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WO2020053381A1 - Composés luminescents émettant dans le bleu - Google Patents

Composés luminescents émettant dans le bleu Download PDF

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Publication number
WO2020053381A1
WO2020053381A1 PCT/EP2019/074474 EP2019074474W WO2020053381A1 WO 2020053381 A1 WO2020053381 A1 WO 2020053381A1 EP 2019074474 W EP2019074474 W EP 2019074474W WO 2020053381 A1 WO2020053381 A1 WO 2020053381A1
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Prior art keywords
light source
light
radiation
compound according
compound
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German (de)
English (en)
Inventor
Mathias RAPPHAHN
Ralf Petry
Ingo Koehler
David BOEHNISCH
Thomas Juestel
Merve YILMAZ
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7737—Phosphates
    • C09K11/7738—Phosphates with alkaline earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • 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
  • 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.
  • 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.
  • 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).
  • Laser diodes but it can only be excited in the UV range up to about 380 nm.
  • 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.
  • (ln, Ga) N semiconductor LED chips which emit between 380 and 420 nm are particularly efficient (FIG. 1) (cf.
  • 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.
  • 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.
  • Examples include aluminates such as SrAli 2 0i9: Eu 2+ ,
  • phosphates such as Ba 3 (ZnB 5 Oi 0 ) PO 4 : Eu 2+ (J. Sun, X. Zhang, T. Li, Mater. Lett. 2018, 212,
  • emitting phosphor for LEDs 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.
  • 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.
  • 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;
  • 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.
  • 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.
  • these blue-emitting phosphors can be used in the UV range and in the violet range
  • 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
  • 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
  • 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.
  • 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;
  • M la and M lb are different from each other.
  • the compounds of the general formula (I) are represented by the following general formulas (Ia) and (Ib):
  • the compounds of the general formula (II) are represented by the following general formulas (IIIa) and (Mb):
  • index n in the general formulas (I), (la), (Ib), (II), (lla) and (Mb): 0 ⁇ n ⁇ 3, more preferably 0 ⁇ n ⁇ 2nd
  • the index n in the general formulas (I), (la), (Ib), (II), (Na) and (Nb) is an integer selected from 1, 2 and 3.
  • n 1.
  • 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 '.
  • 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;
  • 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;
  • 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 (Mb) are: Na3-2y (Kl-a-bRbaCSb) l-2zMg7 (Pl-cASc04) 6: EUx (Nlb),
  • 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 ⁇
  • the compound of the invention may preferably be coated on its surface with another compound, as below
  • 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
  • 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
  • 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
  • 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
  • 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.
  • 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.
  • Suitable non-polar or polar aprotic solvents are
  • 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.
  • 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
  • the desired compound according to the invention is obtained as luminescent material.
  • 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
  • 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
  • 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
  • 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.
  • luminescent materials include luminescent materials.
  • Preferred further luminescent materials are conversion phosphors which are different from the compounds according to the invention, or semiconductor nanoparticles
  • 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.
  • 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.
  • the radiation-converting mixture comprises a compound according to the invention, a conversion phosphor and a quantum material.
  • 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
  • CRI Correlated Color Temperature
  • the Color Rendering Index 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
  • the correlated color temperature 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 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.
  • 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.
  • 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
  • OLED light emitting layer based arrangement
  • the primary light source is a source which shows electroluminescence and / or photoluminescence.
  • 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.
  • suitable further luminescent materials that are suitable in principle for mixtures are conversion phosphors or quantum 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.
  • 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+ ,
  • 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+ ,
  • 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
  • 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+ ,
  • 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+ ,
  • 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+ , 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
  • 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
  • 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.
  • 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
  • the quantum materials preferably consist of semiconductors
  • 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.
  • QMOP quantum material on phosphor matrix
  • 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
  • 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,
  • 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
  • the potting material can (Poly) silazane, such as a modified organic polysilazane (MOPS) or a perhydropolysilazane (PHPS).
  • MOPS modified organic polysilazane
  • PHPS perhydropolysilazane
  • 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.
  • the optical coupling between the luminescent material and the primary light source is realized by a light-guiding arrangement.
  • light-guiding devices such as light-guiding fibers.
  • 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.
  • 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.
  • 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.
  • LC display liquid crystal display device
  • the average particle size of the phosphors according to the invention for use in LEDs is usually between 50 nm and 100 ⁇ m, 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).
  • 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.
  • 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 an emission spectrum with a high blue content and they have a high photoluminescence quantum yield.
  • 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.
  • 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.
  • the compounds according to the invention can be prepared efficiently and inexpensively via a simple synthesis.
  • 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
  • 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.
  • Example 1 Na 2,985 Euo, oi5RbMg6,985Lio, oi5 (P0 4 ) 6 (0.5% Eu 2+ )
  • 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
  • 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 3 Na 2,985 Euo, oi5RbMg6,985Lio, oi5 (As0 4 ) 6 (0.5% Eu 2+ )
  • Example 4 Na2.7Euo, 3RbMg6.7Li 0, 3 (As04) 6 (10% Eu 2+ )
  • 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 1 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 1 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.
  • Emission wavelength The triangles stand for LEDs and the squares for laser diodes.
  • Figure 4 Emission spectrum of Na2.985Euo, oi5RbMg6.985Lio, ois (P0 4 ) 6 with excitation at 350 nm (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) .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne des composés émettant dans le bleu, un procédé de fabrication de ceux-ci, ainsi que leur utilisation comme luminophores ou luminophores de conversion dans des sources de lumière. La présente invention concerne en outre un mélange convertissant un rayonnement qui comprend le composé selon l'invention, ainsi qu'une source de lumière comprenant les composés selon l'invention ou le mélange convertissant un rayonnement. L'invention concerne également des sources de lumière, en particulier des DEL, et des unités d'éclairage comprenant une source de lumière primaire et le composé selon l'invention ou le mélange convertissant un rayonnement. Les composés selon l'invention peuvent être utilisés comme substances luminescentes, en particulier pour produire une lumière bleue ou blanche dans des DEL.
PCT/EP2019/074474 2018-09-14 2019-09-13 Composés luminescents émettant dans le bleu Ceased WO2020053381A1 (fr)

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CN114231283A (zh) * 2022-01-24 2022-03-25 西安建筑科技大学 一种近紫外光激发的磷酸盐蓝色荧光粉及其制备方法和白光led发光装置

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