WO2020053381A1

WO2020053381A1 - Blue-emitting phosphor compounds

Info

Publication number: WO2020053381A1
Application number: PCT/EP2019/074474
Authority: WO
Inventors: Mathias RAPPHAHN; Ralf Petry; Ingo Koehler; David BOEHNISCH; Thomas Juestel; Merve YILMAZ
Original assignee: Merck Patent Gmbh
Priority date: 2018-09-14
Filing date: 2019-09-13
Publication date: 2020-03-19
Also published as: TW202024305A

Abstract

The present invention relates to blue-emitting compounds, to a method for the production thereof and to the use thereof as phosphors or conversion phosphors in light sources. The present invention also relates to a radiation-converting mixture containing the compound according to the invention and to a light source which contains the compounds according to the invention or the radiation-converting mixture. The present invention further relates to light sources, in particular LEDs, and lighting units, which contain a primary light source and the compound according to the invention or the radiation-converting mixture. The compounds according to the invention are suitable as luminescent materials, in particular for generating blue or white light in LEDs.

Description

Blue-emitting fluorescent compounds

Subject of the invention

The present invention relates to blue-emitting compounds, a process for their preparation and their use as phosphors (luminophores or phosphors) or conversion phosphors

(Conversion luminophores or conversion phosphors) for converting radiation with a shorter wavelength into radiation with a longer wavelength, in particular in phosphor-converted light-emitting devices, such as, for example, pc-LEDs (phosphor converted light emitting diodes).

The present invention also relates to a radiation-converting mixture containing the compound according to the invention and a light source which the compound according to the invention or

Mix contains. Another object of the present invention is a lighting unit which comprises a light source with the compound or mixture according to the invention. The compounds and mixtures according to the invention are suitable as luminescent materials, in particular for generating blue or white light in LED solid-state light sources with LED chips which emit in the violet and / or near UV spectral range.

Background of the Invention

Inorganic phosphors have been developed for more than 100 years to spectrally adapt emitting screens, X-ray amplifiers and radiation or light sources in such a way that they optimally meet the requirements of the respective application and at the same time consume as little energy as possible. The type of excitation, i.e. the nature of the primary radiation source, and the emission spectrum required for the selection of the host lattice and the activators is crucial.

In particular, for fluorescent light sources for general lighting, that is, low-pressure discharge lamps and light-emitting diodes, are constantly being used New phosphors developed to further increase energy efficiency, color rendering and (color point) stability. ^Phosphors that are activated with Eu ²⁺ are mostly used as a blue-emitting component in discharge lamps (Hg and Xe discharge lamps) and gas discharge screens (plasma display panels). In particular, be

BaMgAhoOi7: Eu (BAM: Eu) and (Ba, Sr, Ca) ₅ (P0 ₄ ) 3CI: Eu (SCAP), whereby SCAP has so far only been used in fluorescent lamps (TL, CFL, QL, PL).

All Eu ²⁺ -activated phosphors show a decrease in their luminous efficacy as a function of the operating time under UV radiation, ie at wavelengths less than 400 nm, caused by photoionization (photooxidation) of Eu ²⁺ to Eu ³⁺ (T. Jüstel, H. Nikol, Adv. Mater. 12, 2000, 527). Here, for. For example, at BAM: Eu it can be observed that the light yield is reduced only under vacuum UV (VUV) excitation (100-199 nm), while there is no decrease in brightness when excited with longer-wave UV radiation (200-399 nm) watch is. In other words, this finding means that photoionization requires a sufficiently high excitation energy. The phosphor BAM: Eu, which emits at 453 nm, would be a stable blue emitter for use in high-performance LEDs or

Laser diodes, but it can only be excited in the UV range up to about 380 nm.

In the meantime, LEDs have almost completely replaced other light sources in the area of general and backlighting, and laser diodes are opening up more and more fields of application due to the increasing increase in their efficiency. Here, (ln, Ga) N semiconductor LED chips which emit between 380 and 420 nm are particularly efficient (FIG. 1) (cf.

C.A. Hurni et al., Appl. Phys. Lett. 106, 2015, 031 101).

Accordingly, white light LEDs based on UV emitting semiconductors with an RGB phosphor mixture are a real alternative to the widely used white light LEDs based on a blue emitting semiconductor with a yellow or yellow / red emitting converter. However, a blue phosphor must be available for this, which can be excited efficiently in the range from 380 to 420 nm, i.e. via a small Stokes Shift. Although sufficient literature on blue-emitting phosphors has been published to date, the search for an ideal phosphor as a converter for LEDs emitting 380-420 nm continues.

Examples include aluminates such as SrAli ₂ 0i9: Eu ²⁺ ,

SrAI ₄ 0 ₇ : Eu ²⁺ and Sr ₄ Ali ₄ 0 ₂₅ : Eu ²⁺ (D. Dutczak, T. Jüstel, C. Ronda, A.

Meijerink, Phys. Chem. Chem. Phys. 2015, 17, 15236), phosphates, such as Ba ₃ (ZnB ₅ Oi ₀ ) PO ₄ : Eu ²⁺ (J. Sun, X. Zhang, T. Li, Mater. Lett. 2018, 212,

343), Cai ₀ M (PO ₄ ) ₇ : Eu ²⁺ (M = Li, Na, K) (M. Chen et al “Chem. Mater. 2017, 29, 7563), Ca ₅ (P0 ₄ ) 3CI: Eu ²⁺ (X. Zhang, M. Gong, Mater. Chem. Phys.

2010, 124, 1243) and Sr ₅ (P0 ₄ ) ₃ CI: Eu ²⁺ (SJ Dhoble, J. Phys. D 2000, 33, 158). Combinatorial chemistry studies have led to other phosphors, including the materials KSrP0 ₄ : Eu and Gd ₃ AI _{3 + x} Si _3- xOi2 ₊ xN2-x: Eu (Z. Xia et al., Dalton Trans. 45, 2016 , 1 1214).

Despite all efforts, there is still no "perfect" blue

emitting phosphor for LEDs is available, which has an emission maximum in the blue spectral range between 440 and 460 nm, shows a high photoluminescence guant yield, can be efficiently excited in the ultraviolet and violet spectral range from about 250 to about 430 nm, via a high thermal Extinguishing temperature and also has high photochemical stability. That is why the search for a blue-emitting phosphor continues unchanged.

Object of the invention

It is therefore the object of the present invention to provide phosphors for LEDs which emit in the blue spectral range with an emission maximum of around 450 nm, have a high photoluminescence guant yield and are ultraviolet and violet

Efficiently excite the spectral range from about 250 to about 430 nm. In addition, it is an object of the present invention to provide phosphors for LEDs which have a high thermal quenching temperature and also have high photochemical stability. This allows the person skilled in the art to choose from a wide range of suitable materials for producing blue or white-emitting LEDs. In addition, it is an object of the present invention to provide a method for producing the phosphors which have the properties mentioned above. It is also the task of the present

Invention to provide a radiation-converting mixture containing the phosphor, and a light source and lighting unit with the radiation-converting mixture or the phosphor.

Description of the invention

Surprisingly, it was found that the objects described above are achieved by compounds of the general formula (I):

[M ^l ₄ M ^ll 7 (A0 ₄ ) 6] n (I), characterized in that the compounds of the general formula

(I) are doped with RE and Li or with RE,

where for the symbols and indices used:

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

M "is selected from the group consisting of Mg, Ca, Sr, Ba, Cu, Zn and mixtures of two or more thereof;

A is selected from the group consisting of P, As, Sb, Bi, V, Nb, Ta and mixtures of two or more thereof;

RE is selected from the group consisting of Eu, Yb, Sm, Mn and mixtures of two or more thereof;

0 <n <4.

The inventors of the present invention surprisingly found that by doping the compounds of the general formula (I) with RE and Li or with RE luminescent materials which emit in the blue spectral range with an emission maximum around 450 nm, a high photoluminescence quantum yield and can be excited efficiently in the ultraviolet and violet spectral range from about 250 to about 430 nm. The compounds according to the invention show efficient photoluminescence in the blue spectral range and have an emission band with an emission maximum of around 450 nm, preferably between 440 and 460 nm, more preferably between 445 and 455 nm. In a preferred embodiment, the compounds of the general formula (I) have a single emission band whose emission maximum is around 450 nm, more preferably between 440 and 460 nm, most preferably between 445 and 455 nm.

Due to the small Stokes shift, these blue-emitting phosphors can be used in the UV range and in the violet range

Excite the spectral range. The connections are therefore suitable as blue-emitting converters in near-UV emitting LEDs.

The compounds according to the invention can usually be excited in the spectral range from about 250 to about 430 nm, preferably from about 250 to about 405 nm, the absorption maximum being between 250 and 325 nm, and usually emit in the spectral range from about 400 to about 550 nm , the emission maximum in the blue spectral range around 450 nm, preferably in the range between 440 and 460 nm, more preferably in the range between 445 and 455 nm. The compounds according to the invention also have a high photoluminescence quantum yield and high spectral purity and have a high thermal quenching temperature and high photochemical stability. They are therefore suitable for the production of blue or white

emitting LEDs.

In the context of this application, ultraviolet light is referred to as light whose emission maximum is between 100 and 399 nm, violet light is referred to as light with an emission maximum between 400 and 430 nm, blue light is referred to as light with an emission maximum between 431 and 480 nm, as cyan-colored light, is the light with an emission maximum between 481 and 510 nm, as green light with an emission maximum between 511 and 565 nm, as yellow light with an emission maximum between 566 and 575 nm, as orange light such, whose Emission maximum is between 576 and 600 nm and as a red light, the emission maximum is between 601 and 750 nm.

In a preferred embodiment, the compounds of the general formula (I) are represented by the following general formula (II):

[M ^la ₃ M ^lb M ^M 7 (A04) 6] n (II), where:

M ^la is selected from the group consisting of Na, K, Rb and Cs;

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

and the definitions given for the general formula (I) apply to the other symbols and indices used.

It is preferred that M ^la and M ^lb are different from each other.

In a more preferred embodiment, the compounds of the general formula (I) are represented by the following general formulas (Ia) and (Ib):

[M ^l ₄ -xM ^ll 7-x (A0 ₄ ) 6: RE _x , Lix] n (la)

[M ^l ₄ -2xM ^ll 7 (A0 ₄ ) ₆ : REx] n (Lb), where:

0 <x <1;

In a more preferred embodiment, the compounds of the general formula (II) are represented by the following general formulas (IIIa) and (Mb):

[M ^la 3-yM ^lb i-zM ^ll 7-x (A0 ₄ ) 6: REx, Lix] n (lla)

[M ^la 3-2yM ^lb i-2zM ^ll 7 (A0 ₄ ) 6: REx] n (Mb), where:

0 <y <1; 0 <z <1; y + z = x; and

0 <x <1.

It is preferred that the following applies to the index n in the general formulas (I), (la), (Ib), (II), (lla) and (Mb): 0 <n <3, more preferably 0 <n < 2nd

In a particularly preferred embodiment, the index n in the general formulas (I), (la), (Ib), (II), (Na) and (Nb) is an integer selected from 1, 2 and 3.

In a very particularly preferred embodiment the following applies to the index n in the general formulas (I), (la), (Ib), (II), (Na) and (Nb): n = 1.

In the compounds according to the invention, M 'is a single-charged cation (M') ⁺ and M "is a double-charged cation (M") ²⁺ . A is present as A ^v in the + V oxidation state, RE is a doubly charged cation RE ²⁺ , Li is a single charged cation Li ⁺ and oxygen O is an oxide (O ² ). The compounds of the invention are

Conversion materials which are doped with RE and Li or with RE, the charge equalization in the case of doping with RE and Li taking place in that a RE and a Li together replace an M 'and an M "and the charge equalization in the case of doping with RE in that one RE replaces two M '.

It is preferred that the following applies to the compounds of the general formulas (I), (la) and (Ib) according to the invention:

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

M "is Mg, which can be partially replaced by Ca, Sr and / or Ba;

A is P, which can be partially replaced by As, Sb, V, Nb and / or Ta; and

RE is selected from the group consisting of Eu, Yb, Sm, Mn and mixtures of two or more thereof. It is preferred for the compounds of the general formulas (II), (IIIa) and (Mb) according to the invention to apply:

M ^la is selected from the group consisting of Na, K, Rb and Cs;

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

M "is Mg, which can be partially replaced by Ca, Sr and / or Ba;

A is P, which can be partially replaced by As, Sb, V, Nb and / or Ta; and

RE is selected from the group consisting of Eu, Yb, Sm, Mn and mixtures of two or more thereof.

Particularly preferred compounds of the general formula (IIIa) are:

N33-y (Kl-a-bRbaCSb) l-zMg7-x (P 1-cASc04) 6 EUx, l_ix (1113),

K3-y (N3l-a-bRbaCSb) l-zMg7-x (P 1-cASc04) 6 EUx, l_ix (IVs),

Rb3-y (N3l-a-bKaCSb) l-zMg7-x (P 1-cASc04) 6 EUx, Lix (Vs),

CS3-y (N3l-a-bKaRbb) l-zMg7-x (P 1-cASc04) 6 ElJx, Lix (Vl3), where:

0 <a <1, preferably 0.0 <a <0.5;

0 <b <1, preferably 0.0 <b <0.5;

0 <a + b <1;

0 <c <1, preferably 0.0 <c <0.5;

0 <y <1; 0 <z <1; y + z = x; and

0 <x <1.

It is preferred that in the general formulas (purple), (IVa), (Va) and (Via) c = 0 or c = 1.

It is preferred that in the general formulas (lla), (purple), (IVa), (Va) and (Via) y = x and z = 0.

Particularly preferred compounds of the general formula (Mb) are: Na3-2y (Kl-a-bRbaCSb) l-2zMg7 (Pl-cASc04) 6: EUx (Nlb),

K3-2y (Nai-a-bRbaCSb) l-2zMg7 (Pl-cASc04) 6: EUx (IVb),

Rb3-2y (Nai-a-bKaCSb) l-2zMg7 (Pl-cASc04) 6: EUx (Vb),

CS3-2y (Nai-a-bKaRbb) l-2zMg7 (Pl-cASc04) 6: EUx (Vib), where:

0 <a <1, preferably 0.0 <a <0.5;

0 <b <1, preferably 0.0 <b <0.5;

0 <a + b <1;

0 <c <1, preferably 0.0 <c <0.5;

0 <y <1; 0 <z <1; y + z = x; and

0 <x <1.

It is preferred that in the general formulas (IIIb), (IVb), (Vb) and (Vlb) c = 0 or c = 1.

It is preferred that in the general formulas (Mb), (IIIb), (IVb), (Vb) and (Vlb) y = z = x / 2.

It is further preferred that the following applies to the parameter x in the general formulas mentioned above: 0 <x <1, more preferably 0.0 <x <0.5, further more preferably 0.001 <x <0.1, further more preferably 0.001 <x <

0.05 and particularly preferably 0.001 <x <0.04.

It was found that compounds doped with 1% Eu ²⁺ (x = 0.03) achieve a quantum efficiency of 71% at an excitation wavelength of 350 nm. For compounds doped with 0.1% Eu ²⁺ (x = 0.003), the quantum efficiency increases to 88%.

In the general formulas mentioned above, the following applies very particularly preferably: 0.001 <x <0.005, more preferably 0.002 <x <0.004.

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

is described. Another object of the present invention is a process for preparing the compound of the invention according to the above general formulas, comprising the steps of: a) preparing a mixture comprising M ^1, M "A0 _4, RE and

optionally Li; and

b) calcining the mixture produced.

The mixture in step a) is prepared by mixing salts which contain M ¹ , M ", A0 ₄ , RE and optionally Li. The individual salts in step a) can be added and mixed in any order. It is preferred that the mixture prepared in step a) contains M ¹ , M ", A0 ₄ , RE and optionally Li in the quantitative ratio given by the general formula I.

Preferred salts containing M ¹ are carbonates M ^ COs, such as

for example Na2C03, K2CO3, Rb2CÜ3 and CS2CO3; Oxalates M ^ O ^ such as Na ₂ C ₂ 0 ₄ , K ₂ C ₂ 0 ₄ , Rb ₂ C ₂ 0 ₄ and Cs ₂ C ₂ 0 ₄ ; Oxides M ^ O, such as Na ₂ 0, K2O, Rb ₂ 0 and CS2O; Hydroxides M'OH, such as NaOH, KOH, RbOH and CsOH; M'-phosphates, such as NaH2P0 ₄ , Na2HP0 ₄ , Na3P0 ₄ , Na ₄ P207, NasPsOio and Na ₂ P ₄ 0n, KH ₂ P0 ₄ , K ₂ HP0 ₄ , K ₃ R0 ₄ , K ₄ R ₂ 0 ₇ , K5P3O10 and K ₂ P 0n,

RbH2P0 ₄ , Rb2HP0 ₄ , Rb3P0 ₄ , Rb ₄ P20 ₇ , RbsPsOio and Rb2P40, CsH2P0 ₄ , CS2HP0 ₄ , CS3P0 ₄ , CS ₄ P20 ₇ , CS5P3O10 and CS2P4O11; and nitrates M'N03, such as NaN03, KNO3, RbN03 and CSNO3.

Preferred salts containing M "are carbonates M" CO3, such as

for example MgC03, CaC03, SrC03, BaC03, CUCO3 and ZnCOs;

Carbonate-hydroxy mixed compounds M ^N 00 ₃ · M ^N (0H) ₂ · cH ₂ 0, such as MgC03-Mg (0H) ₂ -5H ₂ 0, CaC03-Ca (0H) ₂ -5H ₂ 0,

SrC0 ₃ Sr (0H) ₂ -5H ₂ 0, BaC0 ₃ Ba (0H) ₂ -5H ₂ 0, CuC0 ₃ Cu (0H) ₂ -5H ₂ 0 and ZnC03-Zn (0H) 2-5H20; Oxalate M "C204, such as MgC204, CaC204, SrC204, BaC204, CUC2O4 and Zhq2q ₄ ; Oxide M" 0, such as

for example MgO, CaO, SrO, BaO, CuO and ZnO; Hydroxides M "(OH) 2, such as, for example, Mg (OH) 2, Ca (OH) 2, Sr (OH) 2, Ba (OH) 2, Cu (OH) 2 and Zn (OH) 2; nitrates M" ( N03) 2, such as Mg (N03) 2, Ca (N03) 2, Sr (N03) 2, Ba (N03) 2, Cu (N03) 2 and Zn (N03) 2; M "phosphates, such as

for example Mg (H2P0 ₄ ) 2, MgHP0 ₄ , Mg3 (P0 ₄ ) 2, Mg2P207, Mg2P40i2 and MgP ₄ On; and M ^N carboxylate compounds, such as citrates, lactates and ascorbates.

Preferred salts containing A0 ₄ are ammonium salts (NH ₄ ) 3A0 ₄ , such as (NH ₄ ) 3P0 ₄ , (NH ₄ ) 3As0 ₄ , (NH ₄ ) 3Sb0 ₄ , (NH ₄ ) 3V0 ₄ and

(NH ₄ ) 3Nb0 ₄ ; Hydrogen ammonium salts (NH ₄ ) ₂ HA0 ₄ , such as (NH ₄ ) ₂ HP0 ₄ , (NH ₄ ) ₂ HAS0 ₄ , (NH ₄ ) ₂ HSb0 ₄ , (NH ₄ ) ₂ HV0 ₄ and (NH ₄ ) ₂ HNb0 ₄ ; and Dihydrogenammoniumsalze (NH ₄ ) H ₂ A0 ₄ , such as

(NH ₄ ) H ₂ P0 ₄ , (NH ₄ ) H ₂ AS0 ₄ , (NH ₄ ) H ₂ Sb0 ₄ , (NH ₄ ) H ₂ V0 ₄ and (NH ₄ ) ₂ HNb0 ₄ .

Preferred salts containing RE are EuO, YbO, SmO, EU ₂ O3, Yb ₂ 03, S1TI2O3, Mn02, MnCÜ3 and MnC20 ₄ -2H20.

Preferred salts containing Li are U2CO3, Li ₂ C ₂ 0 ₄ , L12O, LiOH and LiNOs.

The mixture can be prepared at temperatures between -10 and 100 ° C, preferably between 0 and 50 ° C, more preferably between 10 and 40 ° C and most preferably between 15 and 30 ° C.

It is preferred that in step a) the salts containing M ', M ", A0 ₄ , RE and Li are suspended in a non-polar or polar aprotic solvent and mixed together to dryness.

This can preferably be done using an ultrasonic bath and / or an agate mortar.

Suitable non-polar or polar aprotic solvents are

for example aliphatic or aromatic hydrocarbons, e.g. Pentane, hexane, heptane, octane, benzene and toluene; halogenated

Hydrocarbons such as trichloromethane and CCL; as well as acetone and acetonitrile.

The calcination of the mixture prepared in step b) is preferably carried out under reducing conditions. The implementation takes place usually at a temperature above 800 ° C, preferably in the range between 850 and 1100 ° C. The reducing ones

Conditions are preferably realized through a reducing atmosphere in which the mixture is calcined. It is therefore preferred that the calcination in step b) is carried out in the presence of carbon monoxide, nitrogen, hydrogen and / or forming gas or under vacuum. A reducing nitrogen / hydrogen atmosphere, such as e.g. 5 to 70% N2 and 95 to 30% H2 or e.g. 70 to 95% N2 and 30 to 5% H2 set. Reducing agents are very particularly preferred

Nitrogen / hydrogen atmospheres with 70% H2 and 30% N2 or with 90% N ₂ and 10% H ₂ .

The calcination of the mixture prepared in step b) is carried out

preferably in a period of 0.1 to 24 hours, more preferably from 4 to 20 hours, also more preferably from 6 to 14 hours and most preferably from 10 to 14 hours.

After the calcination in step b), the desired compound according to the invention is obtained as luminescent material.

In a further embodiment, the inventive

Connections are coated. All coating methods as are known to the person skilled in the art from the prior art and are used for phosphors are suitable for this. Suitable materials for the coating are, in particular, amorphous carbon (diamond-like carbon, DLC (diamond like carbon)), metal oxides, metal fluorides and metal nitrides, in particular earth metal oxides, such as Al 2 O 3,

Earth metal fluorides such as CaF2 and earth metal nitrides such as AIN and S1O2. The coating can be carried out, for example, by fluidized bed processes or by wet chemistry. Suitable coating processes are known for example from JP 04-304290, WO 91/10715, WO

99/27033, US 2007/0298250, WO 2009/065480 and WO 2010/075908, which are hereby incorporated by reference. The goal of the coating can, on the one hand, be a higher stability of the connections, for example against air or moisture. The goal can also be an improved coupling and decoupling of light by suitable choice of Surface of the coating and the refractive index of the

Be coating material.

Yet another object of the present invention is the use of the compounds according to the invention as a phosphor or conversion phosphor, in particular for the partial or complete conversion of UV light and / or violet light into low-energy light, i.e. in light with a longer wavelength. The is particularly preferred

Use of the compounds according to the invention as a phosphor or conversion phosphor for partial or complete conversion of light in the UV and violet spectral range from approximately 250 to 430 nm into light with a longer wavelength.

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

Another object of the present invention is a radiation-converting mixture comprising a compound according to the invention. The radiation-converting mixture can consist of one or more compounds according to the invention and would therefore be with the term “phosphor” or “conversion phosphor” defined above.

equate.

It is preferred that the radiation-converting mixtures in addition to the one compound according to the invention one or more others

Include luminescent materials. Preferred further luminescent materials are conversion phosphors which are different from the compounds according to the invention, or semiconductor nanoparticles

(Quantum materials).

In a particularly preferred embodiment, the radiation-converting mixture comprises a compound according to the invention and a further conversion phosphor. It is very particularly preferred that the compound according to the invention and the further conversion phosphor each emit light with mutually complementary wavelengths. In an alternative particularly preferred embodiment, the radiation-converting mixture comprises a compound according to the invention and a quantum material. It is very particularly preferred that the compound according to the invention and the quantum material each emit light with mutually complementary wavelengths.

In a further alternative particularly preferred embodiment, the radiation-converting mixture comprises a compound according to the invention, a conversion phosphor and a quantum material.

If the compounds according to the invention are used in small amounts, they already give good LED qualities. The LED quality is based on common parameters such as the color

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

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

The Color Rendering Index (CRI) is a quantity which is known to the person skilled in the art and is unity in terms of light technology, which measures the color fidelity of an artificial light source with that of sunlight and / or

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

The correlated color temperature (CCT) is a lighting parameter with the unit Kelvin that is familiar to the person skilled in the art. The higher the numerical value, the higher the blue component of the light and the colder the white light of an artificial radiation source appears to the viewer. The CCT follows the concept of the black light emitter, whose color temperature describes the so-called Planck’s curve in the CIE diagram.

The lumen equivalent is a light-technical quantity with the unit Im / W, which is known to the person skilled in the art, and describes the size of the photometric luminous flux in lumens of a light source with a specific radiometric radiation power with the unit Watt. The higher the lumen equivalent, the more efficient a light source is. The luminous flux with the unit lumen is a photometric lighting parameter which is known to the person skilled in the art and which describes the luminous flux of a light source, which is a measure of the total visible radiation emitted by a radiation source. The larger the luminous flux, the brighter the light source appears to the observer.

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

All of the quantities listed above can be calculated from the emission spectra of the light source using methods known to those skilled in the art.

The phosphors according to the invention can be excited over a wide range, which ranges from approximately 250 to approximately 430 nm, preferably from approximately 250 to approximately 405 nm, the absorption maximum being between 250 and 325 nm.

The present invention furthermore relates to a light source which contains at least one primary light source and at least one compound according to the invention or a radiation-converting mixture according to the invention. The emission maximum of the primary light source is preferably in the range from approximately 250 to approximately 430 nm, preferably in the range from approximately 250 to approximately 405 nm, the primary radiation being converted partially or completely by the phosphor according to the invention into radiation with a longer wavelength.

In a preferred embodiment of the light source according to the invention, the primary light source comprises a luminescent indium aluminum gallium nitride, in particular of the formula IniGa _j Al _k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1 is.

Possible forms of such light sources are known to the person skilled in the art. These can be light-emitting LED chips of different designs. In a further preferred embodiment of the light source according to the invention, the primary light source is a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC or else an arrangement based on an organic one

light emitting layer based arrangement (OLED).

In a further preferred embodiment of the light source according to the invention, the primary light source is a source which shows electroluminescence and / or photoluminescence. Furthermore, the primary light source can also be a plasma or discharge source.

Corresponding light sources according to the invention are also referred to as light-emitting diodes or LEDs. The light sources according to the invention can be used for signaling, lighting, backlighting, projection, decoration or for photochemical purposes.

The compounds according to the invention can be used individually or as a mixture with suitable further luminescent materials which are known to the person skilled in the art. Corresponding further luminescent materials that are suitable in principle for mixtures are conversion phosphors or quantum materials.

The compounds according to the invention show particular advantages when mixed with other luminescent materials

Fluorescent colors or when used in LEDs together with such other luminescent materials.

Mixtures which, in addition to the compound according to the invention, contain one or more further luminescent materials which emit between 480 and 700 nm in order to obtain white light LEDs are particularly preferred.

In a further preferred embodiment, the compound according to the invention is used as an individual phosphor. The compound according to the invention shows very good results due to the wide emission spectrum with a high proportion of blue, even when used as a single phosphor. Conversion phosphors which can be used together with the compound according to the invention and thus form the radiation-converting mixture according to the invention are not subject to any particular restriction. In general, any possible conversion phosphor can be used. The following are particularly suitable: Ba ₂ Si0 ₄ : Eu ²⁺ , Ba ₃ Si0 ₅ : Eu ²⁺ , (Ba, Ca) ₃ Si0 ₅ : Eu ²⁺ , BaSi ₂ N ₂ 0 ₂ : Eu, BaSi ₂ 0 ₅ : Pb ²⁺ ,

Ba ₃ Si60i ₂ N ₂ : Eu, BaxSri-xF ₂ : Eu ²⁺ (with 0 <x <1), BaSrMgSi ₂ 0 ₇ : Eu ²⁺ , BaTiP ₂ 0 ₇ , (Ba, Ti) ₂ P ₂ 0 ₇ : Ti, BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ Si0 ₄ : Mn ²⁺ , Bi ₄ Ge ₃ 0i ₂ , CaAI ₂ 0 ₄ : Ce ³⁺ , CaLa ₄ 0 ₇ : Ce ³⁺ , CaAI ₂ 0 ₄ : Eu ²⁺ , CaAI ₂ 0 ₄ : Mn ²⁺ ,

CaAI ₄ 0 ₇ : Pb ²⁺ , Mn ²⁺ , CaAI ₂ 0 ₄ : Tb ³⁺ , Ca ₃ AI ₂ Si ₃ 0i ₂ : Ce ³⁺ ,

Ca ₃ AI ₂ Si ₃ 0i ₂ : Ce ³⁺ , Ca ₃ AI ₂ Si ₃ 0i ₂ : Eu ²⁺ , Ca ₂ B ₅ 0 ₉ Br: Eu ²⁺ ,

Ca ₂ B ₅ 0 ₉ CI: Eu ²⁺ , Ca ₂ B ₅ 0 ₉ CI: Pb ²⁺ , CaB ₂ 0 ₄ : Mn ²⁺ , Ca ₂ B ₂ 0 ₅ : Mn ²⁺ , CaB ₂ 0 ₄ : Pb ²⁺ , CaB ₂ P ₂ 0 ₉ : Eu ²⁺ , Ca ₅ B ₂ SiOi ₀ : Eu ³⁺ ,

Cao _, 5Ba _0, 5Ali ₂ Oi ₉ : Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (P0 ₄ ) ₃ CI: Eu ²⁺ , CaBr ₂ : Eu ²⁺ in Si0 ₂ , CaCI ₂ : Eu ²⁺ in Si0 ₂ , CaCI ₂ : Eu ²⁺ , Mn ²⁺ in Si0 ₂ , CaF ₂ : Ce ³⁺ ,

CaF ₂ : Ce ³⁺ , Mn ²⁺ , CaF ₂ : Ce ³⁺ , Tb ³⁺ , CaF ₂ : Eu ²⁺ , CaF ₂ : Mn ²⁺ ,

CaGa ₂ 0 ₄ : Mn ²⁺ , CaGa ₄ 0 ₇ : Mn ²⁺ , CaGa ₂ S ₄ : Ce ³⁺ , CaGa ₂ S ₄ : Eu ²⁺ ,

CaGa ₂ S ₄ : Mn ²⁺ , CaGa ₂ S ₄ : Pb ²⁺ , CaGe0 ₃ : Mn ²⁺ , Cal ₂ : Eu ²⁺ in Si0 ₂ , Cal ₂ : Eu ²⁺ , Mn ²⁺ in Si0 ₂ , CaLaB0 ₄ : Eu ³⁺ , CaLaB ₃ 0 ₇ : Ce ³⁺ , Mn ²⁺ ,

Ca ₂ La ₂ B06 _{, 5} : Pb ²⁺ , Ca ₂ MgSi ₂ 0 ₇ , Ca ₂ MgSi ₂ 0 ₇ : Ce ³⁺ , CaMgSi ₂ 06: Eu ²⁺ , Ca ₃ MgSi ₂ 0 ₈ : Eu ²⁺ , Ca ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , CaMgSi ₂ 0 ₆ : Eu ²⁺ , Mn ²⁺ ,

Ca ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , Mn ²⁺ , CaMo0 ₄ , CaMo0 ₄ : Eu ³⁺ , CaO: Bi ³⁺ , CaO: Cd ²⁺ , CaO: Cu ⁺ , CaO: Eu ³⁺ , CaO: Eu ³⁺ , Na ⁺ , CaO: Mn ²⁺ , CaO: Pb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaO: Tb ³⁺ , CaO: TI, CaO: Zn ²⁺ , Ca ₂ P ₂ 0 ₇ : Ce ³⁺ , a-Ca ₃ (P0 ₄ ) ₂ : Ce ³⁺ , ß-Ca ₃ (P0 ₄ ) ₂ : Ce ³⁺ , Ca ₅ (P0 ₄ ) ₃ CI: Eu ²⁺ , Ca ₅ (P0 ₄ ) ₃ CI: Mn ²⁺ , Ca ₅ (P0 ₄ ) ₃ CI: Sb ³⁺ , Ca ₅ (P0 ₄ ) ₃ CI: Sn ²⁺ , ß-Ca ₃ (P0 ₄ ) ₂ : Eu ^{2 +} , Mn ²⁺ , Ca ₅ (P0 ₄ ) ₃ F: Mn ²⁺ ,

Ca ₅ (P0 ₄ ) ₃ F: Sb ³⁺ , Ca ₅ (P0 ₄ ) ₃ F: Sn ²⁺ , a-Ca ₃ (P0 ₄ ) ₂ : Eu ²⁺ , ß-Ca ₃ (P0 ₄ ) ₂ : Eu ²⁺ , Ca ₂ P ₂ 0 ₇ : Eu ²⁺ , Ca ₂ P ₂ 0 ₇ : Eu ²⁺ , Mn ²⁺ , CaP ₂ 0 ₆ : Mn ²⁺ , a-Ca ₃ (P0 ₄ ) ₂ : Pb ²⁺ , a-Ca ₃ (P0 ₄ ) ₂ : Sn ²⁺ , ß-Ca ₃ (P0 ₄ ) ₂ : Sn ²⁺ , ß-Ca ₂ P ₂ 0 ₇ : Sn, Mn, a-Ca ₃ (P0 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 +} , CaS0 ₄ : Bi, CaS0 ₄ : Ce ³⁺ , CaS0 ₄ : Ce ³⁺ , Mn ²⁺ , CaS0 ₄ : Eu ²⁺ , CaS0 ₄ : Eu ²⁺ , Mn ²⁺ , CaS0 ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , CI, CaS: Pb ²⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , CI, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ ,

CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , CI, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ²⁺ , CI, CaSc ₂ 0 ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ 0i ₂ : Ce, CaSi0 ₃ : Ce ³⁺ , Ca ₃ Si0 ₄ CI ₂ : Eu ²⁺ ,

Lu ₂ Si0 ₅ : Ce ³⁺ , Lu ₂ Si ₂ 0 ₇ : Ce ³⁺ , LuTa0 ₄ : Nb ⁵⁺ , Lui _-x Y _x AI0 ₃ : Ce ³⁺ (with 0 <x <1), (Lu, Y) ₃ (AI, Ga, Sc) ₅ 0i ₂ : Ce, MgAI ₂ 0 ₄ : Mn ²⁺ , MgSrAli ₀ Oi ₇ : Ce, MgB ₂ 0 ₄ : Mn ²⁺ , MgBa ₂ (P0 ₄ ) ₂ : Sn ²⁺ , MgBa ₂ (P0 ₄ ) ₂ : U, MgBaP ₂ 0 ₇ : Eu ²⁺ , MgBaP ₂ 0 ₇ : Eu ²⁺ , Mn ²⁺ , MgBa ₃ Si ₂ 0 ₈ : Eu ²⁺ , MgBa (S0 ₄ ) ₂ : Eu ²⁺ , Mg ₃ Ca ₃ (P0 ₄ ) ₄ : Eu ²⁺ , MgCaP ₂ 0 ₇ : Mn ²⁺ , Mg ₂ Ca (S0 ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ca (S0 ₄ ) ₃ : Eu ²⁺ , Mn ² , MgCeAl _n Oi ₉ : Tb ³⁺ ,

Mg ₄ (F) Ge0 ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) 0 ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ 0 ₄ : Mn ²⁺ , Mg ₈ Ge ₂ 0 F ₂ : Mn ⁴⁺ , MgS: Eu ²⁺ , MgSi0 ₃ : Mn ²⁺ , Mg ₂ Si0 ₄ : Mn ²⁺ ,

Mg ₃ Si0 ₃ F ₄ : Ti ⁴⁺ , MgS0 ₄ : Eu ²⁺ , MgS0 ₄ : Pb ²⁺ , MgSrBa ₂ Si ₂ 0 ₇ : Eu ²⁺ ,

MgSrP ₂ 0 ₇ : Eu ²⁺ , MgSr ₅ (P0 ₄ ) ₄ : Sn ²⁺ , MgSr ₃ Si ₂ 0 ₈ : Eu ²⁺ , Mn ²⁺ ,

Mg ₂ Sr (S0 ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ti0 ₄ : Mn ⁴⁺ , MgW0 ₄ , MgYB0 ₄ : Eu ³⁺ , M ₂ MgSi ₂ 0 ₇ : Eu ²⁺ (M = Ca, Sr, and / or Ba), M ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , Mn ²⁺ (M = Ca, Sr, and / or Ba), M ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , Zr ⁴⁺ (M = Ca , Sr, and / or Ba),

M ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , Mn ²⁺ , Zr ⁴⁺ (M = Ca, Sr, and / or Ba), Na ₃ Ce (P0 ₄ ) ₂ : Tb ³⁺ , Nai _{, 23} Ko _, 42Euo _{, i} 2TiSi ₄ On: Eu ³⁺ , Nai _{, 23} Ko _{, 42} Euo _{, i 2} TiSi ₅ 0i ₃ xFI ₂ 0: Eu ³⁺ ,

Nai _{, 29} Ko _, 46Ero _, o8TiSi ₄ On: Eu ³⁺ , Na ₂ Mg ₃ AI ₂ Si ₂ Oio: Tb, Na (Mg _2- _x Mn _x ) LiSi ₄ OioF ₂ : Mn (with 0 <x <2) , NaYF ₄ : He ³⁺ , Yb ³⁺ , NaY0 ₂ : Eu ³⁺ , P46 (70%) + P47 (30%), β-SiAION: Eu, SrAli ₂ 0i ₉ : Ce ³⁺ , Mn ²⁺ , SrAI ₂ 0 ₄ : Eu ²⁺ , SrAI ₄ 0 ₇ : Eu ³⁺ , SrAh ₂ 0i ₉ : Eu ²⁺ , SrAI ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ 0 ₉ CI: Eu ²⁺ ,

SrB ₄ 0 ₇ : 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 ClzAI ₂ 0 _4- z / 2: Mn ²⁺ , Ce ³⁺ , SrBaSi0 ₄ : Eu ²⁺ ,

(Sr, Ba) 3Si0 ₅ : Eu, (Sr, Ca) Si ₂ N ₂ 0 ₂ : Eu, Sr (CI, Br, l) ₂ : Eu ²⁺ in Si0 ₂ , SrCI ₂ : Eu ²⁺ in Si0 ₂ , Sr ₅ CI (P0 ₄ ) ₃ : Eu, Sr _w FxB ₄ 0 _6.5 : Eu ²⁺ , Sr _w FxByO _z : Eu ²⁺ , Sm ²⁺ , SrF ₂ : Eu ²⁺ , SrGai ₂ 0i ₉ : Mn ²⁺ , SrGa ₂ S ₄ : Ce ³⁺ , SrGa ₂ S ₄ : Eu ²⁺ , Sr _2-y Ba _y Si0 ₄ : Eu (where 0 <y <2), SrSi ₂ 0 ₂ N ₂ : Eu, SrGa ₂ S ₄ : Pb ²⁺ , Srln ₂ 0 ₄ : Pr ³⁺ , Al ³⁺ , (Sr, Mg) ₃ (P0 ₄ ) ₂ : Sn, SrMgSi ₂ 0 ₆ : Eu ²⁺ , Sr ₂ MgSi ₂ 0 ₇ : Eu ²⁺ , Sr ₃ MgSi ₂ 0 ₈ : Eu ²⁺ , SrMo0 ₄ : U,

Sr0-3B ₂ 0 ₃ : Eu ²⁺ , CI, ß-Sr0-3B ₂ 0 ₃ : Pb ²⁺ , ß-Sr0-3B ₂ 0 ₃ : Pb ²⁺ , Mn ²⁺ ,

a-Sr0-3B ₂ 0 ₃ : Sm ²⁺ , Sr ₆ P ₅ B0 ₂ o: Eu, Sr ₅ (P0 ₄ ) ₃ CI: Eu ²⁺ , Sr ₅ (P0 ₄ ) ₃ CI: Eu ²⁺ , Pr ³⁺ , Sr ₅ (P0 ₄ ) ₃ CI: Mn ²⁺ , Sr ₅ (P0 ₄ ) ₃ CI: Sb ³⁺ , Sr ₂ P ₂ 0 ₇ : Eu ²⁺ , ß-Sr ₃ (P0 ₄ ) ₂ : Eu ²⁺ , Sr ₅ (P0 ₄ ) ₃ F: Mn ²⁺ , Sr ₅ (P0 ₄ ) ₃ F: Sb ³⁺ , Sr ₅ (P0 ₄ ) ₃ F: Sb ³⁺ , Mn ²⁺ , Sr ₅ ( P0 ₄ ) ₃ F: Sn ²⁺ , Sr ₂ P ₂ 0 ₇ : Sn ²⁺ , ß-Sr ₃ (P0 ₄ ) ₂ : Sn ²⁺ , ß-Sr ₃ (P0 ₄ ) ₂ : Sn ²⁺ , Mn ²⁺ (AI), SrS: Ce ³⁺ , SrS: Eu ²⁺ , SrS: Mn ²⁺ , SrS: Cu ⁺ , Na, SrS0 ₄ : Bi, SrS0 ₄ : Ce ³⁺ , SrS0 ₄ : Eu ²⁺ , SrS0 ₄ : Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ OioCI ₆ : Eu ²⁺ , Sr ₂ Si0 ₄ : Eu ²⁺ , Sr ₃ Si0 ₅ : Eu ²⁺ ,

(Sr, Ba) ₃ Si0 ₅ : Eu ²⁺ , SrTi0 ₃ : Pr ³⁺ , SrTi0 ₃ : Pr ³⁺ , AI ³⁺ , SrY ₂ 0 ₃ : Eu ³⁺ , Th0 ₂ : Eu ³⁺ , Th0 ₂ : Pr ³⁺ , Th0 ₂ : Tb ³⁺ , YAI ₃ B ₄ 0i ₂ : Bi ³⁺ , YAI ₃ B ₄ 0i ₂ : Ce ³⁺ , YAI ₃ B ₄ 0i ₂ : Ce ³⁺ , Mn, YAI ₃ B ₄ 0i ₂ : Ce ³⁺ , Tb ³⁺ , YAI ₃ B ₄ 0i ₂ : Eu ³⁺ , YAI ₃ B ₄ 0i ₂ : Eu ³⁺ , Cr ³⁺ ,

YAI ₃ B ₄ Oi ₂ : Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAI0 ₃ : Ce ³⁺ , Y ₃ AI ₅ 0i ₂ : Ce ³⁺ , Y ₃ AI ₅ 0i ₂ : Cr ³⁺ , YAI0 ₃ : EU ³⁺ , Y ₃ AI ₅ 0i ₂ : Eu ^3r , Y ₄ AI ₂ 0 ₉ : Eu ³⁺ , Y ₃ AI ₅ 0i ₂ : Mn ⁴⁺ , YAI0 ₃ : Sm ³⁺ , YAI0 ₃ : Tb ³⁺ , Y ₃ AI ₅ 0i ₂ : Tb ³⁺ , YAs0 ₄ : Eu ³⁺ , YB0 ₃ : Ce ³⁺ , YB0 ₃ : Eu ³⁺ ,

YF ₃ : Er ³⁺ , Yb ³⁺ , YF ₃ : Mn ²⁺ , YF ₃ : Mn ²⁺ , Th ⁴⁺ , YF ₃ : Tm ³⁺ , Yb ³⁺ , (Y, Gd) B0 ₃ : Eu, (Y, Gd) B0 ₃ : Tb, (Y, Gd) ₂ 0 ₃ : Eu ³⁺ , Yi _{, 34} Gdo _{, 6} o0 ₃ : (Eu, Pr), Y ₂ 0 ₃ : Bi ³⁺ , YOBr: Eu ³⁺ , Y ₂ 0 ₃ : Ce, Y ₂ 0 ₃ : Er ³⁺ , Y ₂ 0 ₃ : Eu ³⁺ , Y ₂ 0 ₃ : Ce ³⁺ , Tb ³⁺ , YOCI: Ce ³⁺ , YOCI: Eu ³⁺ , YOF: Eu ³⁺ , YOF: Tb ³⁺ , Y ₂ 0 ₃ : Ho ³⁺ , Y ₂ 0 ₂ S: Eu ³⁺ , Y ₂ 0 ₂ S: Pr ³⁺ , Y ₂ 0 ₂ S: Tb ³⁺ , Y ₂ 0 ₃ : Tb ³⁺ , YP0 ₄ : Ce ³⁺ , YP0 ₄ : Ce ³⁺ , Tb ³⁺ , YP0 ₄ : Eu ³⁺ , YP0 ₄ : Mn ²⁺ , Th ⁴⁺ , YP0 ₄ : V ⁵⁺ , Y (P, V) 0 ₄ : EU, Y ₂ Si0 ₅ : Ce ³⁺ , YTa0 ₄ , YTa0 ₄ : Nb ⁵⁺ , YV0 ₄ : Dy ³⁺ , YV0 ₄ : EU ³⁺ , ZnAI ₂ 0 ₄ : Mn ²⁺ , ZnB ₂ 0 ₄ : Mn ²⁺ , ZnBa ₂ S ₃ : Mn ²⁺ , (Zn, Be) ₂ Si0 ₄ : Mn ²⁺ , Zno _, 4Cdo _, 6S: Ag, Zno _, 6Cdo _, 4S: Ag, (Zn, Cd) S: Ag, CI, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ 0 ₄ , ZnGa ₂ 0 ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ Ge0 ₄ : Mn ²⁺ , (Zn, Mg) F ₂ : Mn ²⁺ , ZnMg ₂ (P0 ₄ ) ₂ : Mn ²⁺ , (Zn, Mg) ₃ (P0 ₄ ) ₂ : Mn ²⁺ , ZnO: AI ³⁺ , Ga ³⁺ , ZnO: Bi ³⁺ ,

ZnO: Ga ³⁺ , ZnO: Ga, ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag ⁺ , CI, ZnS: Ag, Cu, CI, ZnS: Ag, Ni, ZnS : Au, ln, ZnS-CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25), ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , CI , ZnS-CdS: Cu, Br, ZnS-CdS: Cu, l, ZnS: C | -, ZnS: Eu ²⁺ , ZnS: Cu, ZnS: Cu ⁺ , AI ³⁺ , ZnS: Cu ⁺ , C | - , ZnS: Cu, Sn, ZnS: Eu ²⁺ , ZnS: Mn ²⁺ , ZnS: Mn, Cu, ZnS: Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ³ , CI, ZnS: Pb ²⁺ , ZnS: Pb ²⁺ , C | -, ZnS: Pb, Cu, Zn ₃ (P0 ₄ ) ₂ : Mn ²⁺ ,

Zn ₂ Si0 ₄ : Mn ²⁺ , Zn ₂ Si0 ₄ : Mn ²⁺ , As ⁵⁺ , Zn ₂ Si0 ₄ : Mn, Sb ₂ 0 ₂ , Zn ₂ Si0 ₄ : Mn ²⁺ , P, Zn ₂ Si0 ₄ : Ti ⁴⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS- ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , CI and ZnW0 ₄ .

Preferred quantum materials which can be used together with the compound according to the invention and which form the radiation-converting mixture according to the invention are not subject to any particular restriction. In general, any possible quantum material can be used. Semiconductor nanoparticles with an elongated, round, elliptical and pyramidal geometry, which can be in a core-shell configuration or in a core-multi-shell configuration, are particularly suitable. Such semiconductor nanoparticles are, for example, from WO 2005075339, WO 2006134599, EP 2 528 989 B1 and US

8,062,421 B2, the disclosures of which are hereby incorporated by reference.

The quantum materials preferably consist of semiconductors

Groups II-VI, III-V, IV-VI or III-VI ₂ or any combination thereof. For example, the quantum material can be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, GaAs, GaP, GaAs, GaSb, GaN, HgS, HgSe, HgTe, InAs, InP, InSb, AIAs, AIP , AlSb, Cu ₂ S, Cu ₂ Se, CuGaS ₂ , CuGaSe ₂ , CulnS ₂ , CulnSe ₂ , Cu ₂ lnGaS ₄ , AglnS ₂ , AglnSe ₂ , Cu ₂ ZnSnS ₄ , alloys thereof and mixtures thereof.

Quantum materials can also be in the form of semiconductor nanoparticles on the surface of non-activated crystalline materials. In such materials there are one or more types of semiconductor nanoparticles on the surface of one or more types of non-activated crystalline materials, such as non-activated phosphor matrix materials. Such materials are also referred to as quantum material on phosphor matrix (QMOP) and are known from WO 2017/041875 A1, the disclosure of which is hereby incorporated by reference. The phosphors or phosphor combinations according to the invention can be in the form of bulk material, powder material, thick or thin layer material or self-supporting material, preferably in the form of a film. It can also be embedded in a potting material.

The luminescent materials or luminescent material combinations according to the invention can either be dispersed in a potting material or, if the proportions are suitable, directly on the primary light source

be arranged or, depending on the application, be arranged at a distance from the latter (the latter arrangement also includes the “remote phosphor technology”). The advantages of "remote phosphor technology" are known to the person skilled in the art and e.g. from the following publication: Japanese Journal of Applied Physics Vol. 44, No. 21 (2005), L649-L651.

The term “potting material” refers to a translucent matrix material that includes the compounds according to the invention and radiation-converting mixtures. The translucent matrix material can be formed from a silicone, a polymer (which is formed from a liquid or semi-solid precursor material such as a monomer or oligomer), an epoxy, a glass or a hybrid of a silicone and an epoxy. Specific but non-limiting examples of the polymers include fluorinated polymers, polyacrylamide polymers, polyacrylic acid polymers, polyacrylonitrile polymers, polyaniline polymers, polybenzophenone polymers, poly (methyl methacrylate) polymers, silicone polymers, aluminum polymers,

Polybispheno polymers, polybutadiene polymers, polydimethylsiloxane polymers, polyethylene polymers, polyisobutylene polymers, polypropylene polymers, polystyrene polymers, polyvinyl polymers, polyvinyl butyral polymers or perfluorocyclobutyl polymers. Silicones can include gels such as Dow Corning® OE-6450, elastomers such as Dow Corning® OE-6520, Dow Corning® OE-6550, Dow Corning® OE-6630, and resins such as Dow Corning® OE-6635, Dow

Corning® OE-6665, Nusil LS-6143 and other products from Nusil, Momentive RTV615, Momentive RTV656 and many other products from other manufacturers. Furthermore, the potting material can (Poly) silazane, such as a modified organic polysilazane (MOPS) or a perhydropolysilazane (PHPS). The proportion of the compound according to the invention or of the radiation-converting mixture, based on the potting material, is preferably in the range from 1 to 300% by weight, more preferably in the range from 3 to 50% by weight.

In a further embodiment, it is preferred if the optical coupling between the luminescent material and the primary light source is realized by a light-guiding arrangement. This makes it possible for the primary light source to be installed at a central location and for it to be optically coupled to the luminescent material by means of light-guiding devices, such as light-guiding fibers. In this way, it is possible to place a strong primary light source in a location that is favorable for the electrical installation and to install luminaires with luminescent materials that are optically coupled to the light conductors without any further electrical wiring, but only by laying light guides at any location.

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

Further objects of the invention are a lighting unit, in particular for the backlighting of display devices, characterized in that it contains at least one light source according to the invention, and a display device, in particular a liquid crystal display device (LC display), with a backlight, characterized in that it contains at least one lighting unit according to the invention.

The average particle size of the phosphors according to the invention for use in LEDs is usually between 50 nm and 100 μm, preferably between 0.1 pm and 25 pm and more preferably between 1 pm and 20 pm. The average particle size is preferably determined in accordance with ISO 13320: 2009 (“Particle size analysis - laser diffracation methods”). The ISO standard is based on measuring the size distribution of particles by analyzing their light scattering properties. The average particle size can also be determined using a suitable multisizer (eg Beckman Coulter Multisizer 3).

For use in LEDs, the phosphors can also be converted into any external shape, such as spherical particles, platelets and structured materials and ceramics. According to the invention, these forms are summarized under the term “shaped body”. The shaped body is preferably a “phosphor body”. Another object of the present invention is thus a shaped body containing the phosphors according to the invention. The skilled worker is familiar with the production and use of corresponding shaped articles from numerous publications.

In addition, the phosphors according to the invention can also be in the form of a phosphor-polymer composite. Suitable polymers for the production of phosphor-polymer composites are the potting materials mentioned above.

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

1) The compounds according to the invention have an emission spectrum with a high blue content and they have a high photoluminescence quantum yield.

2) The compounds according to the invention have a low thermal quenching. The TQi _/ 2 values of the compounds according to the invention are usually in the range of over 900 K.

3) The high temperature stability of the compounds according to the invention enables the use of the material even in thermally highly stressed light sources. 4) Furthermore, the compounds according to the invention are distinguished by a long service life and enable high color rendering and high stability of the color temperature in an LED. In this way, white light-emitting pc LEDs with high color rendering values can be realized.

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

All of the embodiments described here can be combined with one another, provided the respective embodiments are not mutually exclusive. In particular, based on the teaching of this document in the context of routine optimization, it is an obvious process to combine different embodiments described here in order to arrive at a specific, particularly preferred embodiment.

The following examples are intended to illustrate the present invention and in particular show the result of exemplary combinations of the described embodiments of the invention. However, they are by no means to be regarded as restrictive, but rather are intended to stimulate the generalization. All compounds or components used in the production are either known and commercially available or can be synthesized by known methods. The temperatures given in the examples always apply in ° C. It goes without saying that both in the description and in the examples, the amounts of the constituents used in the compositions always add up to a total of 100%. Percentages are always to be seen in the given context. Examples

Measurement methods

The X-ray diffractograms were recorded with a Rigaku Miniflex II, operated in Bragg-Brentano geometry, in 0.02 ° steps with an integration time of 1 s with Cu-K _a radiation.

Reflection spectra were recorded using a fluorescence spectrometer from Edinburgh Instruments Ltd. certainly. For this purpose, the samples were placed in an Ulbricht sphere coated with BaS0 ₄ and in the synchroscan

(Emission and excitation monochromator run in parallel). Reflection spectra were in a range from 250 to 800 nm

added. BaS0 ₄ (Alfa Aesar 99.998%) was used as the white standard. A 450 W Xe high pressure lamp served as an excitation source.

The emission spectra were recorded with a fluorescence spectrometer from Edinburgh Instruments Ltd., equipped with mirror optics for powder samples, at an excitation wavelength of 350 nm. A 450 W Xe lamp was used as the excitation source. The spectrometer was equipped with a cryostat from Oxford Instruments (MicrostatN2) for temperature-dependent measurement of the emission. Nitrogen was used as the coolant.

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

The calculation of the color coordinates for the CIE 1931 color diagram was calculated according to DIN 5033-3 (replaced by DIN EN ISO 1 1664-3).

Example 1: Na _2,985 Euo, oi5RbMg6,985Lio, oi5 (P0 ₄ ) 6 (0.5% Eu ²⁺ )

For the synthesis of 2.2360 g (2.5000 mmol) 0.4152 g (3.9178 mmol) Na2C03, 0.3464 g (1, 5000 mmol) Rb2C03, 1.6961 g (3.4925 mmol) 4 MgC0 ₃ Mg (0H) ₂ -5 H ₂ 0.1.7254 g (15.0000 mmol) (NH ₄ ) H ₂ P0 ₄ , 0.0066 g (0.0188 mmol) EU2O3 and 0.0014 g (0.0188 mmol) U2CO3 in one

Agate mortar mixed in hexane until dry. The powder is then transferred to a beaker and treated in an ultrasonic bath for 15 minutes. The mixture is then ground again to dryness in an agate mortar. Then the

Educt mixture calcined for 12 h at 900 ° C under forming gas (10% H2, 90% N2). Thereafter, the pigment cake obtained is pulverized in an agate mortar to obtain the title compound. FIG. 2 shows the X-ray diffractogram of the compound obtained. The associated reflection, emission and excitation spectra are shown in FIGS. 3, 4 and 5, respectively. FIG. 6 shows a section of the CIE 1931 color diagram with the color point of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6. FIG. 7 shows the relative course of the emission integrals over the temperature.

Example 2: Na ^ Euo.sKMgyiPO ^ e (10% Eu ²⁺ )

For the synthesis of 13.2 g (15,000 mmol) 1.9078 g (18 mmol) Na ₂ CO ₃ , 1.1402 g (8.25000 mmol) K2CO3, 10.014 g (45.000 mmol)

Mg2P207, 0.87 g (15,000 mmol) Mg (OH) 2 and 0.7918 g (0.2249 mmol) EU2O3 mixed in an agate mortar. The starting material mixture is then calcined for 6 h at 950 ° C. under forming gas (70% H2, 30% N2). Thereafter, the pigment cake obtained is pulverized in an agate mortar to obtain the title compound.

Example 3: Na _2,985 Euo, oi5RbMg6,985Lio, oi5 (As0 ₄ ) 6 (0.5% Eu ²⁺ )

For the synthesis of 2.2360 g (2.500 mmol) 0.4152 g (3.9178 mmol) Na2C03, 0.3464 g (1, 5000 mmol) Rb2C03, 1.6961 g (3.4925 mmol)

4 MgC0 ₃ Mg (0H) ₂ -5 H ₂ 0, 2.3846 g (15.0000 mmol) (NH ₄ ) H ₂ As0 ₄ ,

0.0066 g (0.0188 mmol) of E112O3 and 0.0014 g (0.0188 mmol) of U2CO3 were mixed together in an agate mortar in hexane until dry.

The powder is then transferred to a beaker and treated in an ultrasonic bath for 15 minutes. The mixture is then ground again to dryness in an agate mortar. The educt mixture is then calcined for 12 h at 900 ° C under forming gas (10% H2, 90% N2). Thereafter, the pigment cake obtained is pulverized in an agate mortar to obtain the title compound. Example 4: Na2.7Euo, 3RbMg6.7Li _0, 3 (As04) 6 (10% Eu ²⁺ )

For the synthesis of 2.2360 g (2.5000 mmol), 0.3756 g (3.5438 mmol) Na2C03, 0.3464 g (1, 5000 mmol) Rb2C03, 1., 6269 g (3.3500 mmol)

0.1320 g (0.3750 mmol) E112O3 and 0.0277 g (0.3750 mmol) U2CO3 in an agate mortar in hexane until dry.

The powder is then transferred to a beaker and treated in an ultrasonic bath for 15 minutes. The mixture is then ground again to dryness in an agate mortar. The educt mixture is then calcined for 12 h at 900 ° C under forming gas (10% H2, 90% N2). Thereafter, the pigment cake obtained is pulverized in an agate mortar to obtain the title compound.

Example 5: Application 6500K white LED:

0.46g Na2.985Euo, oi5RbMg6.985Lio, oi5 (P0 ₄ ) 6 (0.5% Eu ²⁺ ) from Example 1 are mixed with 0.02g Ba ₂ MgSi ₂ 0 ₇ : Eu and 0.005 g (Sr, Ca) AISiN3: Eu mixed and then dispersed in Dow Corning HF OE6370 silicone. The dispersion is filled in LED chip on board packages with 395 nm LED chip and then cured for one hour at 150 ° C.

Example 6: Application 2800 K white LED:

0.72 g Na2.985Euo, oi5RbMg6.985Lio, oi5 (P0 ₄ ) 6 (0.5% Eu ²⁺ ) from Example 1 are mixed with 0.12 g Lu3AlsOi2: Ce and 0.09 g (Ba.Sr ^ SisNsiEu mixed and then dispersed in two-component silicone Silbione RT Gel 4317 AI Silbione RT Gel 4317 B from Bluestar Silicons, Germany, The cured silicone is applied to a 370 nm LED chip.

Description of the figures

Figure 1: Efficiency of LED and laser diode as a function of

Emission wavelength. The triangles stand for LEDs and the squares for laser diodes.

Figure 2: X-ray diffractogram of

Na2.985Euo, oi5RbMg6.985Lio, oi5 (P0 ₄ ) 6 for Cu-K _a radiation (Example 1).

Figure 3: Reflection spectrum of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 against BaS0 ₄ as a white standard (Example 1).

Figure 4: Emission spectrum of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 with excitation at 350 nm (Example 1).

Figure 5: Excitation spectrum of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 for the Eu ²⁺ emission band at 450 nm (Example 1).

Figure 6: Detail from the CIE 1931 color diagram with the

Color point of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 (Example 1).

Figure 7: Relative course of the emission integrals over the temperature of Na2.985Euo, oi5RbMg6.985Lio, oi5 (P0 ₄ ) 6 with excitation at 350 nm (Example 1).

Figure 8: Emission spectrum of the LED application example at 6500 K color temperature with Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 as a blue component in combination with Ba ₂ MgSi ₂ 0 ₇ : Eu and (Sr, Ca) AISiN3: Eu (see example 5).

Figure 9: Emission spectrum of the LED application example at 2800 K color temperature with Na2.985Euo, oi5RbMg6.985Lio, ois (P0 ₄ ) 6 as a blue component in combination with Lu3AlsOi2: Ce and (Ba.Sr ^ SisNsiEu (see Example 6) .

Claims

1. Compound of the general formula (I):

[M ^l ₄ M ^ll 7 (A0 ₄ ) 6] n (I), characterized in that the compound is doped with RE and Li or with RE,

where for the symbols and indices used:

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

0 <n <4.

2. Compound according to claim 1, represented by the general formula (II):

[M ^la ₃ M ^lb M ^M 7 (A04) 6] n (II), where:

M ^la is selected from the group consisting of Na, K, Rb and Cs; M ^lb is selected from the group consisting of Na, K, Rb, Cs and mixtures of two or more thereof.

3. Compound according to claim 1, represented by the general formula (la) or (Ib):

[M ^l 4-xM ^ll 7-x (A04) 6: REx, Lix] n (la)

[M'4-2XM " ₇ (A04) 6: REX]" (Lb), where: 0 <x <1.

4. A compound according to claim 2, represented by the general formula (Ila) or (Mb):

[M ^la 3-yM ^lb i-zM ^ll 7-x (A0 ₄ ) 6: REx Lix] n (lla)

[M ^la 3-2yM ^lb i-2zM ^ll 7 (A0 ₄ ) 6: REx] n (Mb), where:

0 <y <1; 0 <z <1; y + z = x; and

0 <x <1.

5. A compound as claimed in one or more of claims 1 to 4, where:

M "is Mg, which can be partially replaced by Ca, Sr and / or Ba; and

A is P, which can be partially replaced by As, Sb, V, Nb and / or Ta.

6. A compound according to one or more of claims 1 to 5, where the following applies to x: 0 <x <1, preferably 0.0 <x <0.5, more preferably 0.001 <x <0.1 and particularly preferably 0.001 <x <0.04.

7. Connection according to one or more of claims 1 to 6, characterized in that the connection is coated on the surface with another connection.

8. A process for the preparation of a compound according to one or more of claims 1 to 7, comprising the steps of: a) preparing a mixture comprising M ¹ , M ", A0 ₄ , RE and Li; and b) calcining the mixture prepared.

9. Use a connection according to one or more of the

Claims 1 to 7 as a phosphor or conversion phosphor for partial or complete conversion of UV light and / or violet light into light with a longer wavelength.

10. Radiation-converting mixture comprising a compound according to one or more of claims 1 to 7.

1 1. A radiation converting mixture according to claim 10, further

comprising one or more further luminescent materials selected from conversion phosphors and semiconductor nanoparticles.

12. Light source containing at least one primary light source and

at least one compound according to one or more of claims 1 to 7 or a radiation-converting mixture according to claim 10 or 1 1.

13. The light source of claim 12, wherein the primary light source is a

comprises luminescent indium aluminum gallium nitride.

14. The light source according to claim 13, wherein the luminescent indium aluminum gallium nitride is a compound of the formula IniGa _j Al _k N, where 0 <i, 0 <j, 0 <k and i + j + k = 1.

15. Lighting unit containing at least one light source

one or more of claims 12 to 14.