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    • 专利摘要:
    LIGHTING UNIT; METHOD OF PREPARING A PARTICULATED LUMINESCENT MATERIAL; AND PARTICULATED LUMINESCENT MATERIAL The present invention provides a lighting unit comprising a light source configured to generate light from the light source and a particulate luminescent material configured to convert at least part of the light from the light source into light from the luminescent material, into that the light source comprises a light emitting diode (LED), the particulate luminescent material comprises particles comprising nuclei, said nuclei comprising a phosphor comprising M? (x) M (2-2x) AX (6) doped with tetravalent manganese, M? comprises an alkaline earth cation, M comprises an alkaline cation and ex is in the range of 0-1, where A comprises a tetravalent cation, which comprises at least silicon, X comprises a monovalent anion, which comprises at least fluorine, and the particles further comprise a metal phosphate based coating, wherein the metal phosphate based coating metal is selected from the group consisting of Ti, Si and Al.
    公开号:BR112014020044B1
    申请号:R112014020044-0
    申请日:2013-02-13
    公开日:2021-03-02
    发明作者:Volker Weiler；Peter Josef Schmidt
    申请人:Lumileds Holding B.V.；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to a hexafluorosilicate phosphorus doped with coated manganese, a lighting unit comprising that phosphorus and a method of preparing that phosphorus. BACKGROUND OF THE INVENTION
    [002] Red luminescent materials for LED (light emitting device) applications are known in the art. International Patent Application WO / 2004/036962, for example, describes a light-emitting device that comprises a light-emitting structure capable of emitting primary light with a wavelength of less than 480 nm and a luminescence screen that comprises a phosphorus of general formula (Sr1-a-bCabBacMgdZne) SixNyOz: Usa, where 0.002 <to <0.2; 0.0 <b <0.25; 0.0 <c <0.25; 0.0 <d <0.25; 0.0 <and <0.25; 1.5 <x <2.5; 1.5 <y <2.5 and 1.5 <z <2.5. In addition, WO / 2004/030109 describes a luminescent green material excitable under ultraviolet-blue that consists of a europium-doped oxynitride host grid with a general composition MSi2O2N2, where M is at least one of an alkaline earth metal chosen from from the group Ca, Sr, Ba. SUMMARY OF THE INVENTION
    [003] Current phosphorus-converted (pc) LED solutions suffer from a lack of intensity in the red region of the spectrum, which prohibits the manufacture of warm white devices (especially CCT correlated color temperature <5000 K) and limits supply properties of color, or they need to use matches that have a substantial portion of the energy emitted at wavelengths> 650 nm and impair the luminous efficiency (lm / W) of these devices due to the limited sensitivity of the eye in the dark red region of the spectrum. These latter matches are typically band-emitting materials based on activation by Eu (II) (ie, divalent europium). With this activator, the spectral bandwidth expressed as the maximum half of the total width (FWHM) of the emission spectrum is intrinsically limited to about 50 nm at the required emission wavelengths (maximum peak> 600 nm). Thus, for pcLEDs, luminescent materials with narrow band or line emission in the red region of the spectrum are quite desirable, as they will offer greater spectral efficiency for lighting purposes. In viewfinders, these materials with dots of saturated red color lead to a wider range of colors if used, for example, in LEDs for LCD backlighting.
    [004] The mentioned limitations of materials doped with Eu (II) can, in principle, be overcome with line emission activators, such as Eu (III) or Mn (IV) (ie, tetravalent manganese). Although the former can be excited only by UV light, excluding the use in pcLEDs with blue emission dyes, Mn (IV) phosphors with absorption in the blue region of the spectrum have been known for a long time. These include oxides such as titanates or spinels (for example, Ca2TiO4: Mn, CaAl12O19: Mn), oxofluorides, such as magnesium fluorogermanate (Mg28Ge7,55O32F15.04: Mn), and fluorides, such as hexafluorosilicates (for example, K2SiF6: Oxygen binders are quite covalent, which leads to dark red emissions (> 650 nm), while fluorides exhibit attractive spectral properties.
    [005] However, the stability of many fluorides in water and air humidity is very limited, which results in rapid dissolution of the grid, accompanied by a significant drop in luminescence properties. For example, the solubility of Na2SiF6 is about 35 nmol / l and, for K2SiF6, about 5 mmol / l.
    [006] Thus, it is an aspect of the present invention to provide an alternative red luminescent material, which preferably still at least partially avoids one or more of the disadvantages described above, which preferably absorbs well blue and / or UV, especially blue, and / or converts efficiently absorbed light in red light and / or emitted in red without being positioned in dark red and / or is relatively stable with water and moisture and / or preferably does not absorb substantially at a wavelength longer than blue light (such as green and / or yellow). It is also an aspect to provide an alternative lighting unit, configured to use that alternative red luminescent material. Providing a method of preparing such a luminescent material can also be an aspect of the present invention.
    [007] Many red luminescent materials have been extensively studied and include known luminescent materials, such as, for example, the germanate or titanate indicated above, but nitrides have also been tested. In addition, different types of coatings on different types of luminescent materials were tested.
    [008] Now, surprisingly, apparently a hexafluorosilicate coated with metal phosphate, such as hexafluorosilicate coated with aluminum phosphate, can provide the desired properties, such as stability, correct emission wavelength, narrow band emission, blue absorption and reflectivity of green, efficiency etc. The red-emitting core and coating phosphor according to the present invention exhibits a significant increase in long-term stability in water and air humidity. For example, the K2SiF6 phosphorus activated by red emitting Mn equipped with a “glassy” Al-P coating exhibits significantly better stability in water and air humidity under elevated temperature compared to uncoated phosphorus. The optical properties of the core phosphor, such as quantum efficiency, color point and lumen equivalent, are not significantly affected by the coating and procedure used.
    [009] Thus, in a first aspect, the present invention provides a lighting unit comprising a light source, configured to generate light from a light source and a particulate luminescent material (usually also referred to as "the luminescent material"), configured to convert at least part of the light from the light source into light from luminescent material, where the light source comprises a light emitting diode (LED) and the particulate luminescent material comprises particles comprising nuclei, said nuclei comprising a phosphor which comprises M'xM2-2xAX6 doped with tetravalent manganese, where M 'comprises an alkaline earth cation, M comprises an alkaline cation and ex is in the range 0-1, where A comprises a tetravalent cation, which comprises at least silicon , where X comprises a monovalent anion, comprises at least fluorine and where the particles also comprise a coating based on metal phosphate, where the metal of the coating with metallic phosphate base is selected from the group consisting of Ti, Si and Al.
    [010] In yet another aspect, the present invention also provides a method of preparing a particulate luminescent material comprising particles comprising nuclei and a metallic phosphate coating, wherein the nuclei comprise a phosphorus comprising doped M'xM2-2xAX6 with tetravalent manganese, where M 'comprises an alkaline earth cation, M comprises an alkaline cation and x is in the range 0-1, where A comprises a tetravalent cation, comprises at least silicon, where X comprises a monovalent anion, comprises at least fluorine, in which the coating metal based on metallic phosphate is selected from the group consisting of Ti, Si and Al and in which the method comprises (i) contact of phosphorous particles (ie particles of phosphorus) M'xM2-2xAX6 doped with tetravalent manganese phosphorus) with a liquid comprising a precursor of the coating based on metallic phosphate, in which the said liquid can be obtained by mixing a liquid which and comprises alcohol, a metal salt that is soluble in the liquid that comprises alcohol and a source of phosphate; (ii) recovery of phosphorus particles treated in this way; and (iii) drying the treated phosphorus particles obtained in this way to provide the luminescent (particulate) material.
    [011] In another aspect, the present invention provides the luminescent material intrinsically, as can be obtained by means of the method mentioned above. Thus, in one embodiment, the present invention also provides a particulate luminescent material that comprises particles, where the particles comprise nuclei and a metallic phosphate coating (as a cover for the nucleus), the nuclei comprise a phosphor that comprises M'xM2- 2xAX6 doped with tetravalent manganese, where M 'comprises an alkaline earth cation, M comprises an alkaline cation and x is in the range 0-1, where A comprises a tetravalent cation, which comprises at least silicon, X comprises a monovalent anion , comprises at least fluorine, and the coating metal based on metallic phosphate is selected from the group consisting of Ti, Si and Al.
    [012] This luminescent material can have the advantages indicated above and, therefore, it can be conveniently applied in the lighting unit mentioned above.
    [013] In this document, M'xM2-2xAX6 doped with tetravalent manganese can also be briefly indicated as “phosphorus”; that is, the phrase “phosphorus comprising M'xM2-2xAX6 doped with tetravalent manganese” can, in one embodiment, also be read as M'xM2-2xAX6 doped with tetravalent manganese phosphorus or M'xM2-2xAX6 phosphorus doped by Mn (tetravalent), or just “phosphorus”.
    [014] Relevant alkaline cations (M) are sodium (Na), potassium (K) and rubidium (Rb). Optionally, lithium and / or cesium can also be applied. In a preferred embodiment, M comprises at least potassium. In yet another embodiment, M comprises at least rubidium. The phrase "where M comprises at least potassium" indicates, for example, that of all M cations in a M'xM2-2xAX6 mol, a fraction comprises K + and an optionally remaining fraction comprises one or more monovalent (alkaline) cations (see also below). In another preferred embodiment, M comprises at least potassium and rubidium. Optionally, the luminescent material M'xM2-2xAX6 has a hexagonal phase. In yet another embodiment, the luminescent material M'xM2-2xAX6 has the cubic phase.
    [015] Relevant alkaline earth cations (M ') are magnesium (Mg), strontium (Sr), calcium (Ca) and barium (Ba), especially one or more among Sr and Ba.
    [016] In one embodiment, a combination of different alkaline cations can be applied. In yet another embodiment, a combination of different alkaline earth cations can be applied. In yet another embodiment, a combination of one or more alkaline cations and one or more alkaline earth cations can be applied. For example, KRb0,5Sr0,25AX6 can be applied. As indicated above, x can be in the range 0-1, especially x <1. In one embodiment, x = 0.
    [017] The luminescent or phosphorous compound according to the present invention, that is, the coated particulate M'xM2-2xSiX6: Mn (and analogous compounds, such as in which one or more of the host grade anions or cations are partially substituted by other cations or anions) can have high luminous efficacy (such as> 200 lm / W). Generally, phosphorus emits a spectrum of a pair of narrow lines centered at about 630 nm, has a strong and wide absorption band in the 455 nm region. Thus, it is suitable for the manufacture of pcLEDs with high spectrum efficiency and color supply. Thus, the present invention provides coated narrow band red-emitting fluorosilicates, which are especially suitable for application on semiconductor (or solid-state) LEDs. This can be applied to lighting units for general lighting, but also for backlighting. The terms “: Mn” or “: Mn4 +” indicate that part of the tetravalent A ions is replaced by tetravalent Mn.
    [018] The term “tetravalent manganese” means Mn4 +. This is a well-known luminescent ion. In the formula indicated above, part of the tetravalent cation A (as Si) is replaced by manganese. Thus, M'xM2-2xAX6 doped with tetravalent manganese can also be indicated as M'xM2-2xA1- mMnmX6. The molar percentage of manganese, that is, the percentage that it replaces the tetravalent cation A, will generally be in the range of 0.1-15%, especially 1-12%, that is, m is in the range of 0.001-0.15 , especially in the range of 0.01-0.12.
    [019] A comprises a tetravalent cation and preferably comprises at least silicon. A can optionally comprise (also) one or more of titanium (Ti), germanium (Ge), tin (Sn) and zinc (Zn). Preferably, at least 80%, more preferably at least 90%, as at least 95% of M consists of silicon. Thus, in a specific embodiment, M'xM2-2xAX6 can also be described as M'xM2-2xA1-mtgs-zrMnmTitGegSnsZrzrX6, in which mex are as indicated above and in which t, g, if zr are found, preferably and individually , in the range of 0-0.2, preferably 0-0.1, more preferably 0-0.05, where t + g + s + zr is less than 1, preferably less than or equal to 0.2, of most preferably in the range of 0-0.2, preferably even greater than 0-0.1, preferably greater than 0-0.05 and where A is especially Si. X is preferably fluorine (F).
    [020] As indicated above, M refers to monovalent cations, but preferably comprises at least potassium and / or rubidium. Other monovalent cations that can also be understood by M can be selected from the group consisting of lithium (Li), sodium (Na), cesium (Cs) and ammonium (NH4 +). In one embodiment, preferably at least 80% (ie, 80% of all M-type moles), most preferably at least 90%, as 95% of M consists of potassium and rubidium. The molar ratio between potassium and rubidium is preferably in the range of 0.5-2 (that is, moles of K / moles of Rb in the range of 0.5-2), such as 0.8-1.2, preferably 0.9-1.1, more preferably 0.95-1.05 and especially 1.0. Preferably, in these embodiments, x is zero.
    [021] Thus, in a specific embodiment, M'xM2-2xAX6 can also be described as (K1-rlnc- nhRbrLilNanCsc (NH4) nh) 2AX6, where r is in the range 0-1, preferably 0.2-0 , 8 (and in which the potassium-rubidium ratio may be in an embodiment preferably as indicated above), in which l, n, c and nh are, individually and preferably, in the range of 0-1, preferably 0-0, 2, most preferably 0-0.1, preferably even greater 0-0.05 and where r + l + n + c + nh is in the range of 0-1, preferably l + n + c + nh is less than 1, preferably less than or equal to 0.2, preferably in the range of 0-0.2, more preferably 0-0.1 and, preferably even greater, 00.05. X is preferably fluorine (F).
    [022] As indicated above, instead of or in addition to the alkaline cation (s), one or more alkaline earth cations may be present. Thus, in a specific embodiment, M'xM2-2xAX6 can also be described as MgmgCacaSrsrBaba (KkRbrLilNanCsc (NH4) nh) 2AX6 ek, r, l, n, c and nh are individually in the range 0-1, where mg , ca, sr, ba are found individually in the range of 0-1 and mg + ca + sr + ba + 2 (k + r + l + n + c + nh) = 1.
    [023] As indicated above, X refers to a monovalent anion, but it comprises at least fluorine. Other monovalent anions that may optionally be present can be selected from the group consisting of chlorine (Cl), bromine (Br) and iodine (I). Preferably, at least 80%, more preferably at least 90%, as 95% of X consist of fluorine. Thus, in a specific embodiment, M'xM2-2xAX6 can also be described as M'xM2-2xA (Fl-cl-b- iClclBrbIi) 6, where cl, bei are, preferably and individually, in the range of 0 -0.2, more preferably 0-0.1, preferably even greater 0-0.05 and where cl + b + i is less than l, preferably less than or equal to 0.2, preferably in the range of 0 -0.2, more preferably 0-0.1, preferably even greater 0-0.05. Especially, X consists essentially of F (fluorine).
    [024] Thus, M'xM2-2xAX6 can also be described as (K1-rlnc-nhRbrLilNanCsc (NH4) nh) 2Si1-mtgs-zrMnmTitGegSnsZrzr (F1- cl-b-iClclBrbIi) 6, with values for r, l, n, c, nh, m, t, g, s, zr, cl, b, i as indicated above. X is preferably fluorine (F).
    [025] Most preferably, M'xM2-2xAX6 can also be described as MgmgCa caSrsr Baba (KkRbrLilNanCsc (NH4) nh) 2Si1-mtgs- zrMnmTitGegSnsZrzr (F1-cl-b-iClclBrbIi) 6 ek, r l, c and nh individually are in the range of 0-1, where mg, ca, sr and ba are individually in the range of 0-1, where mg + ca + sr + ba + 2 * (k + r + l + n + c + nh) = 1 and with the values for m, t, g, s, zr, cl, bei as indicated above. X is preferably fluorine (F).
    [026] In a preferred embodiment, M'xM2 -2xAX6 comprises K2SiF6 (indicated in this document also as a KSiF system). As indicated above, in another preferred embodiment, M'xM2-2xAX6 comprises KRbSiF6 (ie, r = 0.5 and l, n, c, nh, t, g, s, zr, cl, bei are 0) (in this document , also indicated as system K, Rb). As indicated above, part of the silicon is replaced by manganese (i.e. the formula can also be described as K2Si1-mMnmF6 or KRbSi1- mMnmF6, with m as indicated above, or as KRbSiF6: Mn and K2SiF6: Mn, respectively). As manganese replaces part of a host grade ion and has a specific function, it is also indicated as a "dopant" or "activator". Thus, hexafluorosilicate is administered or activated with manganese (Mn4 +).
    [027] The luminescent material is a particulate material, that is, it can consist essentially of particles. The particle size may depend on the desired application. In one embodiment, the luminescent particles (uncoated) can have dimensions (ie, length, width and radius) in the range of about 0.5-100 μm, such as 1-20 μm, preferably 2-15 μm; especially, at least 90% of the particles have dimensions in the indicated ranges, respectively (ie, for example, at least 90% of the particles have dimensions in the range of 0.5-20 μm, or preferably at least 90% of the particles have dimensions 2-10 μm).
    [028] The coating can have a thickness in the range of 10-500 nm, such as 50-200 nm. Thus, the luminescent material comprises cover and core particles. The coating may have an amorphous character. Thus, in this document, the coating is also referred to as a glassy coating. Preferably, the metal phosphate based coating comprises an aluminum phosphate coating. In this document, the term “metal phosphate coating” refers to a coating that contains phosphate groups and groups of metal ions. The coating may be an organic metallic coating of phosphoric esters, with preferably at least two esters that coordinate to a metal ion, such as an aluminum ion. Therefore, the metal metallic ion in the coating is preferably at least one bivalent cation, more preferably at least trivalent, such as a trivalent cation or a tetravalent cation. Its examples are Ti4 +, Si4 + and Al3 +. Aluminum can be specially applied, but a combination of two or more of these metal ions can also be applied, such as Si4 + and Al3 +.
    [029] The luminescent material, that is, the coated phosphor particles can, in one embodiment, be obtained by (i) contacting the phosphor particles with a liquid comprising a precursor of the coating based on metallic phosphate and in that said liquid (i.e., said liquid comprising the precursor of the coating based on metallic phosphate) can be obtained by mixing a liquid comprising alcohol, a metallic salt which is soluble in the liquid comprising alcohol and a source of phosphate; (ii) removal of phosphorus particles treated in this way; and (iii) drying the treated phosphorus particles obtained in this way to provide the luminescent material. Thus, the present invention also provides a method of preparing a particulate luminescent material comprising particles comprising cores and a metallic phosphate coating, wherein the cores comprise a phosphorus comprising M'xM2-2xAX6 doped with tetravalent manganese, in which M comprises an alkaline cation, A comprises a tetravalent cation which comprises at least silicon and X comprises a monovalent anion which comprises at least fluorine, in which the coating metal based on metallic phosphate is selected from the group consisting of Ti, Si and Al and the method comprises (i) contact of phosphorus particles with a liquid comprising a precursor of the coating based on metallic phosphate, wherein said liquid can be obtained by mixing a liquid comprising alcohol, a metal salt which is soluble in the liquid comprising alcohol and a source of phosphate; (ii) removal of phosphorus particles treated in this way; and (iii) drying the treated phosphorus particles obtained in this way to provide the luminescent material.
    [030] In one embodiment, the phosphate source comprises P2O5 (sometimes also indicated as P4O10 etc.). In another embodiment, the phosphate source comprises POCl3. Other sources of phosphate are also possible. In one embodiment, the alcohol comprises a C2-C4 alcohol, such as ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, etc. Optionally, higher alcohols can be applied and, optionally, hydrocarbons comprising two or more alcohol groups can also be applied.
    [031] Alcohol reacts with P2O5 and forms phosphoric acid mono and diesters:

    [032] Here, R can be, as indicated above, C2-C4, but R can also be a higher hydrocarbon, such as C2-C26 or C2-C10. The monoester is indicated as H2RPO4, but it could also be indicated as ROPO (OH) 2, that is, a phosphorus that binds to OR and two OH groups, as well as having a double bond with O. The diester is indicated as HR2PO4, but it could also be indicated as (RO) 2PO (OH), that is, a phosphorus that binds two OR groups and an OH group, as well as having a double bond with O.
    [033] The liquid comprising alcohol may be alcohol, that is, substantially consist of alcohol, but it may also optionally contain other liquids. Preferably, the water content is <2% by weight (weight of water / total net weight), preferably <1% by weight, more preferably <0.1% by weight, such as 0.01% by weight.
    [034] The metal salt can, for example, be a nitrate, sulfate, oxalate, tartrate, etc. of Ti, Si or Al. Note that a combination of one or more of Ti, Si and Al can optionally also be applied. However, the metal salt can also be an organic metal salt, such as an isopropoxide, such as aluminum isopropoxide, an ethoxide, such as aluminum ethoxide, a propoxide, as aluminum propoxide, a butoxide, such as aluminum butoxide, etc. Preferably, the solubility of the metal salt in the liquid comprising alcohol is at least 0.1 gram / l of water (at room temperature and 1 bar), as well as at least 1 gram / l of water (at room temperature and 1 bar) , most preferably at least 5 grams / l, more preferably at least 10 grams / l of water (at room temperature and 1 bar).
    [035] The trivalent aluminum cation acts as a crosslinker between the alkyl phosphate esters and thus forms a network around the particle. After drying, a good coating can be obtained (M-P, preferably Al-P).
    [036] In yet another aspect, the present invention provides a method of preparing phosphorus as described in this document, wherein the method comprises mixing (i) a soluble salt of a monovalent cation, wherein the soluble salt of the monovalent cation preferably comprises at least potassium and / or rubidium and / or sodium; (ii) a soluble salt of a tetravalent manganese precursor; (iii) a source of silicon; in (iv) an aqueous solution of inorganic acid which preferably comprises at least HF, which precipitates the phosphorus (as defined) and dries the phosphorus thus obtained, in which drying or any other heat treatment process of the optional later phosphorus is carried out under temperature below 200 ° C. At higher temperatures, the cubic phase may be formed, which may not be desired (this may depend on the specific luminescent material and / or application (intended)). Note that for other systems, such as K2SiF6 or Na2SiF6, higher temperatures may be possible. Furthermore, as mentioned elsewhere, the hexagonal phase is one of the preferred embodiments, especially in the case of the K, Rb system.
    [037] The term "monovalent cation soluble salt" refers especially to a salt (starting material) with one or more anions selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate, acetate, chlorate , citrate, cyanide, format, phosphate, oxalate, sulfate and tartrate, preferably monovalent cation salts with monovalent anions, such as KF, KCl, KNO3, RbF, RbCl, RbNO3 etc. Preferably, the solubility of the soluble salt of the monovalent cation is at least 1 gram / l of water (at room temperature and 1 bar), more preferably at least 5 grams / l, preferably even greater, at least 10 grams / l of water (at room temperature and 1 bar). Fluorides can be specially applied. The soluble salt of the monovalent cation can be a mixed salt, such as (K0,5Rb0,5) F. The term "monovalent cation soluble salt" can also refer to a mixture of salts, such as KF and RbF.
    [038] The term “soluble tetravalent manganese precursor salt” refers especially to a salt (starting material) that can supply tetravalent manganese species, but in which the salt (starting material) does not necessarily already comprise tetravalent manganese, because it can also be formed later. For example, as a reagent, KMnO4 can be used. In this case, manganese is heptavalent (Mn (VII)). During the reaction, Mn (VII) is reduced to Mn (IV). The term “soluble tetravalent manganese precursor salt” refers especially to a manganese salt with one or more cations selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and ammonium, especially precursor manganese salts with monovalent cations selected from the group consisting of potassium and ammonium, such as KMnO4 and NH4MnO4. A permanganate is preferably desired as the soluble salt of the tetravalent manganese precursor. Preferably, the solubility of the soluble tetravalent manganese precursor salt is at least 1 gram / l of water (at room temperature and 1 bar), more preferably at least 5 grams / l, preferably even greater, at least 10 grams / l of water (at room temperature and 1 bar).
    [039] The silicon source (starting material) can be soluble, but preferably SiO2 (and / or Si) can be applied.
    [040] When part of the cations and / or anions is replaced by other cations and / or anions, as indicated above, the same principles are applied.
    [041] The aqueous solution is preferably a mixture of water and hydrogen fluoride, such as concentrated HF acid (liquid state). Other inorganic acids that can be used alternatively or additionally can be selected from the group consisting of HBr acid and HCl acid (liquid state). For pure fluoride phosphorus, preferably only HF as inorganic acid is applied. Thus, the aqueous solution preferably comprises HF and water, as concentrated HF.
    [042] The starting materials (which comprise the soluble salt of a monovalent cation, the soluble salt of the tetravalent manganese precursor and the silicon source) are mixed / dissolved in the aqueous solution. Coprecipitation can be initiated. Then, the liquid can be kept at rest and the co-precipitated product can be separated from the liquid by means of decantation, centrifugation or other methods known in the art.
    [043] After obtaining the (wet) phosphorus, the phosphorus will be dried. This can occur at room temperature or at elevated temperatures. Thus, drying or any other heat treatment process of the optional later phosphorus is preferably carried out under a temperature below 200 ° C, as below 110 ° C. Thus, during the production of the lighting unit (see also below) or subsequent application of the phosphorus, the phosphorus is preferably (also) kept under a temperature below 200 ° C, preferably below 110 ° C. However, for other phases or systems other than the Rb, K system, other and optionally higher temperatures can be applied, if desired.
    [044] In a specific embodiment, the soluble salt of a monovalent cation comprises rubidium fluoride and / or hydrogen and potassium difluoride (KHF2), the soluble salt of tetravalent manganese precursor comprises KMnO4, the aqueous solution of an inorganic acid that it comprises at least HF comprises an aqueous HF solution and the silicon source comprises SiO2.
    [045] The term light source can, in principle, refer to any light source known in the art, but it can especially refer to an LED-based light source, in this document also referred to as LED. The description below - for the sake of understanding - will only address LED-based light sources. The light source is configured to provide UV and / or blue light. In a preferred embodiment, the light emitting diode is configured to generate LED light with a blue component. In other words, the light source comprises a blue LED.
    [046] In yet another embodiment, the light emitting diode is configured to generate LED light with a UV component. In other words, the light source comprises a UV LED. When a UV light source is applied and blue or white light is desired, as a blue component, for example, the well-known material BaMgAl10O17: Eu2 + can be applied. However, other luminescent materials that are capable of converting UV light to blue light can, alternatively or additionally, be applied.
    [047] Preferably, the light source is a light source that, during operation, emits at least light at a wavelength selected from the 200-490 nm range, more preferably a light source that, during operation , emits at least light at a wavelength selected from the range of 400-490 nm, preferably even greater in the range of 440-490 nm. This light can be partially used by the luminescent material (s) (see below). In a specific embodiment, the light source comprises a solid-state LED light source (such as an LED or laser diode). The term “light source” can also refer to a number of light sources, such as 2-20 LED light sources (in solid state). Thus, the term LED can also refer to a series of LEDs. Therefore, in a specific realization, the light source is configured to generate blue light.
    [048] The expression white light in this document is known to the person skilled in the art. It refers especially to light with correlated color temperature (CCT) from about 2000 to 20000 K, preferably from 2700-20000 K, for general lighting preferably in the range of about 2700 K to 6500 K and, for the purpose of backlighting, preferably in the range of about 7000 K to 20000 K and especially within about 15 SDCM (standard color matching variation) from BBL (black body location), preferably about 10 SDCM from BBL and, preferably even greater, within about 5 SDCM of BBL.
    [049] In one embodiment, the light source can also provide light from a light source with a correlated color temperature (CCT) of about 5000 to 20000 K, for example, LEDs converted from direct phosphor (blue light emitting diode with thin layer of phosphorus to obtain, for example, 10000 K). Therefore, in a specific embodiment, the light source is configured to provide light from a light source with a correlated color temperature in the range of 5000-20000 K, preferably in the range of 6000-20000 K, such as 8000-20000 K. An advantage of the high relative color temperature may be the possibility of a high relative blue component in the light from the light source.
    [050] The terms "violet light" or "violet emission" refer preferably to light with a wavelength in the range of about 380-440 nm. The expressions "blue light" or "blue emission" refer preferably to light with a wavelength in the range of about 440-490 nm (some violet and cyan tones are included). The expressions "green light" or "green emission" refer preferably to light with a wavelength in the range of about 490-560 nm. The expressions "yellow light" or "yellow emission" refer preferably to light with a wavelength in the range of about 540-570 nm. The expressions "orange light" or "orange emission" refer preferably to light with a wavelength in the range of about 570-610 nm. The expressions "red light" or "red emission" refer preferably to light with a wavelength in the range of about 600-750 nm. The expressions "pink light" or "pink emission" refer to light with a blue and a red component. The expressions "visible", "visible light" or "visible emission" refer to light with a wavelength in the range of about 380-750 nm.
    [051] The term “luminescent material” can also refer to a number of different luminescent materials. The term luminescent material in this document refers especially to inorganic luminescent materials. Similarly, this applies to the term "phosphorus". These terms are known to the person skilled in the art.
    [052] In another specific embodiment, the luminescent material comprises one or more additional phosphors selected from the group consisting of bivalent europium that contains nitride luminescent material or bivalent europium that contains oxynitride luminescent material. The red luminescent material may, in one embodiment, comprise one or more materials selected from the group consisting of (Ba, Sr, Ca) S: Eu, (Ba, Sr, Ca) AlSiN3: Eu and (Ba, Sr, Ca) 2Si5N8: Me. In these compounds, europium (Eu) is substantially or only divalent and replaces one or more of the indicated divalent cations. Generally, Eu will not be present in amounts greater than 10% of the cation, preferably in the range of about 0.510%, most preferably in the range of about 0.5-5% with respect to the cation (s) that it replaces. The terms ": Me" or ": Eu2 +" indicate that part of the metal ions is replaced by Eu (in these examples, Eu2 +). Considering 2% of Eu in CaAlSiN3: Me, for example, the correct formula may be (Ca0.98Eu0.02) AlSiN3. Generally, bivalent europium will replace bivalent cations, such as the above bivalent alkaline earth cations, preferably Ca, Sr or Ba. The material (Ba, Sr, Ca) S: Eu can also be indicated as MS: Eu, where M is one or more elements selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca ); preferably, in this compound, M comprises calcium or strontium, or calcium and strontium, most preferably calcium. Here, Eu is introduced and replaces at least part of M (that is, one or more among Ba, Sr and Ca). Furthermore, the material (Ba, Sr, Ca) 2Si5N8: Eu can also be indicated as M2Si5N8: Eu, where M is one or more elements selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Here); preferably, in this compound, M comprises Sr and / or Ba. In another specific embodiment, M consists of Sr and / or Ba (does not take into account the presence of Eu), preferably 50-100%, more preferably 50-90% Ba and 50-0%, preferably 50-10% , from Sr, as Ba1,5Sr0,5Si5N8: Eu (ie 75% Ba; 25% Sr). Here, Eu is introduced and replaces at least part of M, that is, one or more among Ba, Sr and Ca. Similarly, the material (Ba, Sr, Ca) AlSiN3: I can also be indicated as MAlSiN3: Eu , where M is one or more elements selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca); preferably, in this compound, M comprises calcium or strontium, or calcium and strontium, most preferably calcium. Here, Eu is introduced and replaces at least part of M (that is, one or more of Ba, Sr and Ca). Preferably, in one embodiment, the first luminescent material comprises (Ca, Sr, Ba) AlSiN3: Eu, most preferably CaAlSiN3: Eu. Furthermore, in another embodiment that can be combined with the previous one, the first luminescent material comprises (Ca, Sr, Ba) 2Si5N8: Me, preferably (Sr, Ba) 2Si5N8: Me. The terms "(Ca, Sr, Ba)" indicate that the corresponding cation can be occupied by calcium, strontium or barium. They also indicate that, in this material, corresponding cation sites can be occupied by cations selected from the group consisting of calcium, strontium and barium. Thus, the material can, for example, comprise calcium and strontium, or just strontium etc.
    [053] Therefore, in one embodiment, the luminescent material may also comprise M2Si5N8: Eu2 +, where M is selected from the group consisting of Ca, Sr and Ba, preferably where M is selected from the group consisting of Mr and Ba. In yet another embodiment, which can be combined with the previous one, the luminescent material can also comprise MAlN3: Eu2 +, in which M is selected from the group consisting of Ca, Sr and Ba, most preferably in which M is selected from from the group consisting of Sr and Ba.
    [054] The luminescent material may also comprise one or more matches selected from the group consisting of a trivalent cerium containing garnet and a trivalent cerium containing oxynitride.
    [055] Preferably, the luminescent material may also comprise a luminescent material M3A5O12: Ce3 +, where M is selected from the group consisting of Sc, Y, Tb, Gd and Lu, where A is selected from the group that consists of Al and Ga. Preferably, M comprises at least one or more of Y and Lu and A comprises at least Al. These types of materials can generate higher efficiencies. In a specific embodiment, the second luminescent material comprises at least two luminescent materials of the M3A5O12 type: Ce3 +, where M is selected from the group consisting of Y and Lu, A is selected from the group consisting of Al and the Y: Lu ratio is different for the at least two luminescent materials. For example, one of them can be purely Y-based, like Y3Al5O12: Ce3 +, and one of them can be a Y-based system, Lu, like (Y0.5Lu0.5) 3Al5O12: Ce3 +. Grenade embodiments preferably include M3A5O12 grenades, where M comprises at least yttrium or lutetium and A comprises at least aluminum. This grenade can be doped with cerium (Ce), praseodymium (Pr) or with a combination of cerium and praseodymium; preferably, however, with Ce. Preferably, A comprises aluminum (Al), but A may also partially comprise gallium (Ga) and / or scandium (Sc) and / or indium (In), preferably up to about 20% Al, more preferably up to about 10% % Al (that is, A ions essentially consist of 90 mol% or more of Al and 10 mol% or less of one or more among Ga, Sc and In); A can preferably comprise up to about 10% gallium. In another variation, A and O can, at least partially, be replaced by Si and N. Element M can be preferably selected from the group consisting of yttrium (Y), gadolinium (Gd), terbium (Tb) and lutetium (Lu). Furthermore, Gd and / or Tb are preferably present only up to an amount of about 20% of M. In a specific embodiment, the luminescent garnet material comprises (Y1-xLux) 3B5O12: Ce, where x is greater than or equal to 0 and less than or equal to 1. The terms ": Ce" or ": Ce3 +" indicate that part of the metal ions (ie, in the grenades: part of the "M" ions) in the luminescent material is replaced by Ce. For example, when assuming (Y1-xLux) 3Al5O12: Ce, part of Y and / or Lu is replaced by Ce. This notation is known to the person skilled in the art. Ce will replace M in general by no more than 10%; in general, the Ce concentration will be in the range of 0.1-4%, preferably 0.1-2% (with respect to M). Considering 1% Ce and 10% Y, the complete correct formula may be (Y0.1Lu0.89Ce0.01) 3Al5O12. Ce in grenades is substantially or only in the trivalent state, as known to those skilled in the art.
    [056] Optionally, one or more of these optional additional matches can also be coated, optionally with the same coating and, in a specific embodiment, with the same coating method. In a specific embodiment, a combination of two or more luminescent (particulate) materials is applied, in which at least one of the luminescent materials comprises M'xM2- 2xAx6 (coated) doped with tetravalent manganese as described in this document and at least one luminescent material additional, as indicated above, for example. By using the same batch coating method, the phosphor particles can be coated at once and can have substantially the same coating. A single particle can then contain as a core M'xM2-2xAX6 doped with tetravalent manganese phosphorus, another phosphorus or even a combination of M'xM2-2xAX6 doped with tetravalent manganese and one or more different matches.
    [057] Thus, the luminescent material may, in one embodiment, also comprise one or more different matches selected from the group consisting of a bivalent europium containing luminescent nitride material, a bivalent europium containing luminescent oxynitride material, a trivalent cerium that contains garnet and a trivalent cerium that contains oxynitride.
    [058] As will be clear to the technician on the subject, combinations of matches can also be applied. In addition, as will be clear to the person skilled in the art, optimization of the luminescent material (s) (or matches) can be applied in relation to one or more constituent elements, activating concentration, particle size, etc. or optimization regarding the combination (s) of luminescent material to optimize the lighting device.
    [059] The light source can be configured in a chamber with a reflective wall (s) (as coated with a reflective material, such as TiO2) and a transparent window. In one embodiment, the window is the light conversion layer. In another embodiment, the window comprises the light conversion layer. This layer can be arranged above the window flow or below the window flow. In yet another embodiment, light conversion layers are applied to both sides of the window.
    [060] The expressions "upstream" and "downstream" refer to an arrangement of items or features in relation to the propagation of light from a light-generating medium (here, the light source), where, in relation to a first position within a light beam from the light generating medium, a second position in the light beam closest to the light generating medium is "upstream" and a third position within of the light beam furthest from the light-generating medium is “downstream”.
    [061] The luminescent material is configured to convert at least part of the light from a light source. In other words, it can be said that the light source is coupled by radiation to the luminescent material. When the light source comprises a light source substantially emitting UV light, the luminescent material can be configured to convert substantially all of the light from the light source that falls on the luminescent material. In case the light source is configured to generate blue light, the luminescent material can partially convert the light from the light source. Depending on the configuration, a part of the light from the remaining light source can be transmitted through a layer comprising the luminescent material.
    [062] Below is a non-limiting series of possible applications of the present invention: - office lighting systems; - home application systems; - store lighting systems; - house lighting systems; - accentuated lighting systems; - localized lighting systems; - theater lighting systems; - optical fiber application systems; - - projection systems systems; auto-illuminated display; - pixelated display systems; - segmented display systems; - warning signal systems; - medical lighting application systems; - indicator signal systems; - decorative lighting systems; - portable systems; - automotive applications; and - greenhouse lighting systems.
    [063] As indicated above, the lighting unit can be used as a backlight unit on an LCD display device. Therefore, in another aspect, the present invention also provides an LCD display device that comprises the lighting unit as defined in this document configured as a backlight unit.
    [064] The term “substantially” in this document, as in “substantially the entire issue” or “consists substantially” will be understood by the person skilled in the art. The term "substantially" can also include achievements with "totally", "completely", "all" etc. Therefore, in realizations, the adverb can also be substantially removed. When applicable, the term "substantially" may also refer to 90% or more, such as 95% or more, preferably 99% or more, most preferably 99.5% or more, including 100%. The term "understands" also includes accomplishments where the term "understands" means "consists of".
    [065] In addition, the terms first, second, third and similar in the specification and in the claims are used to distinguish between similar elements and not necessarily to describe a sequential or chronological order. It is to be understood that the terms used are interchangeable under appropriate circumstances and that the embodiments of the present invention described in this document are capable of operation in sequences other than those described or illustrated in this document.
    [066] The devices in this document are, among others, described during operation. As will be clear to the person skilled in the art, the present invention is not limited to methods of operation or devices in operation.
    [067] It should be noted that the achievements mentioned above illustrate, but do not limit, the present invention and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In claims, no reference sign placed in parentheses should be considered a limitation of the claim. The use of the verb “to understand” and its conjugations does not exclude the presence of elements or steps other than those specified in a claim. Articles “one” or “one” that precede an element do not exclude the presence of a series of those elements. In claiming the device that enumerates various means, several of these means can be accomplished by a single piece of hardware. The mere fact that certain measures are indicated in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
    [068] The present invention also applies to a device that comprises one or more of the characteristic functions described in the specification and / or shown in the attached drawings. The present invention also relates to a method or process that comprises one or more of the characteristic functions described in the specification and / or shown in the accompanying drawings.
    [069] The various aspects discussed in the present patent can be combined to provide additional advantages. In addition, some of the features may form the basis for one or more divisional orders. BRIEF DESCRIPTION OF THE DRAWINGS
    [070] Realizations of the present invention will now be described by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts and in which: - Figures 1a-1c schematically show some realizations of the lighting unit; the drawings are not necessarily to scale; - Figure 2 shows emission spectra (right y axis) and reflection (left y axis) of K2SiF6 doped with uncoated and coated Mn (the latter is indicated as “-ALP”); - Figure 3 shows conductivity measurements, on the y-axis the special conductivity, normalized to 1, and on the x-axis the time in seconds of K2SiF6 doped with uncoated and coated Mn (the latter is indicated as “-ALP”) in deionized water; - Figure 4 shows the quantum efficiency (QE) as a function of time t in days of K2SiF6 doped with uncoated and coated Mn (the latter is indicated as “-ALP”) in an accelerated stress test (85 ° C and 85 % humidity); and - Figure 5 shows the luminescent material 20 in a very schematic way. DETAILED DESCRIPTION OF ACHIEVEMENTS
    [071] Figure 1a schematically shows an embodiment of the lighting unit according to the present invention, indicated with reference 100. The lighting unit comprises a light source 10, which in this schematic drawing is an LED (light emitting diode) ). In this embodiment, above the light source 10, here on the surface (light output) 15, therefore below the flow of the light source 10, a luminescent material 20 is provided. This luminescent material 20 comprises phosphor as described in this document. , indicated with reference 40 (see also Figure 5). As an example, the lighting unit 100 also comprises, for example, for light extraction properties, a dome (transmitter) 61. This is an embodiment of a transmissive optical element 60 which, in this embodiment, is arranged below in the flow of the light source 10 and also below in the flow of the light conversion layer 20. The light source 10 provides light from the light source 11 (not shown in the drawing), which is at least partially converted by the light conversion layer 20 in light of luminescent material 51. The light emanating from the lighting unit is indicated with the reference 101 and contains at least that light of luminescent material 51, but optionally, depending on the absorption of the luminescent material 50, also the source light light 11. In one embodiment, the light from the lighting unit 101 may have a CCT of 5000 K or less. However, a higher CCT may also be possible. The CCT can be adjusted by tuning the amount of luminescent material 20, including the optional presence of phosphors 40 other than the hexafluorosilicate indicated in this document.
    [072] Figure 1b schematically shows another embodiment, without a dome, but with an optional coating 62. This coating 62 is another example of a transmissive optical element 60. Note that coating 62 may, in one embodiment, be one or more of a polymeric layer, a silicone layer or an epoxy layer. Alternatively or additionally, a coating of silicon dioxide and / or silicon nitride can be applied.
    [073] In the two embodiments shown schematically in Figures 1a-1b, the luminescent material 20 is in physical contact with the light source 10 or at least its light-emitting surface (ie surface 15), like the mold of a LED. However, in Figure 1c, the luminescent material 20 is disposed away from the light source 10. In this embodiment, the luminescent material 20 is configured above in the flow of a transmissive support 30 (that is, a light transmitter), as an exit window . The surface of the support 30, to which the light conversion layer 20 is applied, is indicated with the reference 65. Note that the luminescent material 20 can also be laid down in the flow of the support 30, or can be applied to both sides of the luminescent support material 20. The distance between the luminescent material 20 and the light source (especially its light-emitting surface 15) is indicated with the reference d1 and can be in the range of 0.1 mm - 10 cm. Note that, in the configuration of Figure 1c, in principle, more than one light source 10 can also be applied.
    [074] Figure 2 shows emission spectra (right y axis) and reflection (left y axis) of K2SiF6 doped with uncoated and coated Mn (the latter is indicated with “-ALP”). As you can see, the luminescence does not change substantially (the emission spectra overlap) and the reflection in the blue region shows only a very slight decrease for these examples. This can be improved by changing the thickness of the layer, the concentration of the dopant and also the particle size. The indication I on the right y-axis refers to the intensity of photoluminescence, normalized to 1. R refers to reflection, also normalized to 1. As you can see, the luminescence of the phosphor can be considered as narrow band luminescence, since that luminescence consists substantially of line emission (and not band emission, as is the case with most Eu2 + and Ce3 + matches used in the field (and indicated above)).
    [075] Figure 3 shows conductivity measurements, on the y axis the special conductivity, normalized to 1, and on the x axis the time in seconds of K2SiF6 doped with uncoated and coated Mn (the latter is indicated with “-ALP”) in water deionized. The coated sample performs better substantially.
    [076] Figure 4 shows the quantum efficiency (QE) as a function of time t in days of K2SiF6 doped with uncoated and coated Mn (the latter is indicated with “-ALP”) in an accelerated stress test (85 ° C and 85% humidity). Again, the coated sample performs substantially better.
    [077] Figure 5 shows very schematically the luminescent material 20. It can consist substantially of particles 200 with nuclei 201 comprising phosphorus or phosphorus material, indicated with reference 40 and a coating (cover) 202 comprising the phosphate material of aluminum described in this document. The reference d indicates the dimensions of the particle core, especially the diameter, and d1 indicates the thickness of the cover or coating. EXPERIMENTAL PART
    [078] The innovative core coating phosphorus described in this document is obtained in two stages. First, Mn-doped potassium hexafluorosilicate is prepared as coprecipitate at room temperature from an aqueous HF solution containing the Mn dopant. To prepare stoichiometric amounts of K2SiF6 administered with Mn4 + from the starting materials, KHF2 and KMnO4 are dissolved in aqueous HF. Then, a stoichiometric amount of SiO2 is added to the aqueous HF solution. The concentration of Mn4 + in the aqueous HF solution was 8 mol%. The precipitates were filtered, washed repeatedly with 2-propanol and then dried at 100 ° C under vacuum.
    [079] Then, the protected cover of K2SiF6 doped with Mn is prepared by suspending the core powder in a mixture of ethanolic Al (NO3) 3 * 9H2O and P2O5 with K2SiF6 molar ratio: Al: P = 1: 0, 06: 0.06. The solvent is evaporated while stirring at elevated temperatures (about 80 ° C). Finally, the powder is heated to 200 ° C for one hour and thus results in partially hydrolyzed ester alcoholates.
    [080] The photoluminescence spectra (emission spectra, Figure 2) of these hexafluorosilicates doped with Mn cover and core reveal emission in the red region of about 600 to 660 nm. The main emission peak is located at about 631 nm. The equivalent lumen of the displayed spectrum is about 198 lm / W. The reflection in the green and yellow spectrum range is at least R> 0.92, which results in very low absorption of green and yellow emitting phosphors used to heat white applications. In addition, the self-absorption of the cover and core phosphorus according to the present invention is low due to a reflection of at least 0.95 and higher in the 600-660 nm spectrum range.
    [081] X-ray photoelectron spectroscopy (XPS) measurements reveal a significant drop in the K, Si and F core elements and an increase in the cover elements Al, P, O and C, after applying the cover over the core phosphorus with the procedure mentioned above.


    [082] Below is an example of preparation of variant K, Rb of hexafluorosilicate. The coating can be applied as indicated above. VARIATIONS
    [083] Some KSiFs coated with different ratios Al: P (Al: P = 2: 1, 1: 1, 1: 0.5 and 1: 0.25) were developed and all generated good coatings. The results shown above were with an Al: P ratio of 1: 1.
    [084] The mixed alkali metal hexafluorosilicate phosphors described in this document can be obtained as co-precipitated at room temperature from an aqueous HF solution containing the Mn dopant. To prepare stoichiometric amounts of KRbSiF6 doped with Mn4 + from the starting materials, RbF, KHF2 and KMnO4 are dissolved in aqueous HF. Then, a stoichiometric amount of SiO2 is added to the aqueous HF solution. The concentration of Mn7 + in the aqueous HF solution was 8 mol%. The precipitates were filtered, washed repeatedly with 2-propanol and then dried at room temperature under vacuum.
    [085] In addition, it is possible that a variety of other starting materials can be used to produce the hexafluorosilicate phosphorus according to the present invention by means of coprecipitation from aqueous solution (eg rubidium / potassium nitrate, chloride rubidium / potassium).
    [086] The precipitated sample was indexed as a hexagonal grid from its X-ray powder pattern (using Cu-Kα radiation). After heating to 300 ° C, the sample is transformed into a cubic grid as found in the XRD database.
    权利要求:
    Claims (15)
    [0001]
    1. LIGHTING UNIT (100), comprising a light source (10) configured to generate light from the light source (11) and a particulate luminescent material (20), configured to convert at least part of the light from the light source (11) in light of luminescent material (51), characterized by the light source (10) comprising a light emitting diode (LED), in which the particulate luminescent material (20) comprises particles (200) comprising nuclei (201) , the mentioned nuclei (201) comprise a phosphorus (40) comprising M'xM2-2xAX6 doped with tetravalent manganese, M 'comprises an alkaline earth cation, M comprises an alkaline cation and x is in the range 0-1, where A comprises a tetravalent cation, which comprises at least silicon, X comprises a monovalent anion, which comprises at least fluorine, and the particles (200) further comprise a coating based on metal phosphate (202), wherein the metal of the coating with based on metallic phosphate is selected from the group consisting of Ti, Si and Al.
    [0002]
    2. LIGHTING UNIT (100) according to claim 1, characterized in that the coating based on metal phosphate comprises an aluminum phosphate coating.
    [0003]
    3. LIGHTING UNIT (100), according to any one of the preceding claims, characterized in that the particulate luminescent material (20) can be obtained by (i) contacting the phosphorus particles with a liquid comprising a precursor of the coating with metal phosphate base, wherein said liquid can be obtained by mixing a liquid comprising alcohol, a metal salt which is soluble in the liquid comprising alcohol and a source of phosphate; (ii) removing the phosphorus particles treated in this way; and (iii) drying the phosphorus particles treated and obtained in this way to provide the luminescent material.
    [0004]
    4. LIGHTING UNIT (100), according to claim 3, characterized in that the phosphate source comprises P2O5.
    [0005]
    5. LIGHTING UNIT (100) according to any one of the preceding claims, characterized in that M'xM2-2xAX6 comprises K2SiF6.
    [0006]
    6. LIGHTING UNIT (100), according to any one of the preceding claims, characterized in that the light source (10) is configured to generate blue light.
    [0007]
    7. LIGHTING UNIT (100), according to any one of the preceding claims, characterized in that the particulate luminescent material (20) further comprises one or more different matches selected from the group consisting of bivalent europium that contains luminescent nitride material, a divalent europium that contains luminescent material of oxynitride, a trivalent cerium that contains garnet and a trivalent cerium that contains oxynitride.
    [0008]
    8. METHOD OF PREPARING A PARTICULATED LUMINESCENT MATERIAL (20), characterized in that it comprises particles (200) that comprise nuclei (201) and a metallic phosphate coating (202), in which the nuclei (201) comprise a phosphor (40) comprising M'xM2-2xAX6 doped with tetravalent manganese, where M 'comprises an alkaline earth cation, M comprises an alkaline cation and x is in the range 0-1, A comprises a tetravalent cation, which comprises at least silicon, X comprises a monovalent anion, which comprises at least fluorine, the coating metal based on metallic phosphate is selected from the group consisting of Ti, Si and Al and in which the method comprises: (i) contact of phosphorus particles with a liquid comprising a precursor of the coating based on metallic phosphate, wherein the liquid can be obtained by mixing a liquid comprising alcohol, a metallic salt that is soluble in the liquid comprising alcohol and a source of phosphate; (ii) removal of phosphorus particles treated in this way; and (iii) drying the phosphorus particles treated and obtained in this way to provide the luminescent material.
    [0009]
    METHOD according to claim 8, characterized in that the metal of the coating precursor based on metallic phosphate comprises aluminum.
    [0010]
    Method according to either of Claims 8 and 9, characterized in that the phosphate source comprises P2O5 and the alcohol is a C2-C4 alcohol.
    [0011]
    11. METHOD according to any one of claims 8 to 10, characterized in that M'xM2-2xAX6 comprises K2SiF6.
    [0012]
    METHOD, according to any one of claims 8 to 11, characterized in that the phosphorus particles can be obtained by means of a method comprising the mixture of (i) a soluble alkali cation salt, (ii) a soluble salt of precursor of tetravalent manganese and (iii) a source of tetravalent cation, in (iv) an aqueous solution of an inorganic acid comprising at least HF, phosphorus precipitation and drying of the phosphorus thus obtained, in which drying or any other process of Heat treatment of the optional posterior phosphorus is carried out at a temperature below 200 ° C.
    [0013]
    13. METHOD according to any one of claims 8 to 12, characterized in that the alcohol comprises a C2-C4 alcohol.
    [0014]
    14. PARTICULATED LUMINESCENT MATERIAL (20), characterized in that it comprises particles (200) that comprise nuclei (201) and a metallic phosphate coating (202), in which the nuclei (201) comprise a phosphorus (40) that comprises M'xM2 -2xAX6 doped with tetravalent manganese, where M 'comprises an alkaline earth cation, M comprises an alkaline cation, x is in the range 0-1, A comprises a tetravalent cation, which comprises at least silicon, X comprises a monovalent anion , which comprises at least fluorine, and the coating metal based on metallic phosphate is selected from the group consisting of Ti, Si and Al.
    [0015]
    15. PARTICULATED LUMINESCENT MATERIAL (20) according to claim 14, characterized in that M'xM2 -2xAX6 comprises K2SiF6 and the coating based on metal phosphate comprises an aluminum phosphate coating.
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    同族专利:
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    CN104114671B|2016-10-26|
    JP6297505B2|2018-03-20|
    JP2015515118A|2015-05-21|
    US9580643B2|2017-02-28|
    RU2613963C2|2017-03-22|
    US20150048399A1|2015-02-19|
    EP2814905A1|2014-12-24|
    WO2013121355A1|2013-08-22|
    RU2014137244A|2016-04-10|
    CN104114671A|2014-10-22|
    EP2814905B1|2016-04-20|
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    法律状态:
    2018-03-06| B25A| Requested transfer of rights approved|Owner name: LUMILEDS HOLDING B.V. (NL) |
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-01-05| B09A| Decision: intention to grant|
    2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261599458P| true| 2012-02-16|2012-02-16|
    US61/599,458|2012-02-16|
    PCT/IB2013/051163|WO2013121355A1|2012-02-16|2013-02-13|Coated narrow band red-emitting fluorosilicates for semiconductor leds|
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