EP3137576A1

EP3137576A1 - Phosphors

Info

Publication number: EP3137576A1
Application number: EP15720907.3A
Authority: EP
Inventors: Ralf Petry; Holger Winkler; Thomas Juestel; Florian BAUR; Kira Heerdt
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2014-04-28
Filing date: 2015-04-01
Publication date: 2017-03-08
Also published as: JP2017521503A; TW201602310A; US20170051201A1; WO2015165567A1; DE102014006003A1; CN106459752A; KR20160147936A

Abstract

The invention relates to compounds of the formula (I): (A_2-2nB_n)_x(Ge_1-mM_m)_yO_(x+2y): Mn⁴⁺, in which the parameters A, B, M, m, n, x, and y have one of the meanings according to claim 1. The invention further relates to a method for producing the compounds of the formula (I), to the use of said compounds as conversion phosphors, and to an emission-converting material containing at least one compound of the formula (I). The invention further relates to a light-emitting device which contains at least one compound of the formula (I) according to the invention.

Description

phosphors

The present invention relates to compounds of the formula I,

(A2-2nBn) x (Gei-mMm) yO (x ₊ 2y): Mn ⁴⁺ I in which the parameters A, B, M, m, n, x, and y have one of the meanings according to claim 1. Furthermore, the invention relates to a process for the preparation of the compounds of formula I, the use of these compounds as conversion phosphors, and a

Emission converting material containing at least one

A compound of the formula I. Another subject of the present invention relates to a light-emitting device which comprises at least one compound of the formula I according to the invention.

Inorganic fluorescent powders excitable in the blue and / or UV spectral range are of great importance as conversion phosphors for phosphor converted LEDs, in short pc LEDs. Meanwhile, many conversion phosphor systems are known, such as alkaline earth orthosilicates, thiogallates, garnets, nitrides and oxynitrides each doped with Ce ³⁺ or Eu ²⁺ . For the realization of warm white light sources with color temperatures <4000 K based on blue or UV-A emitting (ln, Ga) N LEDs, red-emitting phosphors with emission wavelengths above 600 nm are required in addition to the yellow- or green-emitting garnets or ortho-silicates which emit sufficiently strong at the corresponding wavelength of the primary radiation (370-480 nm). Most of the currently commercially available cold white LEDs contain a colorimetrically optimized Ce ³⁺ -doped garnet phosphor according to the general formula (Y, Gd, Lu, Tb) 3 (Al, Ga, Sc) 50i 2: Ce.

Warm white LEDs also contain a second red-emitting phosphor which is either an Eu ²⁺ -doped ortho-silicate phosphor or an Eu ²⁺ -doped (oxy) nitride phosphor. The main disadvantage of using an LED light source with a broadband emitting Ce ³⁺ -doped garnet phosphor and a broadband emitting Eu ²⁺ -doped ortho-silicate phosphor or (oxy) nitride in the red spectral range are in addition to any chemical instability, especially against moisture, the pronounced reabsorption and the emission of radiation in the NIR range, so that the lumen output of warm white LEDs is significantly lower (about a factor of 2 or more) than that of a corresponding cold white LED.

Reabsorbtion in this context means that fluorescent light generated in the phosphor to a certain extent can not leave the phosphor, because this is totally reflected at the interface to the optically thinner environment and migrated in the phosphor via waveguiding processes and eventually lost.

As near infrared (NIR) the range of electromagnetic becomes

Spectrum called, which connects in the direction of a larger wavelength to the visible light. This range of infrared light usually extends from 701 nm to 3 μιτι.

The previously used phosphors (Ca, Sr) S: Eu, (Ca, Sr) AISiN3.Eu and (Ca, Sr, Ba) 2Si5N8: Eu are all based on the activator Eu ²⁺ , which is characterized by a broad absorption spectrum as well through a wide

Emission band is distinguished. The major drawback of these Eu ²⁺ activated materials is their relatively high sensitivity to photodegradation since divalent Eu ²⁺ tends to photoionize, especially in relatively low band gap host materials.

Another disadvantage is the rather high half-width of the Eu ²⁺

Emission band, which manifests itself in a moderate lumen equivalent (<200 Im / W), when the color point is in the deep red spectral range. This observation is especially true for the phosphors (Ca, Sr) S: Eu ²⁺ and

(Ca, Sr) AISiN3: Eu ²⁺ too.

Due to the problems described above, a red narrow band emitter for LEDs is currently being sought whose Emissipnsmaximum between 615 and 700 nm. Preference is given to a narrow band emitter whose emission band is between 630 and 680 nm and has a maximum half-value width of 50 nm. In this connection, in US Pat. No. 7,846,350, for example, the compound SrGe40g: Mn ^{4+ is} proposed.

An advantage of Mn ⁴⁺ -activated phosphors lies in the underlying optical transition [Ar] 3d ³ - [Ar] 3d ³ , that is a

Intra-configuration transition is. The Tanabe-Sugano diagram for Mn ⁺ shows that this transition lies on the one hand in the red spectral range and on the other hand is optically narrow and thus allows red phosphors with high color saturation and at the same time acceptable lumen equivalent. The Tanabe-Sugano diagram is a diagram in which, for all electronic states of a system, the energy difference E is typically the lowest state against

Crystal field splitting energy (Δ) are applied, both sizes normalized to the Racah parameter. In multi-electron systems occurring electrostatic repulsion can be in their entirety by three linear combinations Slater'scher

Electron interaction integrals Fk (coulombin integral,

Exchange integral, repulsion integral). The

Abbreviations A, B and C for these linear combinations are called Racah parameters.

The number of curves intersected by a vertical line of a given Δ gives the number of possible transitions and thus the number of expected absorption characteristics. The Tanabe-Sugano diagram is thus a correlation diagram, which allows the interpretation of absorption spectra of chemical compounds.

It is thus one of the objects of the present invention to provide suitable red emitting phosphors which should be activated with Mn ⁴⁺ for the reasons mentioned above, should be effectively excitable in the blue or near UV wavelength range and for corresponding ones Solid state light sources, such as (ln, Ga) N LEDs or OLEDs, as

Radiation converter should be suitable.

Surprisingly, the inventors found that

Compounds of the formula I,

(A2-2nBn) x (Gei-mMm) yO (x ₊ 2y): Mn ⁴⁺ I in which

A at least one element selected from the group of Li,

Na, K and Rb,

B (Ci-uDu),

C at least one element selected from the group of

Ca, Ba and Sr,

D at least one element selected from the group of Ca or Ba,

M at least one element selected from the group of Ti,

Zr, Hf, Si and Sn,

0 n ^ 1, preferably 0 or 1,

0 <u ^ 1, preferably 0.2 <u <1, more preferably 0.5 <u <1, ^{α5 £ Χ £ 2} '

0 <m <1, and

1 <y <9 corresponds to the above requirements. The compounds according to the invention are usually excitable in the near UV or blue spectral range, preferably at about 280 to 470 nm, particularly preferably at about 300 to 400 nm, and usually have line emission in the red spectral range of about 600 to 700 nm, preferably about 620 to 680 nm, with a half-width (FWHM) of the main emission peak of a maximum of 50 nm, preferably a maximum of 40 nm. The full width at half maximum (half width or FWHM) is a parameter that is commonly used to describe the width of a peak or function. It is defined in a two-dimensional coordinate system (x, y) by the distance (Δχ) between two points on the curve with the same y-value, at which the function reaches half its maximum value (y _ma x / 2).

In the context of this application, blue light is defined as light whose emission maximum lies between 400 and 459 nm, cyan light whose emission maximum is between 460 and 505 nm, green light whose emission maximum lies between 506 and 545 nm as yellow light such, whose

Emission maximum between 546 and 565 nm, such as orange light whose emission maximum is between 566 and 600 nm and as red light, whose emission maximum is between 601 and 700 nm.

The compound of the invention is preferably a red-emitting conversion phosphor.

Furthermore, the compounds according to the invention are distinguished by a high photoluminescence quantum yield of more than> 80%, preferably more than 90%, particularly preferably more than 95%.

The photoluminescence quantum yield (also called quantum efficiency or quantum efficiency) describes the ratio between the number of emitted and absorbed photons of a compound.

In addition, the compounds according to the invention have high values for the lumen equivalent (> 250 Im / W) and are furthermore distinguished by very good thermal and chemical stability. Furthermore, the compounds according to the invention are excellently suited for use in white LEDs, color-on-demand (COD) applications, TV backlighting LEDs and electric lamps such as, for example

Fluorescent lamps, as well as to improve the efficiency of solar cells. In a preferred embodiment, the compounds of the formula I are selected from the compounds of the following sub-formulas:

((Sri-uBa _u )) x (Gei-mMm) yO (x ₊ 2y): Mn ⁴⁺ Γ

((Sri-uCa _u )) x (Gei-mMm) _y O (x ₊ 2y): Mn ⁺ I "where the parameters M, n, u, x, m and y are one of the formula I

have given meanings.

An advantage of the compounds P of the invention over the known compound SrGe ₄ 09: Mn ⁴⁺ (see US Pat. No. 7,846,350) is the admixture of, for example, a barium source in the

according to the invention, wherein it is for the formation of a

Eutectic comes, and thus to a melting point depression which simplifies the synthesis and ensures a better crystallinity.

In a further preferred embodiment of the present invention

Invention is equal to zero.

Preference is given to compounds of the formula I selected from the group of the compounds of the formula Ia,

(A2) x (Gei-m-z Mm Mn _z ) y 0 (x + 2y) where

A, M, x, y and m have one of the meanings given under formula I and

0 <z <0.01 ^* y.

Preference is given to compounds of the formula I and their sub-formulas in which 0 ^ m <0.8, more preferably in which 0 -S m <0.5, furthermore in which 0 <m <0.3. Further preferred are compounds of the formula I, as well as their

Sub-formulas in which x is 0.5, 0.75, 1, 1.25, 1.5, 1.75 or 2, more preferably x is 1 or 2, in particular x is 1. Further preferred are compounds of formula I, as well as their

Sub-formulas in which y corresponds to an integer in the range 1 <y <9, ie 1, 2, 3, 4, 5, 6, 7, 8 or 9, in particular in which y is equal to 4.

In a further preferred embodiment, the compounds of the formula I are selected from the group of the compounds of the formulas Ia-1 to Ia-4,

A2Gei-z n _z M309 la-1

Α2Θβ2-ζΜη _ζ Μ2θ9 la-2

A2Ge3-zMn _z MO9 la-3

wherein

M, z and A have one of the meanings given under formula Ia.

Depending on the composition, especially with regard to the variation of the parameters A, M and m, the emission in the red

Spectral range in the range of 600 nm to 700 nm can be selectively varied.

In another embodiment, germanium is in the

Partially replaced by silicon according to the invention, wherein M is Si and m> 0. Particularly preferred

Compounds of the formula I, as well as their sub-formulas, in which M is Si, m> 0 and at the same time y is 4, x is 1, and 0.001 <z <0.004.

In an equally preferred embodiment, compounds of the formula I are selected from the compounds in which m is 0, wherein at the same time y is 4, x is 1 and 0.001 <z is 0.004. In one embodiment, A represents exactly one element selected from the group of Li, Na, K and Rb. But they are equal as well

Compounds of the formula I, as well as their sub-formulas, are preferred in which A corresponds to a mixture of these elements, ie at least two elements selected from the group of Li, Na, K and Rb.

The compounds according to the invention are particularly preferably selected from the following sub-formulas:

A2Ge4-zMn _z O9,

further preferred,

K2 Ge4-zMnzOg,

Na2 Ge4-zMnzOg,

further preferred,

Rb2SiGe3-zMn _z Og,

A2Si2Ge2-zMn _z O9,

further preferred,

Rb2 Si2Ge2-zMnzOg, as well

A2 Si3Gei-zMn _z 09, further preferred,

L12 Si3Gei-zMn _z O9,

K2 Si3Gei-zMn _z O9, wherein

z has one of the meanings given under formula Ia, and particularly preferably z = 0.01 ^* y.

Similarly, the above-mentioned compounds are preferred in which A represents at least two elements selected from the group of Li, Na, K and Rb, such as Nai.8Üo.2Geo.999Mno.oo-tSi309.

However, the compounds according to the invention can be present as phase mixtures but also in phase. In a preferred embodiment, the compounds according to the invention are pure in phase.

An X-ray diffractogram can be used to examine the phase purity of a crystalline powder, i. H. whether the sample consists only of one crystalline (pure phase) or more (multi-phase) compounds. In phase-pure powders all reflections can be observed and assigned to the compound.

The particle size of the compounds according to the invention is usually between 50 μm and 1 μm, preferably between 30 μm and 3 μm, particularly preferably between 20 μm and 5 μm.

Another object of the present invention is a process for preparing a compound of the invention, characterized

characterized in that in a step a) suitable starting materials selected from the group of corresponding oxides, carbonates, oxalates or corresponding reactive forms are mixed and the mixture is thermally treated in a step b). The process according to the invention is preferably characterized by the following process steps:

(a) Preparation of a mixture containing at least one

Manganese source; at least one lithium, sodium, potassium, rubidium, calcium, barium and / or strontium source;

at least one source of manganese, at least one

Germanium source, and optionally a titanium, zirconium, hafnium, silicon and / or tin source

(b) calcining the mixture under oxidizing conditions.

The manganese source used in step (a) may be any conceivable manganese compound with which a compound according to the invention can be prepared. The manganese source used is preferably carbonates, oxalates and / or oxides, in particular manganese oxalate dihydrate

As germanium source in step (a), any conceivable

Germanium compound are used with which a compound of the invention can be prepared. Preferably, as

Used germanium source oxides, especially germanium oxide

(GeO ₂ ).

As the lithium, sodium, potassium, rubidium, calcium, barium and / or strontium source in step (a), any conceivable lithium, sodium, potassium, rubidium, calcium, barium and / or strontium compound can be used with which a compound of the invention can be prepared. Corresponding carbonates or oxides, in particular lithium carbonate (U 2 CO 3), sodium carbonate (Na 2 CO 3), potassium carbonate (K 2 CO 3), rubidium carbonate (in the process according to the invention as lithium, sodium, potassium, rubidium, calcium, barium and / or strontium compound) are preferably used. Rb2CO3), as well as calcium carbonate (CaCO3), barium carbonate (BaCO3) and / or strontium carbonate (SrCO3). As the titanium, zirconium, hafnium, silicon and / or tin source in step (a), any conceivable titanium, zirconium, hafnium, silicon and / or tin compound can be used with which an inventive

Connection can be made. Preferably, in

inventive method as titanium, zirconium, hafnium, silicon and / or tin source corresponding nitrides and / or oxides used.

The compounds are preferably used in a ratio to one another such that the atomic number corresponds to the desired ratio in the product of the abovementioned formulas. It will

in particular a stoichiometric ratio is used.

The starting compounds in step (a) are preferably used in powder form and processed together, for example by a mortar, to form a homogeneous mixture. Preferably, to this

Purpose of suspending the starting compounds in an inert organic solvent known to those skilled in the art,

for example, acetone. In this case, the mixture is dried before calcination.

The calcination in step (b) is carried out under oxidizing conditions. By oxidizing conditions is meant any conceivable oxidizing atmosphere, e.g. Air or other

oxygen-containing atmospheres.

As a flux, optionally at least one substance from the group of ammonium halides, preferably ammonium chloride, Aikalifluoride, such as sodium, potassium or lithium fluoride, alkaline earth fluorides such as calcium, strontium or barium fluoride, carbonates, preferably

Ammonium hydrogen carbonate, or various alcoholates and / or oxalates are used.

The calcination is preferably carried out at a temperature in the range of 700 ° C to 1200 ° C, more preferably 800 ° C to 1000 ° C and

in particular 850 ° C to 950 ° C carried out. The period is the calcination preferably 2 to 14 hours, more preferably 4 to 12 hours and especially 6 to 10 hours.

The calcination is preferably carried out so that the resulting mixtures are introduced, for example, in a vessel made of boron nitride in a high-temperature furnace. The high-temperature furnace, for example, a tube furnace containing a support plate made of molybdenum foil. After calcining, the compounds obtained are optionally homogenized, wherein a corresponding grinding process can be carried out wet in a suitable solvent, for example in isopropanol, or dry. The calcined product may optionally be re-selected under the above conditions and with the optional addition of a suitable flux selected from the group of ammonium halides, preferably ammonium chloride, alkali metal fluorides such as sodium, potassium or lithium fluoride, alkaline earth fluorides such as calcium, strontium or

Barium fluoride, carbonates, preferably ammonium bicarbonate, or various alkoxides and / or oxalates, are calcined.

In a further embodiment, the inventive

Compounds are beschichet. Suitable for this purpose are all the coating methods known to the person skilled in the art according to the prior art and used for phosphors. Suitable materials for the coating are, in particular, metal oxides and metal nitrides, in particular earth metal oxides, such as Al 2 O 3, and

Nitrides such as AIN and S1O2. The coating can be carried out, for example, by fluidized bed processes.

Further suitable coating methods are known from JP 04-304290, WO 91/10715, WO 99/27033, US 2007/0298250, WO

2009/065480 and WO 2010/075908. It is also possible, alternatively to the above-mentioned inorganic coating and / or additionally to apply an organic coating. The coating can become have an advantageous effect on the stability of the compounds and the dispersibility.

Another object of the present invention is the use of the compound of the invention as a phosphor, in particular as a conversion phosphor.

For the purposes of the present application, the term "conversion luminescent material" is understood to mean a material which absorbs radiation in a specific wavelength range of the electromagnetic spectrum, preferably in the blue or UV spectral range, and in another wavelength range of the electromagnetic spectrum, preferably in red or orange In this context, the term "radiation-induced emission efficiency" is to be understood, ie the conversion phosphor absorbs radiation in a certain wavelength range and emits radiation in another wavelength range with a certain efficiency. Shifting the emission wavelength "means that a

Conversion luminescent material emits light at a different wavelength, that is shifted to a smaller or larger wavelength compared to another or similar conversion luminescent material. So the emission maximum is shifted.

Another object of the present invention is an emission-converting material comprising one or more

Compound of the invention according to one of the formulas listed above. The emission-converting material may consist of one of the compounds according to the invention and in this case would be equivalent to the term "conversion luminescent substance" as defined above.

It is also possible that the emission-converting material according to the invention contains, in addition to the compound according to the invention, further conversion phosphors. In this case, that contains

inventive emission-converting material is a mixture of at least two conversion phosphors, one of which is a compound according to the invention. It is particularly preferred that which are at least two conversion phosphors, phosphors that emit light of different wavelengths, which are complementary to each other. Since the compound according to the invention is a red emitting phosphor, it is preferably used in combination with a green or yellow emitting phosphor or else with a cyan or blue emitting phosphor. Alternatively, the inventive red-emitting conversion phosphor in combination with (a) blue and green-emitting

Conversion luminescent material (s) are used. Alternatively, the inventive red-emitting conversion phosphor in

Combination with (a) green-emitting conversion phosphor (s) are used. It may therefore be preferred that the conversion phosphor according to the invention is used in combination with one or more further conversion phosphors in the emission-converting material according to the invention, which then together

preferably emit white light.

As a further conversion luminescent substance that can be used together with the compound according to the invention, it is generally possible to use any possible conversion luminescent substance. Suitable examples are: Ba ₂ SiO ₄ : Eu ²⁺ , BaSi ₂ O ₅ : Pb ²⁺ , BaxSri _-x F ₂ : Eu ²⁺ ,

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

BaY ₂ F ₈ : Er ³⁺ , Yb ⁺ , Be ₂ Si0 ₄ : Mn ⁺ , Bi ₄ Ge ₃ Oi ₂ , CaAl ₂ 0 ₄ : Ce ³⁺ , CaLa ₄ O ₇ : Ce ³⁺ , CaAl ₂ O ₄ : Eu ²⁺ , CaAl ₂ O: Mn ²⁺ , CaAl ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , CaAl ₂ 04: Tb ³⁺ ,

Ca ₃ Al ₂ Si ₃ Oi ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ 0i ₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ 0 ₂ : Eu ²⁺ , Ca ₂ B ₅ 0 ₉ Br: Eu ²⁺ , Ca ₂ B ₅ 09Cl: Eu ²⁺ , Ca ₂ B ₅ 09Cl: Pb ²⁺ , CaB ₂ O ₄ : Mn ²⁺ , Ca ₂ B ₂ 0 ₅ : Mn ²⁺ ,

CaB ₂ O: Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ²⁺ , Ca ₅ B ₂ SiOio: Eu ³⁺ ,

Cao.5Bao.5Ali ₂ Oi9.Ce ³⁺ , Mn ²⁺ , Ca ₂ Ba ₃ (PO ₄ ) ₃ Cl: Eu ²⁺ , CaBr ₂ : Eu ²⁺ in SiO ₂ , CaCl ₂ : Eu ²⁺ in SiO ₂ , CaCl ₂ : Eu ²⁺ , Mn ²⁺ in SiO ₂ , CaF ₂ : Ce ³⁺ , CaF ₂ : Ce ³⁺ , Mn ²⁺ , CaF ₂ : Ce ³⁺ , Tb ³⁺ , CaF ₂ : Eu ²⁺ , CaF ₂ : Mn ²⁺ , CaF ₂ : U, CaGa ₂ O ₄ : Mn ⁺ ,

CaGa4O _7: Mn ^2+, CaGa ₂ S _4: Ce ^3+, CaGa ₂ S _4: Eu ^2+, CaGa ₂ S 4: Mn ^2+,

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

Si0 ₂ , CaLaB0 ₄ : Eu ³⁺ , CaLaB ₃ 0 ₇ : Ce ³⁺ , Mn ²⁺ , Ca ₂ La ₂ B0 ₆ .5: Pb ²⁺ , Ca ₂ MgSi ₂ 0 ₇ , Ca ₂ MgSi ₂ O ₇ : Ce ^3+, CaMgSi ₂ O _6: Eu ^2+, Ca ₃ MgSi ₂ 0 _8: Eu ^2+, Ca ₂ MgSi ₂ O _7: Eu ^2+, CaMgSi ₂ 0 _6: Eu ^2+, Mn ^2+, Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , CaMoO _4> CaMoO: 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+, beta-Ca ₃ (PO4) _2: Ce ^3+, Ca ₅ (P04) ₃ Cl: Eu ^2+, Ca ₅ (P0 ₄₎ ₃ Cl: Mn ^2+, Ca ₅ (P04) ₃ CI: Sb ^3+, Ca ₅ (P0 ₄₎ ₃ Cl: Sn ^2+,

beta-Ca ₃ (P04) _2: Eu ^2+, Mn ^2+, Ca ₅ (P04) ₃ F: Mn ^2+, Cas (P0 ₄₎ ₃ F: Sb ^3+,

Ca _s (P0 ₄₎ ₃ F: Sn ^2+, _a-Ca3 (P04) _2: Eu ^2+, beta-Ca ₃ (P0 ₄₎ 2: Eu ^2+, Ca ₂ P ₂ O 7: Eu ^+, Ca ₂ P ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , CaP ₂ O ₆ : Mn ²⁺ , a-Ca ₃ (PO ₄ ) ₂ : Pb ²⁺ , a-Ca ₃ (PO ₄ ) 2: Sn ²⁺ , β-Ca ₃ (PO ₄ ) 2: Sn ²⁺ , β-Ca ₂ P ₂ O 7: Sn, Mn, α-Ca ₃ (PO ₄ ) 2: Tr, CaS: Bi ³⁺ ,

CaS: Bi ³⁺ , Na, CaS: Ce ³⁺ , CaS: Eu ²⁺ , CaS: Cu ⁺ , Na ⁺ , CaS: La ³⁺ , CaS: Mn ²⁺ , CaSO 4: Bi, CaSO 4: Ce ³⁺ , CaSO ₄ : Ce ³⁺ , Mn ²⁺ , CaSO ₄ : Eu ²⁺ , CaSO 4: Eu ²⁺ , Mn ²⁺ , CaSO ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , CI, CaS : Pb ⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , CI, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ , CaS: Sn ^{2 +} , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , CI, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ²⁺ , CI, CaSiO ₃ : Ce ³⁺ ,

Ca ₃ SiO 4 Cl ₂ : Eu ⁺ , 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 ⁺ , CaTio 9Alo.iO ₃ : Bi ³⁺ , CaTiO ₃ : Eu ³⁺ , CaTiO ₃ : Pr ³⁺ , Ca ₅ (VO 4) ₃ CI, CaW0 ₄ , CaW0 ₄ : Pb ²⁺ , CaW0 ₄ : W, Ca ₃ WO ₆ : U, CaYAlO 4: Eu ³⁺ , CaYBO ₄ : Bi ³⁺ , CaYBO ₄ : Eu ³⁺ , CaYBo.8O ₃ .7 Eu ³⁺ , CaY ₂ Zr06: Eu ³⁺ ,

(Ca, Zn, Mg) ₃ (P04) 2: Sn, CeF _3, (Ce, Mg) BaAlnOi _8: Ce, (Ce, Mg) SrAlnOi8.Ce, CeMgAlnOi9: Ce: Tb, Cd ₂ B6Oii: Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: ln, CdS: ln,

CdS: In, Te, CdS: Te, CdW0 ₄ , CsF, CsI, CsI: Na ⁺ , CsII, (ErCl ₃ ) o.25 (BaCl 2) o.75, GaN.Zn, Gd ₃ Ga ₅ 0i ₂ : Cr ^3+, Gd ₃ Ga ₅ O _2: Cr, Ce, GdNbO _4: Bi ^3+, Gd ₂ 0 ₂ S: Eu ^3+, Gd ₂ O ₂ Pr ^3+, Gd ₂ O ₂ S: Pr, Ce, F, Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAInOi ₇ : TI ⁺ , KGaiOi ₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ Oio: Eu, K gF ₃ : Eu ²⁺ , KMgF ₃ : n ²⁺ , K ₂ SiF 6: Mn ⁴⁺ , LaAl ₃ B ₄ Oi ₂ : Eu ³⁺ , LaAIB ₂ O ₆ : Eu ³⁺ , LaAIO ₃ : Eu ³⁺ , LaAlO ₃ : Sm ³⁺ , LaAsO 4 .Eu ³⁺ , LaBr ₃ : Ce ³⁺ , LaBO ₃ : Eu ³⁺ , (La, Ce, Tb) PO 4: Ce: Tb, LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³⁺ , LaOBr: Tm ³⁺ , LaOC!: Bi ³⁺ , LaOCl: Eu ³⁺ , LaOF: Eu ³⁺ , La ₂ O ₃ : Eu ³⁺ , La ₂ 0 ₃ : Pr ³⁺ , La ₂ 0 ₂ S: Tb ^3+, LaPO _4: Ce ^3+, LaP0 _4: Eu ^3+, LASIO ₃ Cl: Ce ^3+,

LaSiO ₃ Cl: Ce ³⁺ , Tb ³⁺ , LaVO ₄ : Eu ³⁺ , La ₂ W ₃ Oi ₂ : Eu ³⁺ , LiAIF ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAlO ₂ : Fe ³⁺ , LiAIO ₂ : Mn ²⁺ , LiAl ₅ O ₈ : Mn ²⁺ , Li ₂ CaP ₂ O ₇ : Ce ³⁺ , Mn ²⁺ ,

LiCeBa4Si4Oi ₄ : Mn ²⁺ , LiCeSrBa ₃ Si40i4: Mn ²⁺ , LilnO ₂ : Eu ³⁺ , LilnO ₂ : Sm ³⁺ , LiLaO ₂ : Eu ³⁺ , LuAlO ₃ : Ce ³⁺ , (Lu, Gd) ₂ SiO ₅ : Ce ³⁺ , Lu ₂ SiO ₅ : Ce ³⁺ , Lu ₂ Si ₂ O ₇ : Ce ³⁺ , LuTaO 4: Nb ⁵⁺ , Lu-x Y x Al ₃ : Ce ³⁺ , MgAl ₂ O ₄ : Mn ²⁺ , MgSrAhoOi ₇ : Ce,

_MgB2 O4: Mn ^+, MgBa ₂ (PO ₄₎ _2: Sn ^2+, MgBa ₂ (PO4) _2: U, MgBaP ₂ 0 _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 20 ₇ : Mn ²⁺ , Mg ₂ Ca (SO ₄ ) ₃ : Eu ²⁺ ,

Mg ₂ Ca (SO 4) ₃ : Eu ²⁺ , Mn ² ₍ MgCeAl _n Oi ₉ : Tb ³⁺ , Mg 4 (F) GeO ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) 06.Mn ²⁺ ²⁺ MgF2.Mn, MgGa20 _4: Mn ^2+, Mg8Ge20nF2.Mn ^+, MgS: Eu ^2+, MgSi03: Mn ^2+, Mg2SiO _4: Mn ²⁺ Mg3SiO3F _4: Ti ^4+, MgSO4: Eu ^2+, MgS04: Pb ^2+, MgSrBa ₂ Si ₂ 07: Eu ^2+, MgSrP ₂ 07: Eu ^+, MGSR ₅ (P0 ₄₎ 4: Sn ²⁺ , MgSr ₃ Si ₂ O ₈ : Eu ²⁺ , Mn ²⁺ , Mg ₂ Sr (SO ₄ ) ₃ : Eu ⁺ , Mg ₂ TiO 4: Mn ⁴⁺ , MgWO ₄ ,

gYB04: Eu ^3+, Na3Ce (P04) 2: Tb ^3+, NaI: TI, Nai.23Ko.4 Euo.i2TiSi40n _2: Eu ^3+, Nai.23Ko.42Euo.i2TiSi5Oi3 xH20: Eu ^3+, Nai.29Ko .46Ero.o8TiSi4Oii: Eu ³⁺ ,

Na ₂ Mg ₃ Al ₂ Si ₂ Oio: Tb, Na (Mg ₂ -x Mn _x ) LiSi 4 OioF 2: Mn, NaYF 4: Er ³⁺ , Yb ³⁺ ,

NaYO ₂ : Eu ³⁺ , P46 (70%) + P47 (30%), SrAli ₂ 0i9: Ce ³⁺ , Mn ²⁺ , SrAl ₂ 0 ₄ : Eu ²⁺ , SrAl ₄ O ₇ : Eu ³⁺ , SrAli20i _9: Eu ^2+, SrAI ₂ S4: Eu ^2+, SR2b O9CI _5: Eu ^2+,

SrB ₄ O ₇ : Eu ²⁺ (F, CI, Br), SrB40 ₇ : Pb ²⁺ , SrB ₄ 07: Pb ²⁺ , Mn ²⁺ , SrB ₈ Oi 3: Sm ²⁺ , SrxBa _y ClzAl ₂ O 4-z / ₂ : Mn ^2+, Ce ^3+, SrBaSi04: Eu ^2+, Sr (CI, Br, l) 2: Eu ²⁺ in S1O2, SrCl _2: Eu ²⁺ in SiO ₂₎ Sr ₅ Cl (PO 4) _3: Eu, SrwFxB ₄ O6.5: Eu ²⁺ , SrwF _x ByOz: Eu ²⁺ , Sm ²⁺ , SrF ₂ : Eu ²⁺ , SrGai 20i ₉ : Mn ²⁺ , SrGa 2S ₄ : Ce ³⁺ , SrGa ₂ S4: Eu ²⁺ , SrGa ₂ S4: Pb ²⁺ , Srln ₂ O ₄ : Pr ³⁺ , Al ³⁺ , (Sr, Mg) 3 (PO ₄ ) 2: Sn, Sr MgSi ₂ Oe: Eu ²⁺ , Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Sr ₃ MgSi ₂ 08: Eu ²⁺ , SrMo 0 ₄ : U, SrO-3B203: Eu ²⁺ , Cl, β-SrO-3B ₂ 0 ₃ : Pb ²⁺ , β-SrO-3B ₂ 0 ₃ : Pb ^{2 +} , Mn ²⁺ , a-SrO-3B ₂ O 3: Sm ²⁺ , Sr ₆ P 5 B 0 ₂ o: Eu,

Sr ₅ (PO ₄ ) 3 Cl: Eu ²⁺ , Sr ₅ (PO ₄ ) 3 Cl: Eu ²⁺ , Pr ³⁺ , Sr ₅ (PO 4) 3 Cl: Mn ²⁺ ,

Sr ₅ (PO ₄₎ 3 Cl: Sb ^3+, Sr ₂ P20 _7: Eu ^2+, Sr-ß ₃ (P04) 2: Eu ^+, Sr ₅ (P04) ₃ F: Mn ^+,

Sr ₅ (PO 4) ₃ F: Sb ^3+, Sr 5 (P0 ₄₎ 3F: Sb ^3+, Mn ^2+, Sr ₅ (PO ₄₎ 3F: Sn ^2+, Sr ₂ P20 _7: Sn ^2+, .beta. Sr ₃ (PO 4) _2: Sn ^2+, Sr-ß ₃ (P04) 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⁺ , SrSO 4: Eu ²⁺ , Mn ⁺ ,

Sr ₅ Si40ioCl6: Eu ²⁺ , Sr ₂ SiO 4: Eu ²⁺ , SrTiO ₃ : Pr ³⁺ , SrTiO ₃ : Pr ³⁺ , Al ³⁺ , Sr ₃ W0 ₆ : U, SrY ₂ O ₃ : Eu ³⁺ , Th0 ₂ : Eu ³⁺ , Th0 ₂ : Pr ³⁺ , Th0 ₂ : Tb ³⁺ , YAI ₃ B40i 2: Bi ³⁺ ,

YAbB4Oi2: Ce ³⁺ , YAl3B ₄ 0i 2: Ce ³⁺ , Mn, YAl ₃ B40i 2: Ce ³⁺ , Tb ³⁺ , YAl 3B ₄ Oi 2: Eu ³⁺ , YAl ₃ B ₄ 0i 2: Eu ³⁺ , Cr ³⁺ , YAI ₃ B40i2: Th ^4+, Ce ^3+, Mn ^2+, YAI0 _3: Ce ^3+, Oi2 Y3AI _5: Ce ^3+, Y ₃ Al ₅ O _2: Cr ^3+, YAI0 _3: Eu ^3+, Y3AI ₅ Oi ₂ : Eu ^3r , Y ₄ Al ₂ O 9: Eu ³⁺ , Y ₃ Al 5 O ₂ : Mn ⁴⁺ , YAl ₃ : Sm ³⁺ , YAl ₃ : Tb ³⁺ , Y ₃ AI ₅ O ₂ : Tb ³⁺ , YAsO 4: Eu ³⁺ , YBO 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) BO _3: Eu, (Y, Gd) B0 _3: Tb, (Y, Gd) 20 _3: Eu ^3+, Yi.34Gdo.6o0 ₃ (Eu, Pr),

Y ₂ 0 ₃ : Bi ³⁺ , YOBr: Eu ³⁺ , Υ ₂ Ο ₃ : ΟΘ, Y ₂ 0 ₃ : Er ³⁺ , Y ₂ O ₃ : Eu ³⁺ (YOE), Y ₂ 0 ₃ : Ce ^{3 +,} Tb3 ^+, YOCI: Ce ^3+, YOCI: Eu ^3+, YOF: Eu ^3+, YOF: Tb ^3+, Y ₂ 03: Ho ^3+, Y ₂ 02S: Eu ^3+, Y ₂ 0 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 ⁺ , Y PO ₄ : V ⁵⁺ , Y (P, V) O ₄ : Eu, Y ₂ SiO 4: Ce ³⁺ , YTaO ₄ , YTaO ₄ : Nb ⁵⁺ , YVO 4: Dy ³⁺ , YVO ₄ : Eu ³⁺ , ηηΑΙ ₂ θ ₄ : ηη ²⁺ , ZnB ₂ O ₄ : Mn ²⁺ ,

ZnBa ₂ S3: Mn ²⁺ , (Zn, Be) 2SiO 4: Mn ²⁺ , ZncuCdo.eSiAg, Zno.6Cdo.4S: Ag,

(Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF ₂ .Mn ²⁺ , ZnGa ₂ 0 ₄ , ZnGa ₂ 04.Mn ²⁺ , ZnGa ₂ S4: Mn ^2+, Zn2Ge04: n ^2+, (Zn, Mg) F _2: Mn ^2+, ZnMg ₂ (P04) 2: Mn ^2+, (Zn, Mg) 3 (P04) 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 ⁺ , CI, ZnS: Ag, Cu, Cl, ZnS: Ag, Ni, ZnS: Au, In, ZnS-CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25) , ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , Cl, ZnS-CdS: Cu, Br, ZnS-CdS: Cu, l, ZnS-Cl ^" , ZnS: Eu ²⁺ , ZnS: Cu, ZnS: Cu ⁺ , Al ³⁺ , ZnS: Cu ⁺ , C | -,

ZnS: Cu, Sn, ZnS: Eu ²⁺ , ZnS: Mn ²⁺ , ZnS: Mn, Cu, ZnS: Mn ²⁺ , Te ²⁺ , ZnS: P, ZnS: P ³ -, C | -, ZnS: Pb ⁺ , ZnS: Pb ⁺ , CI-, ZnS: Pb, Cu, Zn ₃ (PO 4) ₂ : lvln ²⁺ ,

Zn ₂ SiO 4: Mn ^2+, Zri2SiO4: n ^2+, As ^5+, Zn ₂ Si04: 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.

Inventive compounds, used in small amounts, already give good LED qualities. The LED quality is described by common parameters such as the Color Rendering Index, Correlated Color Temperature, Lumen Equivalents or Absolute Lumens, or the color point in CIE x and CIE y coordinates.

Color rendering index, or CRI, is a unitary photometric quantity known to those skilled in the art, which is the color fidelity of an artificial light source to that of sunlight

Filament light sources compare (the latter two have a CRI of 100).

The CCT or Correlated Color Temperature is a photometric quantity with the unit Kelvin familiar to the person skilled in the art. The higher the numerical value, the colder the viewer sees the white light of an artificial radiation source. The CCT follows the concept of

Black light emitter whose color temperature is the so-called Planckian curve in the CIE diagram.

The lumen equivalent is a photometric quantity familiar to the person skilled in the art with the unit Im W, which describes how large the photometric luminous flux in lumens of a light source at a given wavelength

radiometric radiant power with the unit watts, is. The higher the lumen equivalent, the more efficient a light source is. The lumen is a photometric one familiar to those skilled in the art

photometric quantity 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 represent the coordinates in the familiar CIE standard color diagram (in this case normal observer 1931), which describes the color of a light source.

All the variables listed above are calculated from emission spectra of the light source according to methods familiar to the person skilled in the art.

In this connection, a further subject of the present invention is the use of the compounds according to the invention or the emission-converting material according to the invention described above in a light source.

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

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

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

The light source according to the invention is preferably a pc-LED. A pc-LED typically includes a primary light source and an emission converting material. For this purpose, the emission-converting material according to the invention can either be dispersed in a resin (for example epoxy or silicone resin) or with suitable proportions directly on the primary light source or remotely located therefrom, depending on the application (the latter arrangement also includes "Remote Phosphor Technology " with a).

The primary light source may be a semiconductor chip, a luminescent one

Light source such as ZnO, a so-called TCO (Transparent Conducting Oxide), a ZnSe or SiC based arrangement, an organic light-emitting layer based arrangement (OLED) or a plasma or discharge source, most preferably a semiconductor chip. If the primary light source is a semiconductor chip, it is preferably a luminescent indium-aluminum-gallium nitride (InAIGaN), as known in the art. The person skilled in possible forms of such primary light sources are known. Also suitable are lasers as a light source.

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

Moldings around emission-converting moldings.

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

Coupling between the emission-converting material and the primary light source (in particular semiconductor chips), preferably by a light-conducting arrangement. This makes it possible for the primary light source to be installed at a central location and to be connected to it by means of light-conducting devices, such as, for example, photoconductive fibers

emission-converting material is optically coupled. In this way, the lighting requirements adapted lights consisting of one or more different

Conversion phosphors, which may be arranged to a fluorescent screen, and a light guide, which is coupled to the primary light source implement. This makes it possible to place a strong primary light source in a convenient location for the electrical installation and to install without additional electrical wiring, only by laying fiber optics at random locations, lights of emission-converting materials that are coupled to the light guide.

All variants of the invention described here can be combined with each other, as long as the respective embodiments are not mutually exclusive. In particular, it is based on the teaching of this document in the context of routine optimization

obvious process, just different here described

To combine variants in order to arrive at a specific particularly preferred embodiment.

The parameter ranges given in this application, unless otherwise stated, include all rational and integer

Numerical values including the specified limits of the

Parameter range and their error limits. The upper and lower limits specified for respective ranges and properties, in turn, combine to provide additional preferred ones

Areas.

Throughout the specification and claims of this application, the words "comprise" and "contain" and variations of these words, such as "comprising" and "comprising" are not construed as including, but are not limited to, other components The word "including" also includes, but is not limited to, the term "consisting of."

The following examples are intended to illustrate the present invention and, in particular, show the result of such exemplary ones

Combinations of the described variants of the invention. However, they are by no means to be considered limiting, but rather are intended to encourage generalization.

Any compounds or components that can be used in the formulations are either known and commercially available or can be synthesized by known methods.

The indicated temperatures are always in ° C. It goes without saying that both in the description and in the examples, the added amounts of the components in the

Always add up to a total of 100%.

Percentages are always to be seen in the given context.

Examples

a) Nai.8Üo.2Geo.999Mno.ooiSi309

0.9539 g (9000 mmol) of a2CO3, 0.0739 g (1000 mmol) of U2CO3, 1.0453 g (9990 mmol) of GeO2, 1.08025 g (30.000 mmol) of S1O2 and 0.0018 g (0.010 mmol) of ηθ2θ4 · 2Η2θ are carried in an agate mortar Thoroughly rub acetone. The powder is dried, transferred to a covered porcelain crucible and calcined at 600 ° C for 1 hour. The calcined powder is thoroughly rubbed with acetone together with 2.5% by weight of NaF and 2.5% by weight of LiF in an agate mortar. The dried powder is transferred to a covered porcelain crucible and heated at 800 ° C for 4 hours.

1.3820 g (10,000 mmol) K 2 CO 3, 4.1814 g (39.960 mmol) Ge0 ₂ and 0.0072 g (0.040 mmol) θηθ 2θ4 · 2Η2θ are thoroughly triturated with acetone in an agate mortar. The powder is dried, transferred to a covered porcelain crucible and calcined at 600 ° C for 1 hour. The calcined powder is thoroughly triturated with acetone together with 5% by weight of KF in an agate mortar. The dried powder is transferred to a covered porcelain crucible and heated at 800 ° C for 4 hours. c) Rb2Ge3.996 no.oo409

2.3095 g (10,000 mmol) of Rb ₂ C03, 4.1814 g (39.960 mmol) of GeO 2 and 0.0072 g (0.040 mmol) of θηθ 2θ 4 .2θ 2θ are thoroughly triturated with acetone in an agate mortar. The powder is dried, transferred to a covered porcelain crucible and calcined at 600 ° C for 1 hour. The calcined powder is thoroughly triturated with acetone together with 5% by weight RbF in an agate mortar. The dried powder is transferred to a covered porcelain crucible and heated at 780 ° C for 4 hours. d) K2SiGe2.997Mno.oo309

1.5202 g (11,000 mmol) of K 2 CO 3, 0.6008 g of SiO 2 (10.00 mmol), 3.1360 g (29.970 mmol) of GeO 2, and 0.0054 g (0.030 mmol) of MnC ₂ O ₄ ^» 2H ₂ O. thoroughly rubbed with acetone in an agate mortar. The powder is dried, transferred to a covered porcelain crucible and calcined at 850 ° C for 4 hours. Production of a pc-LED using a phosphor according to the invention of the composition

4 g of the phosphor having the composition K2Ge3.996 no 004O9 are weighed, admixed with 1 g of an optically transparent silicone and then homogeneously mixed in a planetary centrifugal mixer so that the phosphor concentration in the total mass is 80 wt.%. The resulting silicone-phosphor mixture is applied by means of an automatic dispenser on the chip of a blue emitting semiconductor LED and under

Heat supply hardened. The blue LEDs used in this example for LED characterization have one

Emission wavelength of 442 nm and are with 350 mA

Amperage operated. The light-technical characterization of the LED is carried out with a spectrometer from the company Instrument Systems - spectrometer CAS 140 and an associated integrating sphere ISP 250. The LED is characterized by determining the wavelength-dependent spectral power density. The spectrum thus obtained of the light emitted by the LED is used to calculate the color point coordinates CIE x and y.

Description of the figures

Fig.1. XRD diagrams with the ICCD reference for Cu K-alpha radiation

Fig.2. Reflection spectrum of K2Ge3.996Mno.oo4Og versus BaSO ₄ as

White standard.

Figure 3. Reflection spectrum of K2SiGe2.997Mno.oo309 against BaSO4 as

White standard.

Figure 4. Reflection spectrum of Rb2Ge3.996Mno.oo40g versus BaSO4 as

White standard.

Figure 5. Excitation spectrum of foGes.ggeMno.ocwOg (A _em = 664 nm) Fig.6. Excitation spectrum of K2 SiGe2.997Mno.oo30g (Aem = 664 nm) Fig.7. Excitation spectrum of Rb2Ge3.996Mno.oo40g (Aem = 654 nm) Fig.8. Emission spectrum of K2Ge3.996Mno.oo4O9 (Aex = 320 nm) Fig.9. Emission spectrum of K2SiGe2.997Mno.oo309 (Aex = 31 0 nm) Fig.10. Emission spectrum of Rb2Ge3.g96 no.oo409 (Aex = 327 nm) Fig.1 1. Detail from the CIE 1931 color chart with the

Color points of K2Ge3.9g6Mno.oo4O9, K2SiGe2. 97Mno.oo3O9 and

Figure 12. LED spectrum of the pc-LED described in Example e).

Claims

Patent claims

1 . Compound of formula I, (A2-2nBn)x(Gei-mMm)yO(x ₊ 2y): Mn ⁴⁺ I wherein

A at least one element selected from the group of Li, Na, K and Rb,

B (Ci-uDu),

C at least one element selected from the group of Ca, Ba and Sr,

D at least one element selected from the group of Ca and Ba, at least one element selected from the group of Ti,

Zr, Hf, Si and Sn,

0 < n < 1,

0 < u < 1 , 0.5 < x < 2, 0 -£ m < 1 , and

1 < y < 9, corresponds

2. Compound according to claim 1, characterized in that n

is equal to 0.

3. Compound according to one of claims 1 or 2, characterized in that the compound of formula I is selected from the group of compounds according to formula la,

(A ₂ )x(Gei-m-zMmMn _z )y 0( _X+ 2y) la where

A, M, x, y and m one of those specified under claim 1

have meanings,

and 0 < z < 0.01 ^* y.

4. Compound according to one or more of claims 1 to 3, characterized in that x is equal to 1.

5. Compound according to one or more of claims 1 to 4, characterized in that y is equal to 4.

6. Compound according to one or more of claims 1 to 5, characterized in that the compound is selected from the group of compounds of the formulas la-1 to la-4,

A ₂ Gei- _z MnzM3Og la-1

A ₂ Ge2- _z Mn _z M209 la-2

A ₂ Ge3-zMn _z M09 la-3

wherein

M, z and A have one of the meanings specified in claim 1.

7. Compound according to one or more of claims 1 to 6, characterized in that M is Si.

8. Compound according to one or more of claims 1 to 7, characterized in that 0.001 <z <0.004.

Compound according to one or more of claims 1 to 8, characterized in that A corresponds to at least two elements selected from the group of Li, Na, K and Rb.

Process for producing a compound according to one or more of claims 1 to 9, characterized in that in a step a) suitable starting materials or corresponding reactive forms are mixed and the mixture is thermally treated in a step b).

The method according to claim 10, wherein the starting materials in step a) are selected from the group of corresponding oxides, carbonates and oxalates.

Use of a compound according to one or more of claims 1 to 9 for the partial or complete conversion of the blue or near-UV emission into visible light of a higher wavelength.

Emission-converting material containing at least one compound according to one or more of claims 1 to 9 and one or more further conversion phosphors.

Light source with at least one primary light source, characterized in that the light source contains at least one compound according to one or more of claims 1 to 9 or an emission-converting material according to claim 13.

A light source according to claim 14, wherein the primary light source corresponds to a luminescent indium aluminum gallium nitride and/or indium gallium nitride.

16. Lighting unit, in particular for the backlighting of display devices, characterized in that it

contains at least one light source according to claim 14 or 15.

17. Display device, in particular liquid crystal display device (LC display), with a backlight, thereby

characterized in that it contains at least one lighting unit according to claim 16.