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    • 专利摘要:
    surface-modified silicate phosphor A surface-modified silicate phosphor including a silicate phosphor and a coating including at least one of (a) a fluorinated coating including a fluorinated inorganic agent, a fluorinated organic agent, or a combination of inorganic agents and fluorinated organics, the fluorine coating generating hydrophobic surface sites, and (b) a combination of the fluorine coating and at least one moisture barrier layer. the moisture barrier layer includes mgo, al2o3, y2o3, la2o3, gd2o3, lu2o3, and sio2 or corresponding precursors, the coating being disposed on the surface of the silicate luminophore.
    公开号:BR112013003416B1
    申请号:R112013003416-5
    申请日:2011-07-29
    公开日:2022-01-11
    发明作者:Chung Hoon Lee；Walter Tews；Detlef Starick；Gundula Roth
    申请人:Seoul Semiconductor Co. Ltd.；Litec-Lp Gmbh；
    IPC主号:
    专利说明:

    Technical Field
    [001] Exemplary embodiments of the present invention relate to inorganic luminophores based on doped alkaline earth metal silicate compounds, which are capable of converting high energy primary radiation such as ultraviolet (UV) radiation or blue light, into a longer-wavelength secondary radiation within the visible region of the spectrum, and can be used as radiation converters in light-emitting devices such as light-emitting diodes (LEDs) that emit colored or white light.
    [002] Exemplary embodiments of the present invention also relate to inorganic silicate luminophores, which may have improved stability with respect to air humidity and other environmental factors, and extended operational life. State of the Technique
    [003] Alkaline earth metal silicate luminophores, which include the europium-doped alkaline earth metal orthosilicate forms, the corresponding oxyorthosilicates and disilicates in the form of Ba(Sr)3MgSi2O8:Eu, have been known for some time. An overview of the classification of alkaline earth metal silicate compounds is documented by Hollemann-Wiberg, in “Lehrbuch der Anorganischen Chemie” Inorganic Chemistry, edition 102, (Walter de Gruyter & Co., Berlin, 2007).
    [004] The preparation and essential luminescence properties thereof have been described in detail in various patents and publications, such as US6,489,716, to Tews et al.; European publication EP0550937, by Ouwerkerk et al; the European publication EP0877070, by Hase et al. and, by W.M. Yen et al., the publication “Phosphor Handbook”, 2nd Ed., CRC Press (2007). Such publications indicate that these luminophores have high quantum and radiation yields for converting high-energy radiation into visible light, and numerous representatives of this class of luminophores, due to such properties, can be used in glow products, lighting, and technology. for displays.
    [005] Patent document US2004239247 titled Plasma Display Unit refers to a plasma display device including a blue phosphor represented by Me3MgSi2O8:Eu, where Me is at least calcium (Ca), strontium (Sr) or barium (Ba ). The concentration of bivalent Eu ions is 45 to 95% and the concentration of trivalent Eu ions is 5 to 55% of the europium (Eu) atoms contained in the blue phosphorus layer. Plasma display device has less luminance degradation in a panel manufacturing process, high luminance and long lifespan.
    [006] Patent application JP2005068343 entitled VACUUM ULTRAVIOLET EXCITATION PHOSPHOR AND PLASMA DISPLAY PANEL refers to a vacuum ultraviolet excitation phosphor endowed with an excellent luminance maintenance rate as a function of ion bombardment. To achieve this objective, a vacuum ultraviolet excitation phosphor is provided, consisting of a vacuum ultraviolet excitation phosphor powder and a coating layer that at least partially coats the surface of the phosphor particles. The main component of the powder particles is manganese activated zinc silicate and the coating layer consists of at least one selected from the group consisting of fluoride, gadolinium fluoride, lanthanum fluoride, yttrium fluoride and ammonium fluoride. .
    [007] The patent application JP2003041247 entitled PLASMA DISPLAY APPARATUS concerns the provision of a plasma display in which the degradation of the brightness of the phosphor layer is avoided. To this end, the phosphor layer comprises a phosphor whose surface is coated with a silicon compound comprising fluorine or nitrogen, so as to result in a high-luminosity plasma display.
    [008] Patent document JPH10125240 entitled PLASMA DISPLAY PANEL, AND MANUFACTURE OF PHOSPHOR FOR PLASMA DISPLAY PANEL refers to improving the luminous efficacy and lifespan of a phosphor layer on a display. To achieve this goal, a uniform coating layer 42 is formed on the surface of a phosphor particle 41, where the thickness of the coating layer satisfies the expression À(2m + 1)/4h, (where À is the wavelength of the ultraviolet rays, h is the refractive index of the coating layer at = 0, 1, 2 or 3). In another embodiment, a granular material is adhered to the surface of the phosphor particle 41 with sufficient clearance between the grains for the passage of ultraviolet rays. Alternatively, a metal oxide is formed on the surface of the phosphor particle 41 with sufficient spacing for the passage of ultraviolet rays, through the hydrolysis reaction of an organometallic compound.
    [009] The patent application JP2005187797 whose title is PHOSPHOR AND LIGHT EMITTING DEVICE USING THE SAME concerns a phosphor capable of providing a light emitting device maintaining a high quality. Such a phosphorus consists of a core particle comprising an alkaline earth metal silicate phosphorus with a composition represented by the formula (M1-xEux)Li2SiyO2y+2 (where M is at least one of the alkaline earth metals, selected from the group which consists of Ca, Sr, and Ba; x is 0.001-0.1; and y is 0.9-1.1). A surface layer is disposed on this particle, wherein the material of this layer comprises at least one selected from a silicone resin, an epoxy resin, a fluorine resin, tetraethoxysilane, silica, zinc silicate, aluminum silicate, silicone oil and silicone grease. The light emission spectrum when excited at a wavelength of 360-500 consists of a main peak comprising a single light emission peak between wavelengths of 540-610 nm.
    [0010] Patent application US2008135862 entitled Light-emitting semiconductor device, light-emitting system and method for manufacturing light-emitting semiconductor device discloses a chip-shaped light-emitting semiconductor device, comprising: a substrate 4; a blue LED 1 mounted on substrate 4; and a luminescent layer 3 made of a mixture of yellow phosphor particles 2 and a base material 13 (translucent resin). Yellow Phosphorus Particle 2 is a silicate phosphor that absorbs the blue light emitted by the blue LED 1 to emit a fluorescence with a main emission peak in the wavelength range 550 nm to 600 nm inclusive, and which contains, as the main component, a compound expressed by the chemical formula: (Sr1-a1-b1-xBaa1Cab1Eux)Li2SiO4 (where 0 < a1 < 0.3; 0 < b1 < 0.8; and 0 < x < 1). Silicate phosphorus particles readily disperse substantially uniformly in the resin. As a result, excellent white light is obtained.
    [0011] The international publication WO2006061747 entitled ILLUMINATION SYSTEM COMPRISING A RADIATION SOURCE AND A LUMINESCENT MATERIAL discloses a lighting system, comprising a radiation source (1) and a luminescent material (3,4,5) which comprises at least one phosphor able to absorb a part of the light emitted by the radiation source and emit light of different wavelength. Said at least one phosphorus is an alkaline earth lithium orthosilicate activated with europium(II) red yellow of general formula (Sr1-x-y-zCaxBay)Li2SiO4:Euz where 0 < x < l; 0 < y < 1; 0.001 < z < 0.3 which can provide light sources with high brightness and color rendering index, especially in conjunction with a light emitting diode as a radiation source. Europium(II) activated alkaline earth lithium orthosilicate with red to yellow emission of general formula (Sr1-x-y-zCaxBay)Li2SiO4:Euz where 0 < x < l; 0 < y < 1; 0.001 < z < 0.3 is efficiently excitable by primary radiation in the near UV-to-blue range of the electromagnetic spectrum.
    [0012] The patent application KR20090023092 entitled LIGHT EMITTING DEVICE EMPLOYING NON STOICHIOMETRIC TETRAGONAL ALKALINE EARTH SILICATE PHOSPHORS discloses a light emitting device with high stability in the presence of humidity and temperature variations, by means of the use of alkaline earth silicates of non tetragonal copper stoichiometric. The light-emitting device comprises the light-emitting diode (6) and a silicate-like luminescent substance. The silicate fluorescent substance is arranged around the light emitting diode. The silicate-like luminescent substance includes the non-stoichiometric luminescent material. The non-stoichiometric luminescent material (3) absorbs light from the LED and then emits light at a different wavelength. The non-stoichiometric luminescent material has a tetragonal crystal structure.
    [0013] However, luminophores based on alkaline earth metal silicates also have several disadvantageous properties. Some of the disadvantages include a low radiation stability and high sensitivity of the luminophores compared to water, air humidity and other environmental factors.
    [0014] The sensitivity depends on the particular composition of the luminophore, the structural conditions and the nature of the activating ions of the luminophores. For some of the usual applications of wavelength conversion luminophores, these properties can be problematic. In view of the need for a long service life, they can be used in LED applications. A known solution is the use of appropriate technologies and materials to generate (on the surface of powdery inorganic luminophores) barrier layers to reduce the influence of water vapor.
    [0015] These processes may include encapsulation with organic polymers, coating with nanoscale oxides such as SiO2 or Al2O3, or chemical vapor deposition (CVD) of such oxides. However, in relation to silicate luminophores, the protection obtained may be insufficient to improve the corresponding lifetime of LED lamps to the desired degree. Furthermore, in the case of coated luminophores, it may be necessary to accept loss of brightness, change in color location, and other loss of quality. Processes for microencapsulating luminophore particles by means of gas phase processes can be cumbersome and expensive. General Description of the Invention The Technical Problem
    [0016] Exemplary embodiments of the present invention pertain to silicate luminophores that can provide stability to moisture, stability to radiation and other environmental influences, and improved operational lifetime.
    [0017] Exemplary embodiments of the present invention also relate to luminophores that have been subjected to a surface treatment with fluorinated organic or inorganic agents.
    [0018] Exemplary embodiments of the present invention also relate to detectably attaching fluorine compounds or finely dispersed fluorides to the surface of the luminophore, or forming surface networks of such compounds that are capable of rendering the surfaces of the luminophore hydrophobic and can heal surface defects.
    [0019] Additional features of the invention are presented below, and will be evidenced by the description, as well as learned by practicing the invention. The Technical Solution
    [0020] An exemplary embodiment of the present invention discloses a surface-modified silicate phosphor, including (a) a silicate phosphor and a coating including at least one fluorinated coating including an inorganic fluorinated agent, an organic fluorinated agent, or a combination of a fluorinated inorganic agent and a fluorinated organic agent, the hydrophobic surface sites generating the fluorine coating and (b) an onation of the fluorine coating and at least one moisture barrier layer, the moisture barrier layer including MgO, Al2O3, Ln2O3 , Y2O3, La2O3, Gd2O3, Lu2O3, and SiO2, or corresponding precursors.
    [0021] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. Brief Description of Figures
    [0022] The accompanying figures, which have been included to provide a further understanding of the invention and are incorporated therein and which form a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
    [0023] Fig. 1a is the emission spectrum of a reference material Sr2.9Ba0.01Ca0.05Eu0.04SiO5, a commercial luminophore Sr3SiO5:Eu, and oxyorthosilicate luminophores F-103, F-202, F-202T, F-320 and F-TS-600, in accordance with exemplary embodiments of the present invention.
    [0024] Fig. 1b shows the emission spectrum of reference material Sr0.876Ba1.024Eu0.1SiO4 and two alkaline earth metal orthosilicate luminophores F-401 and F-401TS, in accordance with exemplary embodiments of the present invention.
    [0025] Fig. 2a shows electron micrographs of fluorinated and non-fluorinated alkaline earth metal oxyorthosilicate luminophores, showing untreated Sr2.9Ba0.01Ca0.05SiO luminophore particles on the left and fluorinated particles of the F-202 luminophore, according to an exemplary embodiment of the present invention at right.
    [0026] Fig. 2b shows enlarged electron micrographs of the surface of the F-202 luminophore in accordance with an exemplary embodiment of the present invention.
    [0027] Fig. 3 shows electron micrographs of uncoated and fluorinated and SiO2 coated alkaline earth metal orthosilicate luminophores of the Sr0.876Ba1.024SiO4:Eu0.1 lattice composition. Eu0.1 showing a scanned electron micrograph of the coated starting material on the left, the fluorinated luminophore surface in the middle, and an additional SiO 2 coated luminophore sample on the right, in accordance with an exemplary embodiment of the present invention.
    [0028] Fig. 4 shows an energy dispersive X-ray (EDX) spectroscopic image of the F-103 luminophore with the fluorinated surface structure manifested, in accordance with the exemplary embodiment of the present invention.
    [0029] Fig. 5 shows an X-ray photoelectronic spectrum (XPS) of the F-103 luminophore in accordance with an exemplary embodiment of the present invention.
    [0030] Fig. 6 shows a representative graph of fluorine XPS peaks for different luminophore samples. Curve 1 refers to the mechanical mixing of the luminophore having the composition Sr2.9Ba0.01Ca0.05Eu0.04SiO5 with an amount of NH4F according to example A1, and Curve 2 refers to the peak 1s of the luminophore F-103 fluorinated, in accordance with the exemplary embodiment of the present invention. Detailed Description of the Invention
    [0031] The invention is described in more detail below with reference to the accompanying drawings, through which exemplary embodiments of the invention are shown. This invention may, however, be carried out in many different ways and should not be construed as being limited to the exemplary embodiments set forth herein. Rather, exemplary embodiments are provided so that this disclosure is thorough, and fully conveys the scope of the invention to those skilled in the art. In the figures, the size and respective dimensions of layers and regions may have been exaggerated for clarity. Reference numerals in the figures indicate similar elements.
    [0032] It should be understood that when an element or layer is referred to as being "on" or "connected to" another element or layer, it may be directly connected or directly on top of another element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly over" or "directly connected to" another element or layer, there are no intervening elements or layers present.
    [0033] On excitation with high energy UV radiation, blue light, electron beams, X-rays or gamma rays and, depending on their specific chemical composition and the nature of the activator, luminophores according to exemplary embodiments of the present invention can emit visible and infrared light radiation with high radiation yields and significantly improved stability of H2O, air humidity, and other environmental factors compared to prior art. For this reason, they can be used in industry in long-life products, for example in cathode ray tubes and other imaging systems (laser ray scanning systems) of X-ray image converters, light, full color LEDs for indoor and outdoor lighting, lighting for LCD screens, solar cells, greenhouse films, and eyewear as radiation converters.
    [0034] Luminophores according to exemplary embodiments of the present invention, including surface-modified silicate luminophores, can be characterized in that their surface is coated with fluorinated organic or inorganic agents for the generation of fluorinated sites. hydrophobic surfaces, or a combination of the fluorine coating with one or more moisture barrier layers composed of layer-forming materials, such as the oxides MgO, A12O3, Ln2O3 (where Ln = Y, La, Gd, or Lu) and SiO2, or the corresponding precursors, or sol-gel technologies.
    [0035] Luminophores, including surface-modified silicate luminophores, according to exemplary embodiments of the present invention may include powdery alkaline earth metal silicate luminophores. Surface-modified silicate luminophores may have the general formula:
    [0036] (Me1+Me2+Me3+) x• (Si, P, Al, B, V, N, C, Ge)y• (O, N)z:(A, R1, R2)
    [0037] Where A is an activator selected from the group of lanthanides or manganese; R1 is a fixed surface and optionally of fluorine compounds or cross-linked fluorine, and R2 features an optional additional coating with non-fluorinated layer-forming materials. Me1+ is a monovalent metal, Me2+ is a divalent metal and Me3+ is a trivalent metal selected from group III of the periodic table or lanthanides. Some of the silicon can be replaced with P, Al, B, V, N, Ge, or C. The coefficients x, y, and z can have the following ranges: 0 < x < 5, 0 < y < 12, and 0 < z < 24.
    [0038] In accordance with exemplary embodiments of the present invention, which can optimize luminescence properties and stability performance, some of the alkaline earth metal ions in the surface-modified silicate luminophores can be replaced by additional divalent ions, for example , Mg, Zn, or, with the implementation of suitable charge balancing measures, of the monovalent or trivalent cations of the alkali or rare earth metals group. In addition, P, B, V, W, Ge, or C can be incorporated into an anion sublattice of the surface-modified silicate luminophores by replacing some of the silicon.
    [0039] According to exemplary embodiments of the present invention, alkaline earth metal silicate luminophores can be fluorinated using fluor-functionalized organosilanes of the form a Si(OR)3X where R = CH3, C2H5, ... , and X = a, F-functionalized organic binder, and controlled hydrolysis and condensation can achieve the formation of a fluorinated barrier layer on a silicate luminophore matrix, which can be a barrier and can also have hydrophobic properties.
    [0040] Surface-modified silicate luminophores, according to an exemplary embodiment of the present invention, can be generically characterized by the formula:
    [0041] Sr3-x-y-zCaxBaySiO5:Euz, R1, R2
    [0042] Where 0 ≤ x ≤ 2, 0 ≤ y ≤ 2 and 0 <z <0.5.
    [0043] The surface modified silicate luminophores according to the exemplary embodiments of the present invention can also be characterized by the formula:
    [0044] Sr3-x-y-zCaxBaySiO5:Euz, R1, R2
    [0045] Where 0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.5 and 0 <z <0.25.
    [0046] Powdered luminophores used as a base for the preparation of surface-modified luminophores in accordance with exemplary embodiments of the present invention can be synthesized by multi-stage high-temperature solid-state reactions at temperatures greater than 1000°C between carbonates of alkaline earth metals that can be used as starting materials or the corresponding metal oxides and SiO2. In addition, mineralization additives (e.g. NH4Cl, NH4F, or alkali metal halides or alkaline earth metals or trivalent metal halides) can be added to the reaction mixture to promote reactivity and to control particle size distribution. of the resulting luminophores. Depending on the specific selection of stoichiometric ratios, it may be possible to produce the desired compositions of the doped alkaline earth metal silicate luminophores, more particularly the corresponding orthosilicate and oxyorthosilicate luminophores.
    [0047] Therefore, the calculated amounts of the starting materials are mixed vigorously and then subjected to a multi-stage calcination process in an inert or reduction atmosphere within the desired temperature range. In order to optimize the properties of the luminophore, the main calcination process can optionally also have several stages of calcination within different temperature ranges. After completion of the calcination process, the samples are cooled to room temperature and subjected to suitable post-treatment processes which are directed, for example, towards the elimination of flux residues, towards the minimization of surface defects, or even , for fine-tuning the particle size distribution. In place of silicon oxide, it is also possible to use, alternatively, silicon nitride (Si3N4) or other silicon-containing precursors, as reagents for the reaction with the alkaline earth metal compounds used. The synthesis of the powdered polycrystalline luminophores used for the production of exemplary embodiments of the luminophores is not restricted to the preparation processes described above.
    [0048] For the fluorination of the surfaces of pulverulent alkaline earth metal silicate luminophores according to the present invention, different inorganic fluor compounds can be used, such as alkali metal fluorides (e.g. LiF, NaF, KF), alkaline earth metal fluorides (MgF2, CaF2, SrF2, BaF2), AlF3 and rare earth fluorides (e.g. YF3, LaF3 or GdF3), NH4F and NH4HF2, as well as other inorganic or organic fluorine compounds (e.g. amines containing fluorine). Selected materials are mixed with powdered silicate luminophore, in which case aqueous suspensions can be employed. The required proportions of the added fluorinating agents depend on the solubility of the compounds and the reaction conditions (pH, temperature, intensity determined experimentally.
    [0049] After the surface treatment is finished, the fluorinated luminophores are removed from the suspension, and can be washed with appropriate solvents and then dried at a temperature between 80°C and 200°C. After cooling and sieving, they will be ready to use.
    [0050] In order to obtain suitable luminophores properties, depending on the specific composition of the inventive luminophores, the type and amount of the fluorinating agents used, and additional factors, it is possible to subject the luminophores produced according to the invention, additionally or in replacement of the drying process, to a post heat treatment (heat treatment) within a temperature range of 300°C to 600°C in a reducing atmosphere. Detailed information on the production of luminophores in accordance with exemplary embodiments of the present invention is provided through various examples below. Example A1
    [0051] Example A1 describes the preparation of a luminophore provided with a fluorinated surface layer and having the lattice base composition Sr2.9Ba0.01Ca0.05SiO5:Eu0.04 according to an exemplary embodiment of the present invention, which is described as sample F-103 together with its optical data in Table 1, and the emission spectrum which is designated as "3" in Fig. 1a.
    [0052] Table 1 contains data on the moisture and optical stability of samples of europium-activated strontium oxyorthosilicate luminophores that were treated with different amounts of NH4F. To synthesize the corresponding luminophore matrix, stoichiometric amounts of SrCO3, BaCO3, CaCO3, Eu2O3, and SiO2 and 0.2 mol of NH4 C1 are vigorously mixed and then subjected, in corundum crucibles, to a process of calcination for 5 hours at 1400°C in an atmosphere of N2/H2 containing 2% hydrogen. After completion of the calcination process, the calcined materials are homogenized, ground and washed with H2O. Subsequently, 100g of sieved dry luminophores are introduced, together with 1.1g of NH4F, 200g of glass beads and 1 liter of water, into a plastic container, and vigorously mixed in a jug mill at low speed for 30 minutes. After a settling time of a few minutes, the supernatant is first decanted and then suction filtered through a Büchner funnel. Subsequently, the final product is dried and sieved. Example A2
    [0053] To prepare the sample containing the F-202 luminophore according to an exemplary embodiment of the present invention, the optical data are shown in Table 2 and the emission spectrum designated as "4" in Fig. 1a, 100 g of matrix of luminophore described in Example A1 are mixed with 2.474 g of NH4HF2. Table 2 contains moisture and optical stability data from europium activated strontium oxyorthosilicate luminophore samples that were treated with different amounts of NH4HF2. In this case, the fluorinated surface layer is applied by wet chemical precipitation, taking the mixture into 1 L of deionized water and 400 g of glass beads on a roller mill. Treatment for one hour is followed by removal of the coated luminophore from the solution and a post-treatment similar to Example A1. Example A3
    [0054] Here, 30 g of the luminophore produced according to Example A2 is heat treated in a corundum crucible at 400°C in an atmosphere of N2/H2 containing 35% hydrogen for 60 minutes. After cooling, the F-202T sample, the optical data specified in Table 2, and the emission spectrum designated "5" in Fig. 1a are homogenized by sieving to produce an exemplary embodiment of the present invention. Example A4
    [0055] An oxyorthosilicate luminophore having a Sr2.948Ba0.01Cu0.002SiO5:Eu0.04 lattice composition according to an exemplary embodiment of the present invention is synthesized in the solid state according to Example A1 and coated with a lattice. of SiO2 using Tetraethoxysilane (TEOS) precursor materials. For this purpose, 50 g of the luminophore is mixed with 500 ml of a solution of 1 L of ethanol, 18.2 g of TEOS and 100 ml of 32% aqueous ammonia, and stirred in a reaction vessel for 2 hours. Thereafter, the coated luminophore is suction filtered, washed with ethanol and dried at 160°C for 24 hours.
    [0056] After this preparative surface treatment, the luminophore is subjected, as in Example A1, to fluorination by NH4F as a fluorinating agent. For this purpose, 80 g of the pre-coated luminophore is reacted with 1.98 g of NH4F under the conditions of Example A1. The luminophore according to the present exemplary embodiment is thus produced in the form of sample F-TS-600. The optical data described in Table 6, and the emission spectrum designated as "7" in Fig. 1a, as well as the luminophore described in Examples A1, A2, and A3, can have significantly improved moisture resistance compared to luminophores. of conventional oxyorthosilicates, and the same base lattice composition as uncoated base luminophores. The performance characteristics of these luminophores according to exemplary embodiments of the present invention are compiled in Tables 1, 2 and 6. Example B1
    [0057] For the production of the luminophore according to the exemplary embodiment of the present invention in the form of sample F-320, a lattice of the composition Sr2.9485Ba0.01Cu0.0015SiO5:Eu0.04 is synthesized. For this, stoichiometric amounts of SrCO3, BaCO3,CuO,Eu2O3, 65 g of SiO2 and 0.3 mol of NH4Cl are mixed, introduced into appropriate calcining crucibles and calcined in a high-temperature oven for a period of 24 hours. The calcination program has two main calcination zones at 1200°C and 1350°C for 3 hours at each temperature. During the first calcination stage, this is carried out under gas formation with a hydrogen concentration of 5%, and the hydrogen concentration being increased to 20% in the subsequent second calcination stage.
    [0058] Cooling, washing, and homogenization of the matrix materials are followed by fluorination of the luminophore surface. For this purpose, the fluorinating agent used is aluminum fluoride, AlF3, in place of NH4F or NH4HF2. For interaction with the surface of the luminophore particles, 1.2 g of AlF3 are introduced into 1 L of H2O at a temperature of 60°C and the mixture is stirred vigorously for 1 hour. Subsequently, 100 g of the synthesized luminophore matrix are added to the suspension. The reaction time can be 60 minutes. The coated luminophore in the form of sample F-320 is post-treated similarly to Examples A1, A2, A3, and A4. Optical data are shown in Table 3, and the emission spectrum thereof is designated as "6" in Fig. 1a. Table 3 contains the optical and stability data of Eu2+-doped strontium oxyorthosilicate fluorinated luminophores. Example C1
    [0059] The following examples relate to alkaline earth metal orthosilicate luminophores, according to exemplary embodiments of the present invention and with a composition of Sr0.876Ba1.024SiO4:Eu0.1. In the present exemplary embodiment, the base material is produced by a high temperature solid state reaction wherein the starting mixture comprises stoichiometric amounts of SrCO3, BaCO3, Eu2O3, SiO2 and 0.2 mol of NH4Cl.
    [0060] The calcination process includes heating the crucible filled with the starting mixture to 1275°C in a nitrogen atmosphere, holding at this temperature for a period of 10 hours and subsequently cooling to room temperature . In performing the elevated temperature ramp, 20% hydrogen is added to the shielding gas. After cooling, the resulting materials are subjected to washing to remove flux residues and then dried and sieved.
    [0061] For fluorination of the base material, 150 g of the luminophore powder and 4.268 g of NH4F are suspended in 3 L of H2O and stirred for a period of 2 hours. After completion of the coating procedure, the fluorinated luminophore is suction filtered to generate sample F-401, washed with ethanol in the suction filter and dried at 130°C for 24 hours. The optical data of sample F-401 is shown in Table 4, and the emission spectrum F-401 is designated by "3" in Fig. 1b. Table 4 contains the optical and stability data of green wavelength emitting alkaline earth metal orthosilicate fluorinated luminophores that were additionally coated with SiO 2 .
    [0062] In an additional step, the luminophore according to the present exemplary embodiment, in the form of sample F-401 can be provided with a coating of SiO2. For this purpose, 50 g of fluorinated Sr0.876Ba1.024SiO4:Eu0.1 luminophore powder are added to 500 ml of TEOS solution consisting of 1 L of ethanol, 25 g of TEOS and 150 ml of 32% aqueous ammonia, prepared 24 hours before use. After a stirring time of 5 hours, the reaction is terminated. The surface coated luminophore in the form of sample F-401TS is suction filtered, washed again with ethanol, and dried. The optical data of sample F-401TS is specified in Table 4, the emission spectrum of F-401TS is designated as "4" in Fig. 1b.
    [0063] The emission spectra of the fluorinated luminophores of different matrix compositions compared to the untreated luminophores, whose case is described in Fig.1a and Fig.1b, which shows the luminescence intensities of the luminophores with the fluorinated surface structure in accordance with exemplary embodiments of the present invention, differ slightly from the spectra of the reference material. This is confirmed by the luminescence data of the luminophore samples according to the exemplary modalities compiled in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6 and Table 7, although some slightly lower luminescence intensities were measured. in some cases for the fluorinated samples and, optionally additionally, for the SiO2 coated samples. There are also examples in the tables designated by the surface treatment leading to a slight increase in luminescence efficiency. This last effect can be attributed to slightly better light emission in the case of coated materials.
    [0064] In Figs. 2a and 2b, electron micrographs of a fluorinated Sr3SiO5:Eu luminophore in accordance with exemplary embodiments of the present invention are compared to those of untreated starting material. These micrographs demonstrate that the surface treatment described in the examples, with suitable fluorinating agents, leads to the formation of specific surface structures, which can be visualized with the aid of a scanning electron microscope.
    [0065] The situation is comparable to the electron micrographs shown in Fig.3 for alkaline earth metal orthosilicate luminophores that emit the wavelength of green light. The micrographs in Fig. 3 show the characteristic particle surface of an untreated luminophore sample, that of the fluorinated material produced in accordance with exemplary embodiments of the present invention, and of an additional sample derived from the starting material, which had additionally been coated with SiO2.
    [0066] At the same time, it becomes clear from the results of the corresponding energy dispersive X-ray spectroscopy (EDX) analyzes shown in Fig. 4 that the surface structures contain fluorine. In addition to the strontium (Sr), silicon (Si) and oxygen (O) peaks that are characteristic of the luminophore matrix, unique sharp reflections with significant peak height are found in the EDX spectrum of fluorinated luminophores according to the invention, which must be unambiguously assigned to the fluorine element (F) based on the peak energy position.
    [0067] In addition, the spectrum shown also contains reflections designated as gold (Au) and palladium (Pd), which result from coating the luminophore sample with gold and palladium for reasons related to the analysis methodology.
    [0068] Further evidence for the attachment of finely dispersed fluorides or fluorine compounds or for the formation of networks of such compounds on the surface of luminophores in accordance with exemplary embodiments of the present invention is documented in Fig. 5 and Fig. 6 with the results of X-ray photoelectron spectroscopy (XPS) analysis. Fixation can include adsorption and similar means for chemisorption or physisorption.
    [0069] The XPS spectrum, shown in Fig. 5, of a base lattice luminophore of composition Sr2.9Ba0.01Ca0.05Eu0.04SiO5 treated with NH4F according to Example 1 also shows that it is possible with this method of analysis in solid state, the element fluorine (F) is detected as a constituent of the surface structures of the fluorinated luminophores. Other conclusions can also be drawn from the XPS spectrum. For example, it is evident from comparing the XPS spectra of the NH4F-fluorinated oxyorthosilicate luminophore (curve 2 in Fig. 6) with those of a sample of a mechanical mixture of the corresponding luminophore matrix with the equivalent amount of NH4F ( curve 1 of Fig. 6), that the F 1s peaks determined in each case have different intensities and also show a shift in binding energy with respect to each other as shown in Fig. 6.
    [0070] The lower intensity of the F 1s peak of the sample marked as curve 2 can be interpreted as the loss of part of the fluorine added from the surface of the luminophore during processing. The shift of the F 1s peak to lower curve 1 binding energies may indicate the formation of a chemical bond between the applied fluorinating agent and the surface of the luminophore matrix.
    [0071] In Tables 1, 2, 3, 4, 5 and 6, various luminescence parameters of the different silicate luminophores configured according to the exemplary embodiments of the present invention and the stability test results are compiled and compared with those of the luminophores powders (i.e. non-fluorinated surface) and, in some cases, with those of commercial comparative luminophores. Table 5 contains optical and stability data of fluorinated SiO2 and Eu2+ coated strontium oxyorthosilicate luminophores. Table 6 contains optical and stability data of SiO2 coated strontium oxyorthosilicate luminophores that have been fluorinated.
    [0072] The moisture stability of the materials was evaluated by storing the luminophore samples in a corresponding climate-controlled cabinet, which was operated at a temperature of 85°C and a relative humidity of 85%, for seven days. Subsequently, the luminophores were dried at 150°C for 24 hours and then subjected to a comparative measurement of the luminescence yield.
    [0073] The results of comparative luminescence measurements demonstrate that both the luminescence efficiencies of the luminophores according to the exemplary embodiments of the present invention and the respective temperature dependencies are the same as those of commercial europium-activated alkaline earth metal oxyorthosilicate phosphors orthosilicate orthosilicate, or even exceed them.
    [0074] Second, the stability test results show that luminophores according to the exemplary embodiments of the present invention, with the fluorinated surface structure and optional additional SiO2 coating, as shown in Tables 4, 5 and 6, have significantly improved strengths compared to unaltered luminophores (non-fluorinated surface, for example) of the same matrix composition.
    [0075] It is clear to those skilled in the art that various modifications and variations may be made to the present invention without departing from the spirit or scope of the invention. Thus, the present invention is intended to cover modifications and variations of this invention so long as they are within the scope of the appended claims and their equivalents.
    权利要求:
    Claims (13)
    [0001]
    1. Surface-modified silicate luminophore, characterized in that it comprises a silicate luminophore, and a fluorinated coating disposed on the surface of the silicate luminophore comprising a fluor-functionalized organosilane comprising the general formula Si(OR)3X where R is a alkyl group having one or two carbon atoms and X comprises a fluorine-functionalized organic ligand, the fluorinated coating generating hydrophobic surface sites.
    [0002]
    2. Surface-modified silicate luminophore, according to claim 1, characterized in that the surface-modified luminophore comprises a powdery alkaline earth metal silicate luminophore.
    [0003]
    3. Surface-modified silicate luminophore, according to claim 1, characterized in that the silicate luminophore comprises the general formula (Me1+Me2+Me3+)x«(Si, P, Al, B, V, N , C, Ge)y*(O, N)z:(A, R1, R2), where the relationship with (A, R1, R2) is an additive relationship, where A is an activator selected from the lanthanide group and /or manganese, R1 is a fluorinated layer comprising a surface-fixed fluorine compound and R2 is a barrier layer comprising at least one of the group consisting of MgO, Al2O3, Y2O3, La2O3, Gd2O3, Lu2O3, Si2 and their precursors , Me1+ is a monovalent metal, Me2+ is a divalent metal, and Me3+ is a trivalent metal selected from group III, or from the lanthanides, some of the Si can be replaced by P, Al, B, V or Ge, where 0 < x < 5; 0 < y < 12; 0 < z < 24.
    [0004]
    4. Surface-modified silicate luminophore, according to claim 1, characterized in that the silicate luminophore comprises the Formula Sr3-xy-zCaxBaySiO5:Euz, R1, R2, where 0 < x < 2, 0 < y < 2, and 0 < z < 0.5 and wherein R1 is a fluorinated coating comprising a surface-fixed fluorine compound, and R2 is a moisture barrier layer comprising at least one selected from the group consisting of MgO , Al2O3, Y2O3, La2O3, Gd2O3, Lu2O3, SiO2 and their corresponding precursors.
    [0005]
    5. Surface-modified silicate luminophore, according to claim 1, characterized in that the silicate luminophore comprises the formula Sr3-x-y-zCaxBaySiO5:Euz, R1, R2, where 0 < x < 0.05; 0 < y < 0.5; and 0 < z < 0.25 and wherein R1 is a fluorinated coating comprising a surface-fixed fluorine compound, and R2 is a moisture barrier layer comprising at least one selected from the group consisting of MgO, Al2O3, Y2O3, La2O3, Gd2O3, Lu2O3, SiO2 and their corresponding precursors.
    [0006]
    6. Surface-modified silicate luminophore, according to claim 2, characterized in that the powdered alkaline earth metal silicate luminophore further comprises alkaline earth metals substituted by divalent ions comprising Mg, Zn, monovalent cations selected from from the group of alkali and rare earth metals, and trivalent cations selected from the group of rare earths.
    [0007]
    7. Surface-modified silicate luminophore, according to claim 2, characterized in that the powdered alkaline earth metal silicate luminophore further comprises the silicon substituted by P, B, V or Ge.
    [0008]
    8. Surface-modified silicate luminophore, comprising the formula Sr3-xy-zCaxBaySiO5:Euz, R1, R2, characterized in that 0 < x < 2, 0 < y < 2, and 0 < z < 0.5, wherein R1 is a fluorinated coating comprising a fluorinated inorganic agent, a fluorinated organic agent or a combination of a fluorinated inorganic agent and a fluorinated organic agent, the fluorinated coating generating hydrophobic surface sites, the fluorinated coating comprising a fluorine ion attached to the surface, or a fluorine compound with a fixed or cross-linked surface and R2 is a moisture barrier layer comprising at least one selected from the group consisting of MgO, Al2O3, Y2O3, La2O3, Gd2O3, Lu2O3, SiO2 and their corresponding precursors.
    [0009]
    9. Surface-modified silicate luminophore, according to claim 8, characterized in that 0 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.5, and 0 < z < 0.25.
    [0010]
    10. A surface-modified silicate luminophore, characterized in that it comprises a silicate luminophore, and a fluorinated coating comprising a fluorinated inorganic agent, a fluorinated organic agent or a combination of a fluorinated inorganic agent and a fluorinated organic agent, the fluorinated coating generating hydrophobic surface sites, and a moisture barrier layer comprising at least one selected from the group consisting of MgO, Al2O3, Y2O3, La2O3, Gd2O3, Lu2O3, SiO2 and their corresponding precursors, wherein said coating is disposed on the surface of the silicate luminophore.
    [0011]
    11. Surface-modified silicate luminophore, according to claim 10, characterized in that it comprises a powdery alkaline earth metal silicate luminophore.
    [0012]
    12. Surface-modified silicate luminophore, according to claim 11, characterized in that the powdered alkaline earth metal silicate luminophore additionally comprises the replacement of the alkaline earth metal by additional divalent ions, comprising Mg, Zn, monovalent cations of alkali metal group, and trivalent rare earth cations.
    [0013]
    13. Surface-modified silicate luminophore, according to claim 11, characterized in that the powdered alkaline earth metal silicate luminophore additionally comprises the silicon substituted by P, B, V or Ge.
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    同族专利:
    公开号 | 公开日
    CN103081140A|2013-05-01|
    RU2569167C2|2015-11-20|
    BR112013003417A2|2020-10-27|
    WO2012023714A2|2012-02-23|
    EP2603937A4|2014-10-22|
    EP2603571A4|2014-10-22|
    DE102010034322A1|2012-02-16|
    US20120205674A1|2012-08-16|
    TWI522444B|2016-02-21|
    KR101761855B1|2017-07-27|
    TW201211208A|2012-03-16|
    WO2012023714A3|2012-05-18|
    TW201211209A|2012-03-16|
    BR112013003416A2|2020-10-27|
    CN103068953A|2013-04-24|
    RU2013111293A|2014-09-20|
    EP2603937A2|2013-06-19|
    US20120037850A1|2012-02-16|
    US8581286B2|2013-11-12|
    TWI541325B|2016-07-11|
    KR101752428B1|2017-07-05|
    JP2013541828A|2013-11-14|
    EP2603937B1|2016-11-23|
    KR20120023496A|2012-03-13|
    US8945421B2|2015-02-03|
    JP2013536283A|2013-09-19|
    KR20120023495A|2012-03-13|
    RU2013111302A|2014-09-20|
    EP2603571A2|2013-06-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS5222584A|1975-08-14|1977-02-19|Fujitsu Ltd|Method for protective treatment of fluorescent substance|
    JPS52156188A|1976-06-21|1977-12-26|Sony Corp|Fluorescent substance|
    ES2100275T3|1992-01-07|1997-06-16|Philips Electronics Nv|DISCHARGE LAMP IN LOW PRESSURE MERCURY.|
    PT877070E|1996-01-22|2003-08-29|Kasei Optonix|PHOSPHORUS PHOSPHORUS|
    JP3234526B2|1996-08-29|2001-12-04|松下電器産業株式会社|Plasma display panel and method of manufacturing phosphor for plasma display|
    US5792509A|1997-02-07|1998-08-11|Industrial Technology Research Institute|Phosphor particle with antireflection coating|
    DE19806213B4|1998-02-16|2005-12-01|Tews, Walter, Dipl.-Chem. Dr.rer.nat.habil.|Compact energy saving lamp|
    US6346326B1|1998-10-15|2002-02-12|Sarnoff Corporation|Coated moisture impervious red phosphors|
    JP2002069442A|2000-09-01|2002-03-08|Showa Denko Kk|Silica film coated with light emitting grain|
    AT410266B|2000-12-28|2003-03-25|Tridonic Optoelectronics Gmbh|LIGHT SOURCE WITH A LIGHT-EMITTING ELEMENT|
    JP4019649B2|2001-04-27|2007-12-12|日亜化学工業株式会社|Light emitting device|
    JP2003041247A|2001-07-31|2003-02-13|Matsushita Electric Ind Co Ltd|Plasma display apparatus|
    TW595012B|2001-09-03|2004-06-21|Matsushita Electric Ind Co Ltd|Semiconductor light-emitting device, light-emitting apparatus and manufacturing method of semiconductor light-emitting device|
    JP4096619B2|2002-05-17|2008-06-04|松下電器産業株式会社|Method for manufacturing plasma display device|
    JP4228098B2|2002-08-29|2009-02-25|東ソー株式会社|Alkaline earth metal silicate phosphor and light emitting device|
    JP2004168846A|2002-11-19|2004-06-17|Asahi Glass Co Ltd|Composite particulate and its preparation method|
    US20030173540A1|2003-02-19|2003-09-18|Mortz Bradford K|Long persistent phosphor incorporated within a settable material|
    JP2005003436A|2003-06-10|2005-01-06|Konica Minolta Medical & Graphic Inc|Method for manufacturing stimulable phosphor, radiation image conversion panel using it and method for manufacturing such panel|
    JP4516793B2|2003-08-22|2010-08-04|パナソニック株式会社|Plasma display panel|
    JP2005068343A|2003-08-27|2005-03-17|Nichia Chem Ind Ltd|Vacuum ultraviolet excitation phosphor and plasma display panel|
    JP4322774B2|2003-12-05|2009-09-02|株式会社東芝|Phosphor and light emitting device using the same|
    BRPI0517584B1|2004-12-22|2017-12-12|Seoul Semiconductor Co., Ltd|LIGHTING DEVICE|
    JP4645089B2|2004-07-26|2011-03-09|日亜化学工業株式会社|Light emitting device and phosphor|
    JP4530755B2|2004-07-28|2010-08-25|株式会社東京化学研究所|Orange phosphor|
    US7601276B2|2004-08-04|2009-10-13|Intematix Corporation|Two-phase silicate-based yellow phosphor|
    US20060027785A1|2004-08-04|2006-02-09|Intematix Corporation|Novel silicate-based yellow-green phosphors|
    JP4562453B2|2004-08-10|2010-10-13|富士フイルム株式会社|Electroluminescent phosphor, method for producing the same, and electroluminescent device|
    EP1794808B1|2004-09-10|2017-08-09|Seoul Semiconductor Co., Ltd.|Light emitting diode package having multiple molding resins|
    JP2008523169A|2004-12-07|2008-07-03|コーニンクレッカフィリップスエレクトロニクスエヌヴィ|Illumination system including a radiation source and a luminescent material|
    JP2006232949A|2005-02-23|2006-09-07|Matsushita Electric Works Ltd|Method for treating phosphor particle, light emitting device, and phosphor particle|
    JP2006286672A|2005-03-31|2006-10-19|Okaya Electric Ind Co Ltd|Light emitting diode and its fabrication process|
    KR101346580B1|2005-04-01|2014-01-02|미쓰비시 가가꾸 가부시키가이샤|Alloy powder for aw material of inorganic functional material and phosphor|
    JP5245222B2|2005-08-10|2013-07-24|三菱化学株式会社|Phosphor and light emitting device using the same|
    US20070125984A1|2005-12-01|2007-06-07|Sarnoff Corporation|Phosphors protected against moisture and LED lighting devices|
    CN101336479A|2005-12-01|2008-12-31|沙诺夫公司|Phosphors protected against moisture and led lighting devices|
    JP4961828B2|2006-05-12|2012-06-27|ソニー株式会社|Method for producing nanoparticle-resin composite material|
    JP2009013186A|2007-06-29|2009-01-22|Mitsubishi Chemicals Corp|Coated phosphor particles, method for producing coated phosphor particles, phosphor-containing composition, light emitting device, image display device and illuminating device|
    WO2009028818A2|2007-08-28|2009-03-05|Seoul Semiconductor Co., Ltd.|Light emitting device employing non-stoichiometric tetragonal alkaline earth silicate phosphors|
    KR101055769B1|2007-08-28|2011-08-11|서울반도체 주식회사|Light-emitting device adopting non-stoichiometric tetra-alkaline earth silicate phosphor|
    US7915627B2|2007-10-17|2011-03-29|Intematix Corporation|Light emitting device with phosphor wavelength conversion|
    KR20090040097A|2007-10-19|2009-04-23|삼성전기주식회사|Light emitting diode package|
    JP5369295B2|2007-11-08|2013-12-18|住友金属鉱山株式会社|Surface-coated strontium silicate phosphor particles, method for producing the same, and light-emitting diode comprising the phosphor particles|
    DE102007056342A1|2007-11-22|2009-05-28|Merck Patent Gmbh|Surface modified phosphor particles, useful e.g. for converting blue or near UV lying emission into visible white radiation, comprise luminescent particles containing silicate compounds|
    CN101939857B|2008-02-07|2013-05-15|三菱化学株式会社|Semiconductor light emitting device, backlight, color image display device and phosphor to be used for them|
    JP4618330B2|2008-05-21|2011-01-26|ソニー株式会社|Phosphor and its manufacturing method, and light emitting device and display device using phosphor|
    DE102009044255A1|2009-10-15|2011-04-28|Leuchtstoffwerk Breitungen Gmbh|Alkaline earth metal silicate phosphors and methods for improving their long-term stability|
    JP2011111506A|2009-11-25|2011-06-09|Panasonic Electric Works Co Ltd|Wavelength conversion particle, wavelength conversion member, and light emitting device|
    EP2554628B1|2010-03-31|2016-07-13|Sekisui Chemical Co., Ltd.|Surface-treated fluorescent bodies and process for production of surface-treated fluorescent bodies|
    DE102010034322A1|2010-08-14|2012-02-16|Litec-Lp Gmbh|Surface modified silicate phosphors|KR101241650B1|2005-10-19|2013-03-08|엘지이노텍 주식회사|Package of light emitting diode|
    DE102010034322A1|2010-08-14|2012-02-16|Litec-Lp Gmbh|Surface modified silicate phosphors|
    US9234129B2|2010-08-14|2016-01-12|Seoul Semiconductor Co., Ltd.|Surface-modified quantum dot luminophores|
    US9196785B2|2010-08-14|2015-11-24|Seoul Semiconductor Co., Ltd.|Light emitting device having surface-modified quantum dot luminophores|
    US9614129B2|2010-08-14|2017-04-04|Seoul Semiconductor Co., Ltd.|Light emitting device having surface-modified luminophores|
    EP2721633B1|2011-06-20|2021-05-05|Crystalplex Corporation|Stabilized nanocrystals|
    DE102012203419A1|2011-07-29|2013-01-31|Osram Ag|Phosphor and fluorescent lamp containing the same|
    JP2013040236A|2011-08-11|2013-02-28|Sekisui Chem Co Ltd|Method for producing surface-treated phosphor and surface-treated phosphor|
    KR101772588B1|2011-08-22|2017-09-13|한국전자통신연구원|MIT device molded by Clear compound epoxy and fire detecting device including the MIT device|
    TWI464235B|2012-11-21|2014-12-11|Lextar Electronics Corp|Phosphor composition and light emitting diode device using the same|
    US10875005B2|2013-02-25|2020-12-29|Lumileds Llc|Coated luminescent particle, a luminescent converter element, a light source, a luminaire and a method of manufacturing a coated luminescent particle|
    DE102013106573B4|2013-06-24|2021-12-09|OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung|Radiation-emitting optoelectronic component, gas sensor with radiation-emitting optoelectronic component and method for producing a radiation-emitting optoelectronic component|
    EP3148712B1|2014-05-29|2021-08-18|Crystalplex Corporation|Dispersion system for quantum dots|
    US10144815B2|2015-09-29|2018-12-04|Portland State University|Modified nano-clays and coating compositions including the same|
    RU2664143C2|2016-03-21|2018-08-15|Закрытое Акционерное Общество "Научно-производственная фирма "Люминофор"|Method for applying protective film on surface of phosphor dots|
    CN106316373A|2016-07-29|2017-01-11|江苏罗化新材料有限公司|Preparing method for high power illuminant fluoride florescent and crystalline ceramics|
    JP6720944B2|2017-08-31|2020-07-08|日亜化学工業株式会社|Nitride phosphor manufacturing method, nitride phosphor and light emitting device|
    RU202047U1|2020-11-16|2021-01-28|Сергей Григорьевич Никифоров|COMBINED RADIATION SOURCE|
    法律状态:
    2020-11-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-11-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-04-27| B06G| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]|
    2021-07-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-12-07| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2022-01-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/07/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102010034322A|DE102010034322A1|2010-08-14|2010-08-14|Surface modified silicate phosphors|
    DE1020100343226|2010-08-14|
    PCT/KR2011/005607|WO2012023714A2|2010-08-14|2011-07-29|Surface-modified silicate luminophores|
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