EP2491094A1

EP2491094A1 - Sm-activated aluminate and borate phosphors

Info

Publication number: EP2491094A1
Application number: EP10759816A
Authority: EP
Inventors: Holger Winkler; Thomas Juestel; Simas Sakirzanovas
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2009-10-23
Filing date: 2010-09-15
Publication date: 2012-08-29
Also published as: US20120224353A1; KR20120099693A; US9102873B2; CN102597160A; WO2011047757A1; KR101752939B1; DE102009050542A1; JP2013508481A; TWI527879B; TW201122084A; JP5808746B2

Abstract

The invention relates to phosphors of formula (I) (Ln_1-a-bGd_aSm_b)_w Mg_xSr_y(AI_1-cB_c) zO_{(3/2w+x+y+3/2z)} (I), wherein Ln = Y, La and/or Lu; a, c = 0.0 to 1.0; 0 < b < 0.2 and a + b < 1.0; w = 1.0 to 3.0; x, y = 1.0 to 2.0 and z > 0.0 to 12.0. The invention also relates to a method for producing said phosphors and to the use thereof as conversion phosphors for converting the near-UV emission of an LED.

Description

Sm-activated aluminate and borate phosphors

The invention relates to phosphors which consist of Sm-activated aluminates and borates, their preparation and their use as LED conversion phosphors for near UV LEDs.

For more than ten years, fluorescent converted LEDs have been developed for general and special lighting (displays, signals, flash lights), with the vast majority of manufacturers relying on the use of blue-emitting InGaN LEDs. This is due to the fact that when using blue LEDs (420-480 nm) the Stokes loss is minimized by the conversion of the blue semiconductor radiation into a white spectrum and thus the highest lumen efficiencies can be achieved. The theoretical limit for a white light source with a color rendition above 80 is about 350 Im / W, and recently the company Nichia has developed a white LED with almost 250 Im / W. This LED is based on a YAG: Ce-converted InGaN semiconductor that emits in the blue spectral range.

A disadvantage of dichromatic white LEDs, which is a yellow

The use of emitting phosphor as a converter is their cold

Light color (T _c = 5000 - 8000 K). The supply of warm-white LEDs succeeds by the addition of a second phosphor in the red

Spectral range (590 - 650 nm) emitted. The previously used

Phosphors, namely CaS: Eu, CaAISiN ₃ : Eu and CaaSisNeiEu are all based on the activator Eu ²⁺ , which is characterized both by a broad

Absorption spectrum as well as characterized by a broad emission band.

The use of red-emitting line emitters as converters in warm-white LEDs is of great interest, as it causes the

Lumenequivalent and thus the lumen yield by about 20 - 30% increase. However, the appropriate activator ions, such as Eu ³⁺ and Pr only over weak absorption bands in the blue spectral range. Thus, the conclusion was that efficient red emitting line emitters based on these ions can be provided, but they are only suitable for near UV emitting LEDs as converters.

From EP 916748 a lanthanum magnesium aluminate compound of the composition LaMgAlnOig (LMA) is known, which, however, is not activated with Sm and thus unsuitable for use in near UV LEDs. From Ceramics Intern. 2006, 32 (6), 665-671, Tang et al., The

photoluminescence of SrA O ^ Sm phosphorus "is the phosphor

SrAI ₂ 0 ₄ : Sm known.

JP-2000144129 describes a codoped SrAl ₄ O ₇ : Eu, Sm.

From EP1121000 as well as EP 1111966 Sm-doped borates of the composition SrB ₄ O ₇ : Sm are described.

From Singh et al. Physica Status Solidi A: Appl. And Mater. Sci, 2006, 203 (8), 2058-2064 "Eu and Sm emission in SrAl ₁₂ 0 ₁₉ phosphorus prepared via combustion synthesis" is a Sm-activated phosphor known.

The object of the present invention is therefore to produce novel Sm-activated phosphors which are the above-mentioned. Meet requirements for high light efficiency and use especially in near UV LEDs.

Surprisingly, it was found that Sm-activated aluminates of the compositions LaMgAlii0 _19: Sm, GdSr ₂ AI0 _5: Sm and LaSr2AI0 _5: Sm and Sm-activated borates of the compositions LnMgB ₅ Oio: Sm, Ln = Y, La, Gd or Lu is to meet those requirements. The present invention thus provides phosphors of the formula I.

in which

Ln = Y, La and / or Lu

a, c = 0.0 to 1.0

0 <b <0.2 and a + b <1.0

w = 1.0 to 3.0

x, y = 1.0 to 2.0 and

z> 0.0 to 12.0

The following phosphors are preferred:

LaMgAl Oi ₉ : Sm (II)

LaSr ₂ AIO ₅ : Sm (III)

GdSr ₂ AIO ₅ : Sm (IV)

LaMgB ₅ Oi ₀ : Sm (V)

GdMgB ₅ Oi ₀ : Sm (VI)

The term scheme of Sm ³⁺ (G. Blasse, BC Grabmeier, Luminescent Materials, Springer-Verlag 1994) shows that the dominant transitions ( ⁴ G _5/2 - ⁶ Hj) are between 14000 and 18000 cm ^-1 , which results in a multiple However, Sm ³⁺ can only be ^excited in the near UV because there are no suitable transitions in the blue spectral region, so that Sm ³⁺ activates

Phosphors are only suitable for near UV LEDs.

Sm ²⁺ is isoelectronic with Eu ³⁺ , making the term scheme almost identical to that of Eu ³⁺ , ie only the splitting of the energy levels is reduced due to the lower ionic charge and thus lower Stark splitting. Thus, Sm ²⁺ -doped luminescent materials show through ⁵ D ₀ - ^7. Fj transitions emission lines caused between 10,000 and 15000 cm ^"1 and are therefore suitable as NIR emitters.The low position of the highly absorbent 4f5d band also allows excitation in the visible spectral range, including by blue emitting LEDs.

The atomic concentrations of the Sm-doping are between 0.1 and 10% bbeezzooggeenn aauuff ddeen crystallographic place on the Sm or

is installed.

The particle size of the phosphors according to the invention is between 50 nm and 30 μιη, preferably between 1 μητι and 20 μητι, more preferably between 2 pm and 12 μηη.

A further subject of the present invention is a process for the preparation of a compound of the 6-3-6-4 alkaline earth silicooxynitride type with europium doping with the following process steps:

a) Preparation of an Sm-doped compound by mixing

at least 4 starting materials selected from lanthanum, magnesium, aluminum, samarium, gadolinium, boron, yttrium, luthetium-containing materials,

b) optionally adding at least one further organic and / or inorganic substance,

c) Thermal aftertreatment of the phosphor.

The starting materials for preparing the compound or phosphor consist of the corresponding oxides, carbonates or nitrates. Suitable starting materials are also other inorganic and / or organic substances such as cyanamides, dicyanamides, cyanides, oxalates, malonates, fumarates, citrates, ascorbates and acetylacetonates.

In the production by solid-state diffusion method, for example, organic solvents such as acetone (see step b) can be added. They serve as auxiliaries of better miscibility of the educts. Should wet-chemical processes (see below more exactly Depending on the method used, organic (eg precipitants such as urea) or inorganic substances (eg acids) are used.

The abovementioned thermal aftertreatment (see process step c) runs for several hours. It can also be under reducing

Conditions, e.g. B with forming gas (e.g., 90/10), pure hydrogen, and / or in an ammonia atmosphere with or without the above-noted atmospheres. The temperatures during the annealing process amount to several hours (preferably 8 h) between 950 ° C and 1800 ° C, preferably from 1000 ° C to 1550 ° C.

In addition to producing the phosphors via solid-state diffusion processes, wet-chemical production processes are also suitable. Preference is given to the combustion process using urea (see Example 1). In this method, e.g. Dissolved nitrate solutions of the corresponding Leuchtstoffedukte in water, then boiled under reflux and mixed with urea, whereby the phosphor precursor is formed slowly.

In addition, the following other wet-chemical methods are also conceivable:

Co-precipitation with an NH ₄ HC0 ₃ solution {see, for example, Jander, Blasius Lehrbuch der analyt. u. prep. anorg. Chem. 2002)

• Pecchini method with a solution of citric acid and

Ethylene glycol (see, e.g., Annual Review of Matehals Research Vol. 36: 2006, 281-331)

Spray drying of aqueous or organic salt solutions (educts)

■ spray pyrolysis (also called spray pyrolysis) aqueous or

organic salt solutions (educts)

■ Evaporation of nitrate solutions and thermal reaction of the residue With the aid of the abovementioned process, it is possible to produce any desired external forms of the compounds or phosphors according to the invention, such as spherical particles, platelets and structured materials and

Ceramics. According to the invention, these forms are combined under the term "shaped body." The shaped body is preferably a "phosphor body".

Another object of the present invention is thus a

Shaped body containing the compounds according to the invention, wherein it has a rough surface, the nanoparticles of S1O2, ΤΊΟ2, Al2O3, ZnO, ZrO ₂ and / or Y2O3 or mixed oxides thereof and / or particles with the inventive compound with or without samarium as activator.

In another preferred embodiment, the molded article has a patterned (e.g., pyramidal) surface on the side opposite an LED chip (see WO2008 / 058619, Merck, which is fully incorporated by reference into the context of the present application). Thus, as much light as possible can be coupled out of the phosphor.

The structured surface on the shaped article is formed by subsequent coating with a suitable material, which is already structured, or in a subsequent step by (photo) lithographic

Process, etching or by writing process with energy or matter beams or exposure to mechanical forces produced.

In a further preferred embodiment, the

Moldings of the invention on the, an LED chip

opposite side a rough surface, the nanoparticles of S1O2, ΤΊΟ2, Al2O3 ZnO _2, ZrO2 and / or Y ₂ O ₃ or combinations of these materials and / or particles with the phosphor composition according to formula I with or without dopants samarium carries. It has a rough surface has a roughness of up to several 100 nm. The coated surface has the advantage that total reflection can be reduced or prevented and the light can be better decoupled from the phosphor according to the invention (see WO2008 / 058619 (Merck)) which is full-circumference is incorporated by reference in the context of the present application)

It is further preferred if the shaped bodies according to the invention have a refractive index-adapted layer on the surface facing away from the chip, which facilitates the decoupling of the primary radiation and / or the radiation emitted by the phosphor body.

In a further preferred embodiment, the molded bodies have a closed surface coating consisting of SiO _2, TiO _2, Al ₂ O 3, _ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides and / or from the compounds according to formula I without the activator samarium consists. These

Surface coating has the advantage that a suitable grading of the refractive indices of the coating materials a

Adjustment of the refractive index with the environment can be achieved. In this case, the scattering of light on the surface of the

Luminescent decreases and a greater proportion of the light can penetrate into the phosphor and absorbed and converted there.

It also allows the refractive index-matched

Surface coating that gives more light from the phosphor

is decoupled, because the total internal reflection is reduced.

In addition, a closed layer is advantageous if the

Phosphor must be encapsulated. This may be necessary to counter sensitivity of the phosphor or parts thereof to diffusing water or other materials in the immediate environment. Another reason for the encapsulation with a

closed shell is a thermal decoupling of the actual Fluorescent from the heat that arises in the chip. This heat leads to a reduction in the fluorescent light output of the phosphor and may also affect the color of the fluorescent light. Finally, it is possible by such a coating to increase the efficiency of the phosphor by preventing lattice vibrations arising in the phosphor from propagating to the environment.

It is furthermore preferred if the shaped body is a porous one

Has surface coating consisting of S1O2, TiO ₂ , AfcOa. ZnO, Zr0 ₂ and / or Y2O3 or mixed oxides thereof and / or from the compounds according to formulas I with or without dopant samarium. These porous coatings offer the possibility of further reducing the refractive index of a single layer. The preparation of such porous coatings can be accomplished by three conventional methods as described in WO 03/027015, which is incorporated by reference in its entirety in the context of the present application: the etching of glass (eg soda-lime glasses (see US Pat 4019884)), the application of a porous layer and the combination of porous layer and an etching process.

In a further preferred embodiment, the shaped body has a surface which carries functional groups which allow a chemical or physical connection to the environment, preferably consisting of epoxy or silicone resin. These functional groups may e.g. oxo group-attached esters or other derivatives which can form linkages with components based on epoxides and / or silicones. Such surfaces have the advantage that a homogeneous mixing of the phosphors is made possible in the binder. Furthermore, this can be the

Theological properties of the system phosphor / binder and also the pot life can be adjusted to a certain extent. This simplifies the processing of the mixtures. From a physical In this context, connection to the environment is referred to as electrostatic interactions between the systems

Charge fluctuations or partial charges act.

Since the invention applied to the LED chip

Phosphor layer preferably consists of a mixture of silicone and homogeneous phosphor particles, and the silicone one

Surface tension, this phosphor layer is on

at the microscopic level, or the thickness of the layer is not consistently constant.

The production of platelet-shaped phosphors as further

preferred embodiment is done by conventional methods from the corresponding metal and / or rare earth salts. The

Manufacturing method is described in detail in EP 763573 and WO2008 / 058620, which are fully incorporated by reference into the context of the present application. These platelet-shaped phosphors can be produced by atomically etching a natural or synthetically produced highly stable support or a substrate of, for example, mica, S1O2, Al2O3, ZrO2, glass or TiO2 platelets, which has a very high aspect ratio has smooth surface and an adjustable thickness, can be coated by precipitation reaction in aqueous dispersion or suspension with a phosphor layer. In addition to mica, ZrO2, S1O2, Al2O3, glass or TiO ₂ or mixtures thereof, the platelets may also consist of the phosphor material itself, or be composed of a material. If the plate itself only as a carrier for the

Phosphor coating is used, it must be made of a material that is transparent to the primary radiation of the LED, or the

Absorbs primary radiation and transfers this energy to the phosphor layer. The platelet-shaped phosphors are in a resin (eg Silicone or epoxy resin), and this dispersion is applied to the LED chip.

The platelet-shaped phosphors can be produced on a large scale in thicknesses of 50 nm up to about 20 μm, preferably between 150 nm and 5 μm. The diameter is from 50 nm to 20 pm. It usually has an aspect ratio (ratio of diameter to particle thickness) of 1: 1 to 400: 1, and in particular 3: 1 to 100: 1. The platelet expansion (length x width) depends on the arrangement. Platelets are also suitable as scattering centers within the conversion layer, especially if they have particularly small dimensions.

The surface of the platelet-shaped phosphor according to the invention facing the LED chip can be provided with a coating which acts in an anti-reflection manner with respect to the primary radiation emitted by the LED chip. This leads to a reduction in the backscattering of the primary radiation, as a result of which it can be better coupled into the phosphor body according to the invention.

Suitable for this purpose are, for example, refractive index-adapted coatings which must have a following thickness d: d = [wavelength of the

Primary radiation of the LED chip / (4 ^* refractive index of the phosphor ceramic)], s. for example, Gerthsen, Physik, Springer Verlag, 18th edition, 1995. This coating can also consist of photonic crystals. This also includes a structuring of the surface of the platelet-shaped phosphor in order to achieve certain functionalities.

The production of the shaped bodies according to the invention in the form of ceramic bodies takes place analogously to the process described in WO 2008/017353 (Merck), which is incorporated by reference in its entirety into the context of the present application. In this case, the phosphor is prepared by mixing the corresponding reactants and dopants, then isostatically pressed and in the form of a homogeneous thin and non-porous platelets directly on the surface applied to the chip or at a distance from the chip (remote phosphor concept). The particular arrangement depends, inter alia, on the architecture of the LED device, the skilled person being capable of the advantageous

Select arrangement. Thus, no location-dependent variation of the excitation and emission of the phosphor takes place, as a result of which the LED equipped with it emits a homogeneous and color-constant light cone and has a high light output. The ceramic phosphor bodies may e.g. be produced industrially as platelets in thicknesses of a few 100 nm to about 500 pm. The

Platelet expansion (length x width) depends on the arrangement. When directly applied to the chip, the size of the chip according to the chip size (from about 100 pm ^* 100 pm up to several mm ² ) with a certain excess of about 10% - 30% of the chip surface with a suitable chip arrangement (eg Flip Chip arrangement) or to choose accordingly. If the phosphor plate is placed over a finished LED, the emerging cone of light is completely covered by the plate.

The side surfaces of the ceramic phosphor body can be mirrored with a light or noble metal, preferably aluminum or silver. The mirroring causes no light to escape laterally from the

Phosphor body exits. Lateral exiting light can reduce the luminous flux to be coupled out of the LED. The mirroring of the

ceramic phosphor body takes place in a process step after the isostatic pressing to bars or plates, which may be done before the mirroring a tailor of the rods or plates in the required size. The side surfaces are for this purpose e.g. wetted with a solution of silver nitrate and glucose and then exposed at elevated temperature to an ammonia atmosphere. Here, e.g. a silver coating on the side surfaces.

Alternatively, electroless metallization processes are also suitable, see, for example, Hollemann-Wiberg, Lehrbuch der Inorganischen Chemie, Walter de Gruyter Verlag or Ullmann's Encyclopedia of Chemical Technology.

The ceramic phosphor body can, if necessary, be fixed with a water glass solution on the substrate of an LED chip.

In a further embodiment, the ceramic has

Phosphor body has a patterned (e.g., pyramidal) surface on the side opposite an LED chip. Thus, as much light as possible can be coupled out of the phosphor body. The structured

Surface on the phosphor body is thereby produced, in which during isostatic pressing, the pressing tool has a structured pressing plate and thereby embosses a structure in the surface. Structured surfaces are desired when thin phosphor bodies or platelets are to be produced. The

Press conditions are known to those skilled in the art (see J. Kriegsmann, Technische keramische Materialien, Chapter 4, Deutscher Wirtschaftsdienst, 1998). It is important that as pressing temperatures 2/3 up to 5/6 of the

Melting temperature of the substance to be pressed are used.

Another object of the present invention is a process for the preparation of a shaped body, preferably phosphor body, with the following process steps:

a) preparing a samarium-doped compound by mixing at least 4 starting materials selected from lanthanum, magnesium, aluminum samarium, gadolinium, boron, yttrium, luthetium-containing materials, b) optionally adding at least one further organic and / or inorganic substance,

c) thermal aftertreatment of the phosphors and formation of a shaped body with a rough surface,

d) coating the surface with nanoparticles of S1O2

T1O2, Al2O3, ZnO, Z> 2 and / or Y2O3 or mixed oxides thereof or with nanoparticles of the compounds according to the invention. The excitability of the phosphors according to the invention also extend over a wide range, ranging from about 350 nm to 530 nm, preferably 430 nm to about 500 nm. Thus, these phosphors are not only suitable for excitation by UV or blue emitting primary light sources such as LEDs or conventional discharge lamps (eg based on Hg), but also for light sources such as those which exploit the blue ln ³⁺ line at 451 nm.

Another object of the present invention is a

Lighting unit with at least one primary light source whose emission maximum or maximum ranges in the range 250 nm to 530 nm, preferably 350 nm to about 500 nm. Particularly preferred is a range between 440 and 480 nm, wherein the primary radiation is partially or completely converted by the compounds or phosphors according to the invention into longer-wave radiation. Preferably, this lighting unit emits white or emits light with a certain color point (color-on-demand principle).

In a preferred embodiment of the invention

Lighting unit is the light source to 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.

The person skilled in possible forms of such light sources are known. These may be light emitting LED chips

act different construction.

In a further preferred embodiment of the illumination unit according to the invention, the light source is a

luminescent on ZnO, TCO (transparent conducting oxide), ZnSe or SiC based arrangement or even on an organic light emitting layer based arrangement (OLED).

In a further preferred embodiment of the illumination unit according to the invention, the light source is a source which

Electroluminescence and / or photoluminescence shows. Furthermore, the light source may also be a plasma or discharge source. The phosphors of the present invention may be dispersed either in a resin (e.g., epoxy or silicone resin) or in suitable ones

Sizes may be placed directly on the primary light source or remotely located therefrom, depending on the application (the latter arrangement also includes "remote phosphor technology") .The advantages of "remote phosphor technology" are known to those skilled in the art, e.g. in the following publication: Japanese Journ. of Appl. Phys. Vol. 44, no. 21 (2005). L649-L651.

In a further embodiment, it is preferred if the optical coupling of the illumination unit between the phosphor and the primary light source is realized by a light-conducting arrangement.

This makes it possible that the primary light source is installed at a central location and this by means of light-conducting devices, such as

for example, light-conducting fibers, to the phosphor optically

is coupled. In this way, the lighting requirements adapted lights can only consist of one or

different phosphors, which may be arranged to form a luminescent screen, and a light guide, which is connected to the primary light source

is connected, realize. In this way, it is possible to place a strong primary light source at a convenient location for electrical installation and without further electrical wiring, but only by Laying light guides anywhere you want to install lights from phosphors that are coupled to the light guides.

Another object of the present invention is the use of the shaped body according to the invention as a phosphor body.

Another object of the present invention is the use of the compounds of the invention for the partial or complete conversion of the near UV emission of a light-emitting diode.

Further preferred is the use of the invention

Compounds for the conversion of near-UV emission into visible white radiation. Furthermore, the use of the

Compounds according to the invention for the conversion of the primary radiation in a particular color point according to the "color on demand" - concept preferred.

The compounds of the formula I according to the invention can be used individually or as a mixture with the following phosphors familiar to the person skilled in the art:

The following examples are intended to illustrate the present invention. However, they are by no means to be considered limiting. 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 temperatures given in the examples always apply in ° C. It goes without saying that both in the description and in the examples, the added amounts of the components in the compositions always add up to a total of 100%. Given percentages are always to be seen in the given context. However, they usually refer to the mass of the specified partial or total quantity. Examples

Example 1: Preparation of ₉ after the

Combustion Method

To prepare 10.0 g of the abovementioned phosphor, 2.1106 g of La ₂ O ₃ and 0.0228 g of S1TI ₂ O _{3 are} dissolved in 200 ml of dilute nitric acid (prepared from 10 ml of HNO ₃ conc. To 200 ml of water), and the excess acid is then removed by evaporation. The resulting residues are distilled in 500 ml. Dissolved water and then successively 3.3556 g of Mg (N0 ₃ ) 2 6H ₂ O and 54.0036 g of Al (NO ₃ ) ₃ 9H ₂ O added to 80 to 90 ° C heated. Thereafter, 10.30 g of tris (hydroxymethyl) amino methane (in the molar ratio 1: 0.5 to the cations) is added. It ensteht a brown powder mixture.

The mixture is first heated at 1000 C for 2 hours and then again at about 1500 ° C for 8 hours.

Example 2: Preparation of according to the solid-state diffusion method

For the preparation of 4 g of the above phosphor are 1.5314g La ₂ 0 _3l 0.0166g Sm ₂ 0 _3, 2.803g 0.4841g SRC0 ₃ and nano-AI ground in a mortar ₂ 0 ₃ and 50 ml of acetone. The mixture is then heated for 4 hours at approx. 1400 ° C.

Example 3: Preparation of according to the solid-state diffusion method

For the preparation of 4 g of the above phosphor 1.6335 g Gd ₂ 0 ₃ ,

Grind 0.0159 g Sm ₂ O ₃ , 2.6878 g SrC0 ₃ and 0.4641 g nano-Al ₂ O ₃ in a mortar and add 50 ml acetone. It is then heated for 4 hours at about 1400X. Example 4: Preparation of Lao.99Smo. ₀ iMgB ₅ 0 ₁₀ according to the solid-state diffusion method

For the preparation of 4 g of the above phosphor are 1.7095g La20 ₃ ,

0.0185 g Sm ₂ 0 ₃ , 0.8937 g MgCO ₃ and 3.4409 H ₃ B0 ₃ (5% by weight)

In a mortar and mixed with 50 ml of acetone. It is then heated for 8 hours at 1020 ° C.

Example 5: Preparation of Gdo. ₉₉ Sm ₀ .oiMgB ₅ Oio according to the solid-state diffusion method

For the preparation of 4 g of the abovementioned phosphor 1.8146 g Gd ₂ 0 ₃ , 0.0176 g Sm ₂ O ₃ , 0.8527 g MgC0 ₃ and 3.2829 g H ₃ BO ₃ (5 wt.%

Description of the pictures

In the following the invention will be explained in more detail with reference to several embodiments. Show it:

Fig. 1: shows the excitation spectrum of

Fig. 2: shows the emission spectrum of

Fig. 3: shows the excitation spectrum of

Claims

claims

1. Phosphor of the formula I. in which

Ln = Y, La and / or Lu

a, c = 0.0 to 1.0

0 <b <0.2 and a + b <1.0

w = 1.0 to 3.0

x, y = 1.0 to 2.0 and

z> 0.0 to 12.0

is.

2. phosphor according to claim 1, characterized in that they are the following phosphors:

LaMgAln0 ₉ : Sm (II)

LaSr ₂ AI0 ₅ : Sm (III)

GdSr ₂ AI0 ₅ : Sm (IV)

LaMgB ₅ Oi ₀ : Sm (V)

GdMgB ₅ O ₁₀ : Sm (VI)

3. A process for the preparation of a phosphor according to claim 1 and / or 2 with the following process steps:

a) preparing a samarium-doped compound by mixing at least 4 starting materials selected from lanthanum, magnesium, aluminum, samarium, gadolinium, boron, yttrium or luthetium-containing materials, b) optionally adding at least one further organic or inorganic substance,

c) Thermal aftertreatment of the phosphor.

4. Shaped body containing a phosphor according to claim 1 and / or 2,

characterized in that it has a rough surface which

Nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O ₃ ZnO, ZrO ₂ and / or Y ₂ O ₃ or

Mixed oxides thereof and / or particles with the phosphor according to claim 1 and / or 2.

5. Shaped body containing a phosphor according to claim 1 and / or 2, characterized in that it has a closed

Has surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3i ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or from the phosphor according to one or more of claims 1 and / or 2 without the activator samarium consists.

6. Shaped body containing a compound according to one or more of claims 1 to 5, characterized in that it is a porous

Has surface coating consisting of SiO ₂ , TiO ₂ , Al ₂ O _3, ZnO, ZrO ₂ and / or Y ₂ O ₃ or mixed oxides thereof and / or from the phosphor according to claim 1 and / or 2 with or without activator samarium.

7. molded body containing a phosphor according to claim 1 and / or 2, characterized in that the surface carries functional groups, which allows a chemical or physical connection to the environment, preferably consisting of epoxy or silicone resin.

8. A process for producing a shaped article according to one or more of claims 4 to 7 with the following process steps: a) preparing a samarium-doped compound by mixing at least 4 starting materials selected from lanthanum, magnesium, aluminum, samarium, gadolinium, boron, yttrium or Luthetium-containing materials, b) optionally adding at least one further organic and / or inorganic substance,

c) thermal aftertreatment of the phosphor and formation of a shaped body with a rough surface,

d) coating the surface with nanoparticles of SiO ₂ , TiO ₂ , Al ₂ O 3 _, ZnO _, ZrO 2 and / or Y 2 O 3 or mixed oxides thereof or with nanoparticles of the phosphor according to claim 1 and / or 2 with or without samarium.

9. lighting unit with at least one primary light source whose

Emission maximum in the range 250 nm to 530 nm, preferably between 350 nm and 500 nm, wherein this radiation is partially or completely converted into longer wavelength radiation by a compound and / or phosphor body according to one or more of claims 1 to 7.

10. Lighting unit according to claim 9, characterized in that it is at the light source to a luminescent

Indiumaluminum gallium nitride, in particular of the formula InjGajAl _k N, where 0 <i, 0 <j, 0 <k, and i + j + k = 1.

11. Lighting unit according to claim 9, characterized in that it is at the light source to a luminescent to ZnO, TCO (Transparent

conducting oxide), ZnSe or SiC based compound.

12. Illumination unit according to claim 9, characterized in that the light source is a material based on an organic light-emitting layer.

13. Lighting unit according to claim 9, characterized in that it is the light source is a plasma or discharge lamp.

14. Lighting unit according to one or more of claims 9 to 13, characterized in that the phosphor directly on the

Primary light source and / or is arranged away from it.

15. Lighting unit according to one or more of claims 9 to 14, characterized in that the optical coupling between the phosphor and the primary light source is realized by a light-conducting arrangement.

16. Use of at least one phosphor according to claim 1 and / or 2 as a conversion phosphor for the partial or complete conversion of the near UV emission of a light emitting diode.

17. Use of a shaped article according to one or more of claims 4 to 7 as a phosphor body.