the elements Mg and/or Zn and/or Ge and/or S. The content of Mg and/or Zn and/or Ge and/or S herein is preferably within the range indicated above for these elements.

A preferred embodiment of the compound of the formula (2) is a compound of the following formula (2a), and a preferred embodiment of the compound of the formula (3) is a compound of the following formula (3a), and a compound of the formula (4) is preferred. An example is a compound of the following formula (4a), (Mg _o Ca _p Sr _q Ba _r Zn _s ) _2-x+1.5z Eu _x (Si _t Ge _u ) ₅ N _8-2/3y+z (O _v S _w ) _y ̇m SiO ₂ ̇n Si ₃ N ₄ (2a)

(Mg _o Ca _p Sr _q Ba _r Zn _s ) _{2-x-0.5y+1.5z} Eu _x (Si _t Ge _u ) ₅ N _8-y+z (O _v S _w ) _y ̇m SiO ₂ ̇n Si ₃ N ₄ type (3a)

(Mg _o Ca _p Sr _q Ba _r Zn _s ) _2-x+1.5z Eu _x (Si _t Ge _u ) ₅ N _8-y+z (O _v S _w ) _3/2y ̇m SiO ₂ ̇n Si ₃ N ₄ type (4a)

Where x, y, and z have the meanings given above, and in addition: 0 o 0.4;0 p 1;0 q 1;0 r 1;0 s 0.4;0 t 1;0 u 1; 0 v 1;0 w 1; the constraint is o + p + q + r + s = 1 and t + u = 1 and v + w = 1; and furthermore, the constraint is at least one of the indices o, s, u and / or w >0, that is, at least one of the elements Mg, Zn, Ge, and/or S is present, wherein the ratios indicated above are preferably applied to such elements.

In the compounds of the formulae (1) to (4) and the formulae (2a) to (4a), the m range is preferably from 0 to 1 and the n range is preferably from 0 to 0.3, particularly preferably 0.

If m>0, SiO ₂ may be in a crystalline and/or amorphous form. If n>0, Si ₃ N ₄ may be in a crystalline and/or amorphous form.

Furthermore, the invention relates to a process for the preparation of a compound according to the invention, characterized in that the process step comprises: (a) preparing a mixture comprising a source of ruthenium, osmium and/or ruthenium and a nitrogen of the formula EA ₃ N ₂ a compound wherein EA has the meaning given above; (b) calcining the mixture under non-oxidizing conditions.

If the compound according to the invention contains sulphur, then at least one of the above-mentioned components in the form of a sulphur-containing compound (for example in the form of a sulphate or a sulphide), and/or the addition of elemental sulphur, is additionally employed.

The ruthenium source used in step (a) can be any conceivable ruthenium compound which can be used to prepare bismuth-doped alkaline earth metal ruthenium oxynitride. The germanium source used is preferably cerium oxide (especially Eu ₂ O ₃ ) and/or cerium nitride (EuN), especially Eu ₂ O ₃ .

The ruthenium or osmium source employed in step (a) can be any conceivable ruthenium or osmium compound which can be used to prepare cerium-doped alkaline earth metal cerium oxynitride or the corresponding cerium compound. In this hair The germanium source used in the method is preferably tantalum nitride and/or hafnium oxide, and the germanium source used in the method of the present invention is preferably tantalum nitride and/or hafnium oxide.

The compounds employed are preferably in a ratio to each other such that the number of atoms of the elements EA, hydrazine and/or hydrazine, hydrazine, nitrogen and oxygen and/or sulphur substantially corresponds to those in the products of the formulas mentioned above. Need ratio. In particular, stoichiometric ratios are used here, but there may also be a slight excess of nitride EA ₃ N ₂ .

The starting compounds in powder form are preferably employed in step (a) and are processed into each other, for example by means of a mortar, to obtain a homogeneous mixture.

The calcination in step b) is carried out under non-oxidizing conditions. Non-oxidizing conditions refer to any conceivable non-oxidizing atmosphere, in particular a substantially oxygen-free atmosphere, that is to say an atmosphere having a maximum oxygen content of <100 ppm, in particular <10 ppm, wherein in the case of the invention vacuum is not suitable for use as a non-oxidizing atmosphere. A non-oxidizing atmosphere can be generated, for example, by using a shielding gas, especially nitrogen or argon. Preferably, the non-oxidizing atmosphere is a reducing atmosphere. The reducing atmosphere is defined to include at least one gas having a reducing action. It is known to those skilled in the art which gases have a reducing effect. Examples of suitable reducing gases are hydrogen, carbon monoxide, ammonia or ethylene, more preferably hydrogen, wherein such gases can also be combined with other non-oxidizing gases. The reducing atmosphere is particularly preferably produced by a mixture of nitrogen and hydrogen, preferably in a ratio of H ₂ :N _{2 in} a range of from 10:50 to 33:30 by volume.

The calcination is preferably carried out at a temperature ranging from 1200 ° C to 2000 ° C, particularly preferably from 1400 ° C to 1800 ° C and, in particular, from 1500 ° C to 1700 ° C. The calcination time here is preferably from 2 h to 14 h, more preferably from 4 h to 12 h and specifically from 6 h to 10 h.

Calcination is preferably carried out by introducing the resulting mixture into a boron nitride vessel such as a high temperature furnace. The high temperature furnace is, for example, a tube furnace containing a molybdenum foil tray.

After calcination, the obtained compound is preferably treated with an acid to wash out unreacted EA ₃ N ₂ . The acid used is preferably hydrochloric acid. In this operation, the obtained powder is preferably suspended in 0.5 M to 2 M hydrochloric acid (especially about 1 M hydrochloric acid) for 0.5 h to 3 h, particularly preferably 0.5 to 1.5 h, and then filtered off, rinsed with water and in a range Dry at a temperature of 80 ° C to 150 ° C.

In another embodiment of the invention, another calcination step is carried out after calcination and treatment by acid treatment as described above. This is preferably carried out at a temperature ranging from 200 ° C to 400 ° C, particularly preferably from 250 ° C to 350 ° C. 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. This type of post calcination process is described, for example, in WO 2014/008970.

In another preferred embodiment of the invention, after the calcining step, another calcination step in which one or more alkaline earth metal nitrides and/or zinc nitride are combined is carried out. For this purpose, the product from the first calcination step is mixed with an alkaline earth metal nitride, wherein the alkaline earth metal may already be present in or different from the product from the first calcination step and the mixture is calcined under non-oxidative conditions. This type of post calcination step can have a beneficial effect on the emission efficiency.

Here, the weight ratio of the product from the first calcination step to the alkaline earth metal nitride is preferably in the range of 2:1 to 20:1 and more preferably in the range of 4:1 to 9:1.

This type of method can increase the emission efficiency and also increase the shift of the emission wavelength depending on the alkaline earth metal nitride employed, and thus can be advantageous. The emission wavelength shift can occur here, especially when the alkaline earth metal in the product from the first calcination step and the alkaline earth metal in the alkaline earth metal nitride in the post-calcination step are different from each other.

For example, if ruthenium is used as the alkaline earth metal in the process for preparing the compound according to the invention mentioned above and lanthanum nitride is used as the alkaline earth metal in the post-calcination, the post-calcined product exhibits a red light shift. Move to launch.

In another embodiment, the compounds according to the invention may be coated. All coating methods known to those skilled in the art and used for phosphors according to the prior art are suitable for this purpose. In particular, suitable materials for coating are metal oxides and nitrides, especially alkaline earth metal oxides (such as Al ₂ O ₃ ) and alkaline earth metal nitrides (such as AlN); and SiO ₂ . The coating here can be carried out, for example, by a fluidized bed process. Other 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. It is also possible to apply an organic coating as an alternative and/or to apply an organic coating in addition to the inorganic coatings mentioned above.

Furthermore, the invention relates to the use of the compounds according to the invention as phosphors, in particular as conversion phosphors.

In the sense of the present application, the term "converting phosphor" means radiation absorbed in a certain wavelength region of the electromagnetic spectrum, preferably in the blue or UV spectral region, and emitted in another wavelength region of the electromagnetic spectrum. A material that is preferably visible in the red or orange spectral region, especially in the red spectral region. In this connection, the term "radiation-induced emission efficiency" should also be understood, that is, the conversion phosphor absorbs radiation in a certain wavelength region and emits radiation in another wavelength region with a certain efficiency. The term "emission wavelength shift" refers to the conversion of a phosphor at different wavelengths, i.e., to a shorter or longer wavelength than another or similar conversion phosphor. Therefore the maximum emission value is offset.

Furthermore, the invention relates to an emission conversion material comprising one of the compounds of the formula according to the invention mentioned above. The emission conversion material may consist of a compound according to the invention and in this case will be equivalent to the term "conversion phosphor" as defined above.

In addition to the compounds according to the invention, it is also possible for the luminescence conversion material according to the invention to comprise further conversion phosphors. In this case, the emission conversion material according to the invention comprises a mixture of at least two conversion phosphors, wherein one of the conversion phosphors is a compound according to the invention. It is especially preferred that at least two of the conversion phosphors are phosphors that emit light of different wavelengths, complementary to each other. Since the compound according to the invention is a red-emitting phosphor, this is preferably used in combination with a phosphor that emits green or yellow light or also with a phosphor that emits cyan or blue light. Alternatively, the red-emitting conversion phosphor according to the present invention may also be used in combination with a blue- and green-emitting conversion phosphor. Or according to the invention The red-emitting conversion phosphor can also be used in combination with a green-emitting conversion phosphor. Accordingly, the conversion phosphor according to the present invention is preferably used in combination with one or more other conversion phosphors in the emissive conversion material according to the present invention, which together preferably emit white light.

In the context of the present application, blue light means light having a maximum emission value between 400 nm and 459 nm, cyan means light having a maximum emission value between 460 nm and 505 nm, and green light means a maximum emission value between 506 nm and 545 nm. Light, yellow light indicates light having a maximum emission value between 546 nm and 565 nm, orange light indicates light having a maximum emission value between 566 nm and 600 nm, and red light indicates light having a maximum emission value between 601 nm and 670 nm. The compound according to the invention is preferably a red-emitting conversion phosphor.

In general, any possible conversion phosphor can be employed as another conversion phosphor that can be employed with the compounds according to the invention. Here, for example, the following are suitable: Ba ₂ SiO ₄ :Eu ²⁺ , BaSi ₂ O ₅ :Pb ²⁺ , Ba _x Sr _1-x F ₂ :Eu ²⁺ , BaSrMgSi ₂ O ₇ :Eu ²⁺ , BaTiP ₂ O ₇ , (Ba, Ti) ₂ P ₂ O ₇ : Ti, Ba ₃ WO ₆ : U, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ SiO ₄ : Mn ²⁺ , Bi ₄ Ge ₃ O ₁₂ , CaAl ₂ O ₄ :Ce ³⁺ , CaLa ₄ O ₇ :Ce ³⁺ , CaAl ₂ O ₄ :Eu ²⁺ , CaAl ₂ O ₄ :Mn ²⁺ , CaAl ₄ O ₇ :Pb ²⁺ , Mn ²⁺ , CaAl ₂ O ₄ :Tb ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ :Ce ³⁺ , Ca ₃ Al ₂ Si ₃ Oi ₂ :Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₂ :Eu ²⁺ Ca ₂ B ₅ O ₉ Br:Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl:Eu ²⁺ , Ca ₂ B ₅ O ₉ Cl:Pb ²⁺ , CaB ₂ O ₄ :Mn ²⁺ , Ca ₂ B ₂ O ₅ : Mn ²⁺ , CaB ₂ O ₄ : Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ²⁺ , Ca ₅ B ₂ SiO ₁₀ : Eu ³⁺ , Ca _0.5 Ba _0.5 Al ₁₂ O ₁₉ : Ce ^{3+ _{, Mn 2+, Ca 2 Ba 3}} (PO 4) 3 Cl: Eu 2+, SiO 2 in the CaBr _2: Eu ^2+, SiO ₂ in the CaCl _2: Eu ^2+, SiO ₂ in the CaCl _2: Eu ²⁺ , Mn 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+, SiO 2 in the CaI _2: Eu ^2+, SiO ₂ in the ^{_{CaI 2: Eu 2+, Mn 2+}} , CaLaBO 4: Eu 3+ , CaLaB ₃ O ₇ :Ce ³⁺ , Mn ²⁺ , Ca ₂ La ₂ BO ₆ . ₅ : Pb ²⁺ , Ca ₂ MgSi ₂ O ₇ , Ca ₂ MgSi ₂ O ₇ :Ce ³⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Ca ₃ MgSi ₂ O ₈ :Eu ²⁺ , Ca ₂ MgSi ₂ O ₇ :Eu ²⁺ , CaMgSi ₂ O ₆ :Eu ²⁺ , Mn ²⁺ , Ca ₂ MgSi ₂ O ₇ :Eu ²⁺ , Mn ²⁺ , CaMoO ₄ , CaMoO ₄ :Eu ³⁺ , CaO:Bi ³⁺ , CaO:Cd ²⁺ , CaO:Cu ⁺ ,CaO:Eu ³⁺ ,CaO:Eu ³⁺ ,Na ⁺ ,CaO:Mn ^{2 +} , CaO: Pb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaO: Tb ³⁺ , CaO: Tl, CaO: Zn ²⁺ , Ca ₂ P ₂ O ₇ : Ce ³⁺ , α-Ca ₃ (PO ₄ ) ₂ :Ce ³⁺ , β-Ca ₃ (PO ₄ ) ₂ :Ce ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl:Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Eu ²⁺ , Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F: Mn ²⁺ _{Ca s (PO 4) 3 F} : Sb 3+, Ca s (PO 4) 3 F: Sn 2+, α-Ca 3 (PO 4) 2: Eu 2+, β-Ca 3 (PO 4) 2: Eu ²⁺ , Ca ₂ P ₂ O ₇ :Eu ²⁺ , Ca ₂ P ₂ O ₇ :Eu ²⁺ , Mn ²⁺ , CaP ₂ O ₆ :Mn ²⁺ , α-Ca ₃ (PO ₄ ) ₂ :Pb ²⁺ , α-Ca ₃ (PO ₄ ) ₂ :S ²⁺ , β-Ca ₃ (PO ₄ ) ₂ :S ²⁺ , β-Ca ₂ P ₂ O ₇ :Sn,Mn,α-Ca ₃ (PO ₄ ) ₂ : Tr, CaS: Bi ³⁺ , CaS: Bi ³⁺ , Na, CaS: Ce ³⁺ , CaS : Eu ²⁺ , CaS : Cu ⁺ , Na ⁺ , CaS : La ³⁺ , CaS : Mn ^{2 +} , CaSO ₄ : Bi, CaSO ₄ : Ce ³⁺ , CaSO ₄ : Ce ³⁺ , Mn ²⁺ , CaSO ₄ : Eu ²⁺ , CaSO ₄ : Eu ²⁺ , Mn ²⁺ , CaSO ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , Cl, CaS: Pb ²⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , Cl, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ , CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , Cl, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ^{2 +} , Cl, CaSiO ₃ : Ce ³⁺ , Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ , Ca ₃ SiO ₄ Cl ₂ : Pb ²⁺ , CaSiO ₃ : Eu ²⁺ , CaSiO ₃ : Mn ²⁺ , Pb, CaSiO ₃ : Pb ²⁺ , CaSiO ₃ : Pb ²⁺ , Mn ²⁺ , CaSiO ₃ : Ti ⁴⁺ , CaSr ₂ (PO ₄ ) ₂ :Bi ³⁺ , β-(Ca,Sr) ₃ (PO ₄ ) ₂ :Sn ²⁺ Mn ²⁺ , CaTi ₀ . ₉ Al ₀ . ₁ O ₃ :Bi ³⁺ , CaTiO ₃ : Eu ³⁺ , CaTiO ₃ :Pr ³⁺ , Ca ₅ (VO ₄ ) ₃ Cl, CaWO ₄ , CaWO ₄ :Pb ²⁺ , CaWO ₄ :W, Ca ₃ WO ₆ :U, CaYAlO ₄ :Eu ³⁺ , CaYBO ₄ : Bi ³⁺ , CaYBO ₄ :Eu ³⁺ , CaYB ₀ . ₈ O ₃ . ₇ :Eu ³⁺ , CaY ₂ ZrO ₆ :Eu ³⁺ , (Ca,Zn,Mg) ₃ (PO ₄ ) ₂ :Sn, CeF ₃ , (Ce, Mg) BaAl ₁₁ O ₁₈ :Ce, (Ce,Mg)SrAl ₁₁ O ₁₈ :Ce, CeMgAl ₁₁ O ₁₉ :Ce:Tb, Cd ₂ B ₆ O ₁₁ :Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: In, CdS: In, CdS: In, Te, CdS: Te, CdWO ₄ , CsF, Csl, CsI: Na ⁺ , CsI: Tl, (ErCl ₃ ) _0.25 (BaCl ₂ ) _0.75 , GaN: Zn, Gd ₃ Ga ₅ O ₁₂ : Cr ³⁺ , Gd ₃ Ga ₅ O ₁₂ : Cr, Ce, GdNbO ₄ : Bi ³⁺ , Gd ₂ O ₂ S: Eu ³⁺ , Gd ₂ O ₂ Pr ³⁺ , Gd ₂ O ₂ S: Pr, Ce, F, Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAl ₁₁ O ₁₇ : Tl ⁺ , KGa ₁₁ O ₁₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ O ₁₀ :Eu, KMgF ₃ :Eu ²⁺ , KMgF ₃ :Mn ²⁺ , K ₂ SiF ₆ :Mn ⁴⁺ , LaAl ₃ B ₄ O ₁₂ :Eu ³⁺ , IaAlB ₂ O ₆ :Eu ³⁺ , LaAlO ₃ :Eu ³⁺ , LaAlO ₃ :Sm ³⁺ , LaAsO ₄ :Eu ³⁺ ,LaBr ₃ :Ce ³⁺ ,LaBO ₃ :Eu ³⁺ ,(La,Ce,Tb) PO ₄ : Ce: Tb, LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³⁺ , LaOBr: Tm ³⁺ , LaOCl : Bi ³⁺ , LaOCl : Eu ³⁺ , LaOF : Eu ³⁺ , La ₂ O ₃ :Eu ³⁺ , La ₂ O ₃ :Pr ³⁺ , La ₂ O ₂ S:Tb ³⁺ , LaPO ₄ :Ce ³⁺ , LaPO ₄ :Eu ³⁺ ,LaSiO ₃ Cl:Ce ³⁺ , LaSiO ₃ Cl:Ce ³⁺ , Tb ³⁺ , LaVO ₄ :Eu ³⁺ , La ₂ W ₃ O ₁₂ :Eu ³⁺ , LiAlF 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 ₁₄ : Mn ²⁺ , LiCeSrBa ₃ Si ₄ O ₁₄ :Mn ²⁺ , LiInO ₂ :Eu ³⁺ , LiInO ₂ :Sm ³⁺ , LiLaO ₂ :Eu ³⁺ , LuAlO ₃ :Ce ³⁺ , (Lu,Gd) ₂ Si0 ₅ :Ce ³⁺ , Lu ₂ SiO ₅ :Ce ³⁺ , Lu ₂ Si ₂ O ₇ :Ce ³⁺ , LuTaO ₄ :Nb ⁵⁺ , Lu _1-x Y _x AlO ₃ :Ce ³⁺ , MgAl ₂ O ₄ :Mn ²⁺ , MgSrAl ₁₀ O ₁₇ :Ce, MgB ₂ O ₄ :Mn ²⁺ , MgBa ₂ (PO ₄ ) ₂ :Sn ²⁺ , MgBa ₂ (PO ₄ ) ₂ :U, MgB aP ₂ O ₇ :Eu ²⁺ , MgBaP ₂ O ₇ :Eu ²⁺ ,Mn ²⁺ , MgBa ₃ Si ₂ O ₈ :Eu ²⁺ , MgBa(SO ₄ ) ₂ :Eu ²⁺ ,Mg ₃ Ca ₃ (PO ₄ ) ₄ :Eu ²⁺ , MgCaP ₂ O ₇ :Mn ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ :Eu ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ :Eu ²⁺ ,Mn ² ,MgCeAl _n O ₁₉ : Tb ³⁺ , Mg ₄ (F) GeO ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) O ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ O ₄ : Mn ²⁺ , Mg ₈ Ge ₂ O ₁₁ F ₂ :Mn ⁴⁺ , MgS:Eu ²⁺ , MgSiO ₃ :Mn ²⁺ , Mg ₂ SiO ₄ :Mn ²⁺ , Mg ₃ SiO ₃ F ₄ :Ti ⁴⁺ , MgSO ₄ :Eu ²⁺ , MgSO ₄ :Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ :Eu ²⁺ , MgSrP ₂ O ₇ :Eu ²⁺ , MgSr ₅ (PO ₄ ) ₄ :Sn ²⁺ , MgSr ₃ Si ₂ O ₈ :Eu ²⁺ , Mn ²⁺ , Mg ₂ Sr(SO ₄ ) ₃ :Eu ²⁺ , Mg ₂ TiO ₄ :Mn ⁴⁺ , MgWO ₄ , MgYBO ₄ :Eu ³⁺ , Na ₃ Ce(PO ₄ ) ₂ :Tb ^{3 +} , NaI: Tl, Na _1.23 K _0.42 Eu _0.12 TiSi ₄ O ₁₁ : Eu ³⁺ , Na _1.23 K _0.42 Eu _0.12 TiSi ₅ O ₁₃ . xH ₂ O:Eu ³⁺ , Na _1.29 K _0.46 Er _0.08 TiSi ₄ O ₁₁ :Eu ³⁺ , Na ₂ Mg ₃ Al ₂ Si ₂ O ₁₀ :Tb, Na(Mg _2-x Mn _x )LiSi ₄ O ₁₀ F ₂ : Mn, NaYF ₄ : Er ³⁺ , Yb ³⁺ , NaYO ₂ : Eu ³⁺ , P46 (70%) + P47 (30%), SrAl ₁₂ O ₁₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ : Eu ²⁺ , SrAl ₄ O ₇ :Eu ³⁺ , SrAl ₁₂ O ₁₉ :Eu ²⁺ , SrAl ₂ S ₄ :Eu ²⁺ , Sr ₂ B ₅ O ₉ Cl:Eu ²⁺ , SrB ₄ O ₇ : Eu ²⁺ (F, Cl, Br), SrB ₄ O ₇ : Pb ²⁺ , SrB ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ O ₁₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al _{2 O 4-z / 2: Mn} 2+, Ce 3+, SrBaSiO 4: Eu 2+, SiO 2 in the Sr (Cl, Br, I) 2: Eu 2+, SiO 2 in the SrCl _2: Eu ²⁺ , Sr ₅ Cl(PO ₄ ) ₃ :Eu, Sr _w F _x B ₄ O _6.5 :Eu ²⁺ , Sr _w F _x B _y O _z :Eu ²⁺ ,Sm ²⁺ ,SrF ₂ :Eu ²⁺ ,SrGa ₁₂ O ₁₉ :Mn ²⁺ , SrGa ₂ S ₄ :Ce ³⁺ , SrGa ₂ S ₄ :Eu ²⁺ , SrGa ₂ S ₄ :Pb ²⁺ , SrIn ₂ O ₄ :Pr ³⁺ ,Al ³⁺ ,(Sr ,Mg) ₃ (PO ₄ ) ₂ :Sn, SrMgSi ₂ O ₆ :Eu ²⁺ , Sr ₂ MgSi ₂ O ₇ :Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ :Eu ²⁺ , SrMoO ₄ :U, SrO. 3B ₂ O ₃ :Eu ²⁺ , Cl, β-SrO. 3B ₂ O ₃ : Pb ²⁺ , β-SrO. 3B ₂ O ₃ : Pb ²⁺ , Mn ²⁺ , α-SrO. 3B ₂ O ₃ :Sm ²⁺ , Sr ₆ P ₅ BO ₂₀ :Eu, Sr ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ ,Pr ³⁺ ,Sr ₅ (PO ₄ ) ₃ Cl:Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl:Sb ³⁺ , Sr ₂ P ₂ O ₇ :Eu ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :Eu ²⁺ ,Sr ₅ (PO ₄ ) ₃ F:Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F:Sb ³⁺ , Sr ₅ (PO ₄ ) ₃ F:Sb ³⁺ , Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F :S ²⁺ , Sr ₂ P ₂ O ₇ :S ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :S ²⁺ , β-Sr ₃ (PO ₄ ) ₂ :Sn ²⁺ , Mn ²⁺ (Al) , SrS:Ce ³⁺ , SrS:Eu ²⁺ , SrS:Mn ²⁺ , SrS:Cu ⁺ ,Na,SrSO ₄ :Bi,SrSO ₄ :Ce ³⁺ , SrSO ₄ :Eu ²⁺ ,SrSO ₄ :Eu ^{2 +} , Mn ²⁺ , Sr ₅ Si ₄ O ₁₀ Cl ₆ :Eu ²⁺ , Sr ₂ SiO ₄ :Eu ²⁺ , SrTiO ₃ :Pr ³⁺ , SrTiO ₃ :Pr ³⁺ ,Al ³⁺ ,Sr ₃ WO ₆ :U, SrY ₂ O ₃ :Eu ³⁺ , ThO ₂ :Eu ³⁺ , ThO ₂ :Pr ³⁺ , ThO ₂ :Tb ³⁺ , YAl ₃ B ₄ O ₁₂ :Bi ³⁺ , YAl ₃ B ₄ O _{12 ^{: Ce 3+, YAl 3 B 4}} O 12: Ce 3+, Mn, YAl 3 B 4 O 12: Ce 3+, Tb 3+, YAl 3 B 4 O 12: Eu 3+, YAl 3 B 4 O 12 :Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ O ₁₂ :Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAlO ₃ :Ce ³⁺ , Y ₃ Al ₅ O ₁₂ :Ce ³⁺ , Y ₃ Al ₅ O ₁₂ :Cr ³⁺ , YAlO ₃ :Eu ³⁺ , Y ₃ Al ₅ O ₁₂ :Eu ^3r , Y ₄ Al ₂ O ₉ :Eu ³⁺ , Y ₃ Al ₅ O ₁₂ :Mn ⁴⁺ , YAlO ₃ :Sm ³⁺ , YAlO ₃ :Tb ³⁺ , Y ₃ Al ₅ O ₁₂ :Tb ³⁺ , YAsO ₄ :Eu ³⁺ ,YBO ₃ :Ce ³⁺ , YBO ₃ :Eu ³⁺ , YF ₃ :Er ³⁺ , Yb ³⁺ , YF ₃ :Mn ²⁺ , YF ₃ :Mn ²⁺ , Th ⁴⁺ , YF ₃ :Tm ³⁺ ,Yb ^{3 +} , (Y, Gd) BO ₃ : Eu, (Y, Gd) BO ₃ : Tb, (Y, Gd) ₂ O ₃ : Eu ³⁺ , Y _1.34 Gd _0.60 O ₃ (Eu, Pr), Y ₂ O ₃ : Bi ³⁺ , YOBr : Eu ³⁺ , Y ₂ O ₃ : Ce, Y ₂ O ₃ : Er ³⁺ , Y ₂ O ₃ : Eu ³⁺ (YOE), Y ₂ O ₃ : Ce ³⁺ , Tb ³⁺ , YOCl: Ce ³⁺ , YOCl: Eu ³⁺ , YOF: Eu ³⁺ , YOF: Tb ³⁺ , Y ₂ O ₃ : Ho ³⁺ , Y ₂ O ₂ S: Eu ³⁺ , Y ₂ O ₂ S: Pr ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ O ₃ : Tb ³⁺ , YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO ₄ : Mn ²⁺ , Th ⁴⁺ , YPO ₄ : V ⁵⁺ , Y (P, V) O ₄ : Eu, Y ₂ SiO ₅ : Ce ³⁺ , YTaO ₄ , YTaO ₄ : Nb ⁵⁺ , YVO ₄ :Dy ³⁺ , YVO ₄ :Eu ³⁺ , ZnAl ₂ O ₄ :Mn ²⁺ , ZnB ₂ O ₄ :Mn ²⁺ ZnBa ₂ S ₃ :Mn ²⁺ , (Zn,Be) ₂ SiO ₄ :Mn ²⁺ , Zn _0.4 Cd _0.6 S:Ag, Zn _0.6 Cd _0.4 S:Ag, (Zn,Cd)S:Ag,Cl, (Zn, Cd)S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ O ₄ , ZnGa ₂ O ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ GeO ₄ : Mn ²⁺ , (Zn ,Mg)F ₂ :Mn ²⁺ , ZnMg ₂ (PO ₄ ) ₂ :Mn ²⁺ , (Zn,Mg) ₃ (PO ₄ ) ₂ :Mn ²⁺ , ZnO:Al ³⁺ ,Ga ³⁺ ,ZnO: Bi ³⁺ , ZnO : Ga ³⁺ , ZnO : Ga, ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag ⁺ , Cl ^- , 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, I, 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- , Cl ^- , ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , Cl ^- , ZnS: Pb, Cu, Zn ₃ (PO ₄ ) ₂ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ^{2 +} , As ⁵⁺ , Zn ₂ SiO ₄ : Mn, Sb ₂ O ₂ , Zn ₂ SiO ₄ : Mn ²⁺ , P, Zn ₂ SiO ₄ : Ti ⁴⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS-ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , Cl or ZnWO ₄ .

Furthermore, the invention relates to the use of an emissive conversion material according to the invention for a light source. The light source is particularly preferably an LED, in particular a phosphor converted LED, referred to as a pc-LED. Here, in addition to the conversion phosphor according to the invention, the emission-converting material particularly preferably comprises at least one further conversion phosphor, in particular such that the light source emits white light or has a certain color point (colour-on-option). Demand principle)) light. "On-demand color selection principle" refers to the generation of light having a certain color point as the pc-LED uses one or more conversion phosphors.

Furthermore, the invention is therefore directed to a light source comprising a primary light source and a emitting conversion material.

Here, in addition to the conversion phosphor according to the present invention, the emission conversion material particularly preferably comprises at least one other conversion phosphor such that the light source preferably emits white light or light having a certain color point.

The light source according to the invention is preferably a pc-LED. The pc-LED generally includes a primary light source and a transmissive conversion material. For this purpose, the emissive conversion material according to the present invention may be dispersed in a resin such as epoxy or polyoxymethylene resin, or directly disposed on or away from the primary light source if the size ratio is suitable ( The latter configuration also includes "remote phosphor technology", depending on the application.

The primary light source may be a semiconductor wafer, an illuminating light source such as ZnO, a so-called TCO (transparent conductive oxide), a ZnSe-based or SiC-based configuration, an organic light-emitting layer (OLED)-based configuration or a plasma or discharge source, preferably Semiconductor wafer. As is known from the prior art, if the primary source is a semiconductor wafer, it is preferably indium aluminum gallium nitride (InAlGaN). Possible forms of this type of primary light source are known to those skilled in the art. In addition, lasers are suitable for use as a light source.

For use with light sources, in particular pc-LEDs, the emissive conversion material according to the invention can also be converted into any desired external shape, such as spherical particles, flakes and structured materials and ceramics. These shapes are outlined under the term "formed body". Therefore, the formed body is an emission conversion molded body.

Furthermore, the invention relates to a lighting unit comprising at least one light source according to the invention. This type of lighting unit is mainly used for display devices, in particular liquid crystal display devices (LC displays) that use backlights. Accordingly, the present invention is also directed to display devices of this type.

In the illumination unit according to the invention, the optical coupling between the emission conversion material and the primary light source, in particular the semiconductor wafer, is preferably carried out by means of a light guide arrangement. In this way, it is possible for the primary light source to be mounted in a central position and optically coupled to the emission conversion material by means of a light guiding device, such as an optical fiber. In this way, it is possible to obtain a lamp suitable for illumination, which is configurable to form one or more different conversion phosphors of the screen and coupled to one The optical waveguide of the secondary light source is composed of. In this way, a stronger primary light source is likely to be placed in a position that is advantageous for the electrical device, and no further cable routing is required, and the optical waveguide is arranged at any desired location to mount the optical conversion waveguide-coupled emission-converting material. light.

The following examples and drawings are intended to illustrate the invention. However, it should never be considered limiting.

Example: General procedure for measuring emissions

The powder emission spectrum was measured by the following general method: in a cumulative sphere of an Edinburgh Instruments FL 920 fluorescence spectrometer having a xenon lamp as an excitation source, a bed of loose phosphor powder having a depth of 5 mm was irradiated at a wavelength of 450 nm (the surface thereof) The glass plate has been used for leveling and the intensity of the emitted fluorescent radiation is measured in steps of 1 nm in the range of 465 nm to 800 nm.

Comparison example: Comparative Example V1: Synthetic Ca _0.50 Ba _1.32 Eu _0.08 Si ₅ N _7.8 O _0.2

1.408 g of Eu ₂ O ₃ (4.00 mmol), 18.979 g (43.13 mmol) of Ba ₃ N ₂ , 21.074 g of Si ₃ N ₄ (150.33 mmol), and 2.471 g of Ca ₃ N ₂ (16.67) were weighed together in a glove box. Methyl) and 1.399 g (23.3 mmol) of SiO ₂ ; and mixed in a hand mortar until a homogeneous mixture has formed. The mixture was transferred to a boron nitride boat and placed on a molybdenum foil tray at the center of the tube furnace at a nitrogen/hydrogen atmosphere (70 l/min N ₂ +10 at 1650 ° C). Calcined for 8 h under H ₂ ) of l/min. The phosphor obtained in this manner was suspended in 1 M hydrochloric acid for one hour, then it was filtered off, washed with water and dried.

Comparative Example V2: Synthesis of Sr _0.885 Ba _0.885 Eu _0.08 Si ₅ N _7.7 O _0.3

0.443 g of Eu ₂ O ₃ (1.26 mmol), 3.500 g of Ba ₃ N ₂ (7.95 mmol), 5.552 g of Si ₃ N ₄ (39.58 mmol), and 0.376 g of SiO ₂ (6.25 mmol) were weighed together in a glove box. And 2.313 g of Sr ₃ N ₂ (7.95 mmol); and mixed in a hand mortar until a homogeneous mixture had formed. The mixture was transferred into a boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace at a nitrogen/hydrogen atmosphere (70 l/min N ₂ +10 l/min H at 1625 ° C). ₂ ) Calcined for 8 h. The phosphor obtained in this manner was suspended in 1 M hydrochloric acid for one hour, then it was filtered off, washed with water and dried.

According to an embodiment of the invention: Example 1: Synthetic Mg _0.25 Ca _0.25 Ba _1.32 Eu _0.08 Si ₅ N _7.8 O _0.2

2.115 g of Eu ₂ O ₃ (6.00 mmol), 27.205 g of Ba ₃ N ₂ (63.00 mmol), 33.998 g of Si ₃ N ₄ (242.35 mmol), and 2.075 g of Ca ₃ N ₂ (11.50) were weighed together in a glove box. Methyl), 1.611 g of Mg ₃ N ₂ (11.50 mmol) and 2.253 g of SiO ₂ (37.50 mmol); and mixed in a manual mortar until a homogeneous mixture has formed. The mixture was transferred to a boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace. Calcination is carried out using various holding points. The first holding point was at 700 ° C and the residence time was 2 h. This was carried out under pure nitrogen. The temperature was then raised to 1600 ° C under nitrogen. The holding time was 8 h, during which time 5 vol% of hydrogen was delivered for 2 h. The phosphor obtained in this manner was suspended in 1 M hydrochloric acid for one hour, then it was filtered off, washed with water and dried.

Example 2: Synthesis of Sr _0.885 Ba _0.885 Eu _0.08 Si _4.37 Ge _0.63 N _7.7 O _0.3

1.761 g of Eu ₂ O ₃ (5 mmol), 14.004 g of Ba ₃ N ₂ (31.668 mmol), 9.211 g of Sr ₃ N ₂ (31.668 mmol), and 19.395 g of Si ₃ N ₄ (138.300 mmol) were weighed together in a glove box. ), 5.476 g Ge ₃ N ₄ (20.000 mmol) and 1.502 g SiO ₂ (25.000 mmol); and mixed in a hand mortar until a homogeneous mixture has formed. The mixture was transferred into a boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace at a nitrogen/hydrogen atmosphere (60 l/min N ₂ +5 l/min H at 1600 ° C). ₂ ) Calcined for 8 h. The phosphor obtained in this manner was suspended in 1 M hydrochloric acid for one hour, then it was filtered off, washed with water and dried.

Example 3: Synthesis of Sr _0.885 Ba _0.885 Eu _0.08 Si ₅ N _7.7 O _0.2 S _0.1

0.443 g of Eu ₂ O ₃ (1.26 mmol), 2.807 g of Ba ₃ N ₂ (6.38 mmol), 0.932 g of BaSO ₄ (4.00 mmol), and 5.272 g of Si ₃ N ₄ (37.58 mmol) were weighed together in a glove box. 0.376 g of SiO ₂ (6.25 mmol) and 2.313 g of Sr ₃ N ₂ (7.95 mmol); and mixed in a manual mortar until a homogeneous mixture had formed. The mixture was transferred together with 2.00 g of sulfur into a covered boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace at 1600 ° C under a nitrogen/hydrogen atmosphere (40 l/min) H ₂ ) of N ₂ + 40 l/min was calcined for 8 h. The phosphor obtained in this way was suspended in 1 M hydrochloric acid for 1 h, which was then filtered off, washed with water and dried.

Example 4: Synthesis of Sr _0.85 Ba _0.85 Eu _0.10 Si ₅ N _7.6 O _0.2 S _0.2

0.443 g of Eu ₂ O ₃ (1.26 mmol), 3.500 g of Ba ₃ N ₂ (6.08 mmol), 1.166 g of BaSO ₄ (5.00 mmol), and 5.552 g of Si ₃ N ₄ (39.58 mmol) were weighed together in a glove box. 0.376 g of SiO ₂ (6.25 mmol) and 22.313 g of Sr ₃ N ₂ (7.95 mmol); and mixed in a manual mortar until a homogeneous mixture had formed. The mixture was transferred together with 2.00 g of sulfur into a covered boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace at 1600 ° C under a nitrogen/hydrogen atmosphere (40 l/min) H ₂ ) of N ₂ + 40 l/min was calcined for 8 h. The phosphor obtained in this way was suspended in 1 M hydrochloric acid for 1 h, which was then filtered off, washed with water and dried.

Example 5: Synthesis of Ca _0.42 Ba _1.32 Zn _0.09 Eu _0.07 Si ₅ N _7.8 O _0.2

1.309 g of Eu ₂ O ₃ (3.72 mmol), 18.979 g of Ba ₃ N ₂ (40.00 mmol), 0.702 g of Zn ₃ N ₂ (3.13 mmol), and 21.074 g of Si ₃ N ₄ (150.33) were weighed together in a glove box. Methyl), 2.471 g Ca ₃ N ₂ (16.67 mmol) and 1.399 g SiO ₂ (23.3 mmol); and mixed in a manual mortar until a homogeneous mixture has formed. Transfer the mixture into a boron nitride boat and place it on a molybdenum foil tray in the center of the tube furnace at a temperature of 1650 ° C in a nitrogen/hydrogen atmosphere (70 °/min N ₂ +2 l/min H) ₂ ) Calcined for 8 h. The phosphor obtained in this way was suspended in 1 M hydrochloric acid for 1 h, which was then filtered off, washed with water and dried.

Example 6: Synthesis (Mg, Ca, Ba) _1.82 Eu _0.08 Si ₅ N _7.8 O _0.2 (via post-calcination)

2.115 g of Eu ₂ O ₃ (6.00 mmol), 17.600 g of Ba ₃ N ₂ (40.00 mmol), 33.998 g of Si ₃ N ₄ (242.35 mmol), 4.151 g of Ca ₃ N ₂ (23.00) were weighed together in a glove box. Methyl), 2.321 g of Mg ₃ N ₂ (23.00 mmol) and 2.253 g of SiO ₂ (37.50 mmol); and mixed in a manual mortar until a homogeneous mixture has formed. The mixture was transferred to a boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace. Calcination is carried out using various holding points. The first holding point was at 700 ° C and the residence time was 2 h. This was carried out under pure nitrogen. The temperature was then raised to 1600 ° C under nitrogen. The holding time was 8 h, during which time 5 vol% of hydrogen was delivered for 2 h.

A mixture of 60 g of phosphor obtained in this manner and 20% by weight of 8.554 g of tantalum nitride, 2.050 g of calcium nitride and 1.396 g of magnesium nitride was mixed in a glove box until a homogeneous mixture had formed. Another calcination is then carried out, during which the conditions are the same as in the first calcination step. In order to remove excess calcium nitride, tantalum nitride and magnesium nitride, the phosphor obtained in this way was suspended in 1 M hydrochloric acid for an additional 1 h, which was then filtered off, washed with water and dried.

Example 7: Synthesis (Sr, Ba) _1.77 Eu _0.08 (Si, Ge) ₅ N _7.7 O _0.3 (via post-calcination)

1.761 g of Eu ₂ O ₃ (5 mmol), 28.008 g of Ba ₃ N ₂ (63.336 mmol), 19.395 g of Si ₃ N ₄ (138.300 mmol), and 5.476 g of Ge ₃ N ₄ (20.000 mmol) were weighed together in a glove box. And 1.502 g of SiO ₂ (25.000 mmol); and mixed in a hand mortar until a homogeneous mixture has formed. The mixture was transferred into a boron nitride boat and placed on a molybdenum foil tray in the center of the tube furnace at a nitrogen/hydrogen atmosphere (60 l/min N ₂ +5 l/min H at 1600 ° C). ₂ ) Calcined for 8 h.

The phosphor obtained in this way was mixed with 20% by weight of tantalum nitride in a glove box until a homogeneous mixture had formed. Another calcination is then carried out, during which the conditions are the same as in the first calcination step. In order to remove excess tantalum nitride, the phosphor obtained in this way was suspended in 1 M hydrochloric acid for another 1 h, which was then filtered off, washed with water and dried.

Example 8: Production of pcLED

The phosphors of mass m _p (in g) displayed in individual LED instances are weighed and mixed with m _-polyoxygen (in g) optically transparent polyfluorene, and then in a planetary centrifugal mixer were mixed to produce a homogeneous mixture so that the concentration of the phosphor to the total mass of c _p (in% by weight). The polyoxyn/phosphor mixture obtained in this way is applied to the wafer of the blue semiconductor LED by means of an automatic dispenser and cured by supplying heat. The blue semiconductor LED used for LED characterization in the examples of the present invention has an emission wavelength of 442 nm and operates at a current intensity of 350 mA. LED photometric characterization was performed using an Instrument Systems CAS 140 spectrometer and the accompanying ISP 250 integrated sphere. LEDs are characterized by measuring wavelength dependent spectral power densities. The color point coordinates CIE x and CIE y are calculated using the resulting spectra of the light emitted by the LEDs. The amount of phosphor applied is adjusted such that all LEDs have similar color point coordinates CIE x. The larger the peak wavelength of the phosphor used, the smaller the color point coordinate CIE y produced by the individual LED spectra. The results are shown in Table 1 below.

Figure 1: Emission spectrum of a phosphor according to Comparative Example V1; peak wavelength: 652 nm; CIE 1931 x = 0.647, CIE 1931 y = 0.350.

Figure 2: Excitation spectrum of the phosphor according to Comparative Example V1.

Figure 3: Emission spectrum of the phosphor according to Comparative Example V2; peak wavelength: 621 nm; CIE 1931 x = 0.620, CIE 1931 y = 0.372.

Figure 4: Excitation spectrum of the phosphor according to Comparative Example V2.

Figure 5: Emission spectrum of the phosphor according to Example 1; peak wave compared with Comparative Example V1 The long shift is 5 nm in red light; the peak wavelength is 657 nm, CIE 1931 x=0.672, CIE 1931 y=0.326.

Figure 6: Excitation spectrum of the phosphor according to Example 1; the best excitability is present at 450 nm.

Figure 7: The emission spectrum of the phosphor according to Example 2; due to the incorporation of yttrium, the red shift of the spectrum occurs; peak wavelength: 624 nm; CIE 1931 x = 0.635, CIE 1931 y = 0.362; The half value width was reduced from 90 nm (Comparative Example V2) to 86 nm.

Figure 8: Emission spectrum of the phosphor according to Example 5; red light shift of the emission band occurs due to incorporation of zinc; peak wavelength: 665 nm; CIE 1931 x = 0.661, CIE 1931 y = 0.330.

Figure 9: Location of the color point coordinates CIE x and CIE y of the LED example shown in Table 1.

Claims (16)

A compound of the formula (1), EA _a Eu _x E _e N _f Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ Formula (1) wherein the following applies to the symbols and indices used: EA means selected from Mg, Ca, One or more elements of the group consisting of Sr, Ba, and Zn; E represents one or more elements selected from the group consisting of Si and Ge; Y represents one or more elements selected from the group consisting of O and S; a 1.995; 0.005 x 0.20; 4.00 e 6.00;5.00 f 8.70;0.01 y 3.00; wherein, for the indices a, x, e, f and y: 2a + 2x + 4e = 3f + 2y; m 4.00;0 n 0.50; characterized in that the compound contains at least one of the elements Mg and/or Zn and/or Ge and/or S. The compound of claim 1, wherein each of the following applies independently of the index: 1.20 a 1.995;0.01 x 0.20; 4.50 e 5.50; 6.00 f 8.00; 0.1 y 2.5; 0 m 3.00;0 n 0.50. The compound of claim 1 or 2, wherein each of the following applies independently of the index: 1.60 a 1.995;0.02 x 0.16; 4.80 e 5.20;6.00 f 7.90; 0.15 y 1.5;0 m 2.50;0 n 0.20. The compound of any one of claims 1 to 3, wherein the compound contains Mg and the ratio is at most 40% of the element EA; and/or wherein the compound contains Zn and the ratio is at most 40% of the element EA; And/or wherein the compound contains Ge and the proportion is at most 100% of the element E; and/or wherein the compound contains S and the proportion is at most 100% of the element Y. The compound of any one of claims 1 to 4, wherein the compound contains Mg in a ratio of 5% to 40% of the element EA; and/or wherein the compound contains Zn and the ratio is 5% of the element EA Up to 40%; and/or wherein the compound contains Ge in a ratio of from 1% to 100%, preferably from 2% to 20%, of the element E; and/or wherein the compound contains S and the ratio is the element Y 1% to 100%, preferably 2% to 100%. A compound according to any one of claims 1 to 5, which is selected from the group consisting of compounds of formula (2), formula (3) and formula (4), EA _2-x+1.5z Eu _x E ₅ N _{8-2/ 3y+z} Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ Formula (2) EA _{2-x-0.5y+1.5z} Eu _x E ₅ N _8-y+z Y _y ̇m SiO ₂ ̇n Si ₃ N ₄ (3) EA _2-x+1.5z Eu _x E ₅ N _8-y+z Y _3/2y ̇m SiO ₂ ̇n Si ₃ N ₄ (4) where EA, E, Y and these indices x, y, m, and n have the meanings given in claim 1, and in addition: 0 z 3.0; wherein the compound contains at least one of the elements Mg and/or Zn and/or Ge and/or S. The compound according to any one of claims 1 to 6, which is selected from the group consisting of a compound of the formula (2a), the formula (3a) and the formula (4a), (Mg _o Ca _p Sr _q Ba _r Zn _s ) _{2-x+ 1.5z} Eu _x (Si _t Ge _u ) ₅ N _8-2/3y+z (O _v S _w ) _y ̇m SiO ₂ ̇n Si ₃ N ₄ Formula (2a) (Mg _o Ca _p Sr _q Ba _r Zn _s ) _{2-x-0.5y+1.5z} Eu _x (Si _t Ge _u ) ₅ N _8-y+z (O _v S _w ) _y ̇m SiO ₂ ̇n Si ₃ N ₄ Formula (3a) (Mg _o Ca _p Sr _q Ba _r Zn _s ) _2-x+1.5z Eu _x (Si _t Ge _u ) ₅ N _8-y+z (O _v S _w ) _3/2y ̇m SiO ₂ ̇n Si ₃ N ₄ (4a) where x, y, and z have the meanings given in claims 1 and 6, and in addition: 0 o 0.4;0 p 1;0 q 1;0 r 1;0 s 0.4;0 t 1;0 u 1;0 v 1;0 w 1; the constraint is o + p + q + r + s = 1 and t + u = 1 and v + w = 1; and furthermore, the constraint is that the indices o, s, u and / or w At least one >0. The compound of any one of claims 1 to 7, wherein m ranges from 0 to 1 and n ranges from 0 to 0.3. The compound of any one of claims 1 to 8, wherein the compound has an organic and/or inorganic coating on its surface. A process for the preparation of a compound according to any one of claims 1 to 9 comprising the steps of: a) preparing a mixture comprising a source of cerium, lanthanum and/or cerium and a nitride of the formula EA ₃ N ₂ , Wherein EA has the meaning given above; b) calcining the mixture under non-oxidizing conditions. The method of claim 10, wherein after the calcining step, another calcining step of combining the same or a plurality of alkaline earth metal nitrides and/or zinc nitride is performed. A use of a compound according to any one of claims 1 to 9 as a phosphor. An emission conversion material comprising at least one compound according to any one of claims 1 to 9, and optionally other conversion phosphors. A use of a compound according to any one of claims 1 to 9 or an emission conversion material according to claim 13 for a light source. A light source, in particular a phosphor converted LED, comprising a primary light source and a compound according to any one of claims 1 to 9 or an emission conversion material according to claim 13. A lighting unit comprising at least one light source as claimed in item 15.