EP2831016A1 - Kompositkeramik, die einen konversionsleuchtstoff und ein mit einem negativen thermischen ausdehnungskoeffizienten material enthält - Google Patents
Kompositkeramik, die einen konversionsleuchtstoff und ein mit einem negativen thermischen ausdehnungskoeffizienten material enthältInfo
- Publication number
- EP2831016A1 EP2831016A1 EP13707280.7A EP13707280A EP2831016A1 EP 2831016 A1 EP2831016 A1 EP 2831016A1 EP 13707280 A EP13707280 A EP 13707280A EP 2831016 A1 EP2831016 A1 EP 2831016A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite ceramic
- thermal expansion
- light source
- range
- conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the present invention relates to a composite ceramic and a method for their production. Furthermore, the present invention also relates to the use of the composite ceramic according to the invention as an emission-converting material, preferably in a white light source, as well as a light source, a lighting unit and a display device.
- conversion phosphors are used either in the form of powders or as ceramics in light sources.
- the most well-known conversion phosphors are YAG: Ce (cerium-doped yttrium-aluminum garnet) or LuAG: Ce (cerium-doped lutetium-aluminum garnet), which, due to their emission in the yellow spectral range, allow a white light source when excited by blue light.
- conversion phosphors are used in the form of powders, they have the disadvantage of high backscattering of the emitted light of the light source, so that the "package gain" (possible packing density in a light source) and thus the efficiency is reduced
- the use of rare earth doped conversion phosphors in the form of nanoparticles due to high surface defects and strong agglomeration due to the small particle size leads to the use of conversion-phosphor powders dependent on the particle size, the nanoparticles to reduce the unwanted scattering effects
- certain conversion phosphors used in the form of powders such as YAG: Ce or LuAG: Ce, show a good efficiency due to low scattering effects, the light quantum yield can still be increased here as well.
- Conversion phosphors in the form of ceramics are suitable, for example, for the conversion of high-energy radiation, such as X-ray or Gamma radiation, in visible light.
- Such scintillator ceramics are usually doped with rare earths and consist for example of
- Ce Ce
- Pr Ce
- different cerium-doped ceramics can also be used in light sources, such as LEDs (Light Emitting Devices) as conversion phosphors (WO 2007/107915) to achieve a certain color distribution.
- LEDs Light Emitting Devices
- conversion phosphors WO 2007/107915
- Rare earth doped YAG ceramics known for use in LEDs known (WO 2008/02712).
- the emission of various, doped rare earth garnet compounds (US Pat. No. 2,010,277,673 A1) is also utilized in LCDs (liquid crystal displays) as backlighting.
- LCDs liquid crystal displays
- most conversion phosphors, such as YAG: Ce have low thermal conductivity, the energy lost as heat can not be easily dissipated. This thermal stress leads to defect and crack formation in the ceramic, as a result of which the thermal conductivity decreases even more and the scattering power in turn greatly increases.
- a light source containing such a ceramic as an emission-converting material greatly decreases in efficiency in the course of the operation time.
- composite in “composite ceramics” is intended to take into account the fact that their microstructure has at least two types of grain.
- One grain type is formed by the conversion phosphor and the other grain type by the other material mentioned.
- One grain type is formed by the conversion phosphor and the other grain type by the other material mentioned.
- conversion luminescent material 1 is understood as meaning a material which absorbs radiation in a specific wavelength range of the electromagnetic spectrum, preferably in the blue or UV range, in particular in the blue spectral range, and is visible in another wavelength range of the electromagnetic spectrum Emitted light.
- emission-converting material should be understood in the present application, a material containing at least one conversion phosphor and optionally another material, preferably a material having a negative coefficient of thermal expansion.
- the conversion phosphor is preferably a Ce, Eu and / or Mn-containing material.
- the Ce, Eu and / or Mn-containing material is preferably an inorganic ceramic material, with particular preference being given to a part of the lattice sites of Ce 3+ , Eu 2+ , Eu 3+ and / or Mn 2+ or Mn 4+ ions is occupied.
- the content of Ce, Eu and / or Mn in the Ce-, Eu- and / or Mn-containing material is preferably in the range of 0.01 to 5 atm%, more preferably 0.05 to 3 atm% to the total number of atoms on the lattice sites that the Ce, Eu, and / or Mn in the ce, eu, and / or Mn-containing material replaced, that is, for example, based on Y in YAG.
- Ce, Eu and / or Mn-containing materials which are preferred according to the invention are those which are known per se to the person skilled in the art for their suitability as conversion luminescent material in light-emitting diodes.
- silicates such as ortho-silicates, oxy-ortho-silicates, disilicates, sialones, silicooxynitrides, siliconitrides, aluminates, garnets, and other ternary and quaternary oxides and nitrides.
- the Ce, Eu and / or Mn-containing material is a garnet containing Ce, Eu and / or Mn.
- a garnet is preferably understood to mean rock-forming minerals having a chemical composition of the form
- E are divalent or trivalent cations surrounded by 8 oxygen anions
- G divalent, trivalent or tetravalent cations, preferably trivalent
- T are trivalent or tetravalent cations surrounded by 4 oxygen anions.
- the garnet is preferably a Ce- containing garnet.
- This is understood according to the invention preferably a garnet, in which a part of the cations E is replaced by Ce 3+ ions.
- the Ce-containing garnet is abbreviated as E 3 G 2 (TO 4 ) 3: Ce.
- G and T can also be used for the combination Mg / Si or Mg / Ge or mixtures thereof, wherein Mg and the tetravalent element Si or Ge then present in equal molar proportions.
- thermal expansion coefficient refers to a parameter that describes the behavior of a substance with respect to changes in its dimensions in the event of temperature changes.
- the effect is thermal expansion, which depends on the substance used, ie, it is a material-specific material constant. Its unit of measurement is K '1. If it is positive, then a substance expands as the temperature increases, and if it is a negative quantity, the expansion of the substance decreases as the temperature increases, since for many substances thermal expansion does not occur uniformly over all temperature ranges
- the thermal expansion coefficient itself is also temperature-dependent and is therefore specified for a specific reference temperature or a specific temperature range depends strongly on the microstructure of the ceramic, the value for the composite must be determined experimentally with the help of a dilatometer.
- the change in length of the composite ceramics under the action of heat is measured in accordance with DIN standard 51045. Accordingly, the thermal expansion coefficient of the further material which is present in the composite ceramic and which according to the invention has a negative coefficient of thermal expansion is determined.
- the negative thermal expansion coefficient of the other material is preferably in the range of 1 ⁇ 10 -6 to 2 ⁇ 10 -6 K -1 , particularly preferably in the range of 3 ⁇ 10 -6 to 10 ⁇ 10 -6 at a temperature change in Range from 20 ° C to 200 ° C.
- the further material in the composite material according to the invention which has a negative coefficient of thermal expansion is preferably a tungstate or molybdate or a mixed oxide thereof.
- the additional material is selected from the group consisting of Al2W 3 O 12, Y2W3O12, YAIW 3 0 12 2 0 8 ZrW, AI2M03O12, Y2M03O12 YAIMo 3 0 12 , ZrMo 2 0 8 , AI 2 WMo 2 0 12 , Y 2 WMo 2 0 12 , YAIWMo 2 0 12 , ZrWMo0 8 , AI 2 MoW 2 Oi 2> Y 2 MoW 2 Oi 2> YAIMoW 2 Oi 2 or mixtures thereof. It may also be preferred if the material is coated with the negative thermal expansion coefficient. As a coating, for example, inorganic oxides, such as. For example, alumina or silica. The molar ratio of the conversion phosphor to the other
- Material is preferably in the range from 1: 0.5 to 10: 1, preferably from 1: 1 to 5: 1.
- the exact molar ratio depends, in particular, on how the thermal expansion coefficients of the conversion luminescent material and of the further material relate to one another.
- the conversion phosphor usually has a positive coefficient of thermal expansion and thus expands as the temperature rises. To compensate for this extension, as another
- the coefficient of expansion of the conversion phosphor As the coefficient of expansion of the conversion phosphor is positive, the coefficient of expansion of the other material should be negative. In this ideal case, the two materials should be used in a molar ratio of 0.9: 1 to 1: 0.9. To the extent that the positive coefficient of expansion of the conversion phosphor is greater than the amount of the negative expansion coefficient of the other material, the molar ratio of the two components should be adjusted to each other. In other words, the molar ratio of the two components in the composite ceramic should be approximately in direct proportion to the ratio of
- the present invention also relates to a process for producing a composite ceramic, preferably the composite ceramic according to the invention, comprising the following steps: a) providing a conversion luminescent material;
- the conversion luminescent substance provided in step a) should be defined according to the invention as well as with regard to the composite ceramics according to the invention.
- the conversion luminescent substance is preferably provided here in powder form.
- the average particle size of the conversion phosphor powder is preferably in the range from 0.1 to 1 ⁇ m.
- the material with the negative coefficient of thermal expansion provided in step b) should be defined herein as well as the further material defined with respect to the composting ceramic. It is also preferably used in powder form and its average particle size is preferably in the range of 1 to 10 ⁇ m.
- step c) of the process according to the invention the materials provided under steps a) and b) are mixed together.
- the powders can be mixed together in the dry state or by adding a solvent in the form of a suspension. Suitable solvents are customary solvents, for example ethanol or isopropanol.
- the mixing in step c) is preferably carried out in a ball mill. It is preferable that the mixing is carried out until the average particle size of the powder is in the range of 0.1 to 1 ⁇ m. It is helpful to use special additives to counteract the formation of agglomerates.
- polyelectrolytes used, for. B. Darvan (Vanderbilt), Dolapix (Zschimer and Schwertz), KD1 (Uniqema).
- the powder mixture thus obtained can be further processed.
- the powder mixture is compressed in two stages uniaxially and isostatically in the form of thin slices, wherein the pressing pressure is in the range of 100 to 300 MPa.
- the sintering in step d) takes place according to the invention at a suitable temperature. If the conversion phosphors are provided in step a) without a coating, the sintering takes place at a temperature below the melting point of the material with a negative coefficient of thermal expansion. It has been found that good results are obtained when the sintering temperature is 2/3 to 5/6 of the melting temperature of the negative thermal expansion coefficient material.
- sintering in the region of the melting temperatures or slightly above it.
- sintering is carried out at a temperature in the range of 800 to 1600 ° C, more preferably in the range of 1000 to 1600 ° C.
- the sintering preferably takes place in a sintering furnace.
- the sintering preferably takes place under a protective gas atmosphere (N 2 or Ar), alternatively under a reducing atmosphere, such as forming gas.
- the present invention also relates to an alternative process for producing a composite ceramic, preferably a composite ceramic according to the invention, which comprises the following steps: a ' ) coating a conversion luminescent substance with an oxide of the invention
- step b ' mixing the coated conversion phosphor obtained in step a ' ) with a W or Mo-containing component to obtain a mixture;
- step b' sintering the mixture obtained in step b') at a temperature in the range of 1000 to 1600 ° C, preferably in the range of 1400 to 1600 ° C.
- the conversion luminescent substance provided in step a ' ) should be defined according to the invention as well as with regard to the composite ceramics according to the invention.
- the conversion luminescent substance is preferably provided here in powder form.
- the average particle size of the conversion phosphor powder is preferably in the range of 1 to 10 ⁇ .
- the oxide of the aluminum any oxidic aluminum compound capable of forming a material having a negative coefficient of thermal expansion upon sintering in step c ' ) with the W or Mo-containing compound may be used.
- the oxide of the aluminum Al 2 O 3 is particularly preferably used as ⁇ -modification.
- a W or Mo-containing component is meant an inorganic compound which can be reacted with the oxide of the aluminum by sintering to a material having a negative coefficient of thermal expansion.
- W 3 or M0O 3 are used as W or Mo-containing components.
- the negative coefficient of thermal expansion material shall be defined herein as well as the other material defined with respect to the composite ceramic.
- step c ' By the alternative manufacturing method in step c ' ) a
- Get composite ceramic are surrounded in the particles of the conversion phosphor of the material with the negative coefficient of thermal expansion.
- a further subject of the present invention is the use of the composite ceramic according to the invention or of the composite ceramic produced according to the inventive method as an emission converging material. Due to the presence of a conversion luminescent material in the composite ceramics, the composite ceramics also have the property that light / radiation of one excitation wavelength can be converted into light of a different wavelength.
- the emission-converging material is therefore preferably used in a light source. It is particularly preferred that the light source is or includes an LED (Light Emitting Diode). It is further preferred for the light source to emit white light.
- Another object of the present invention is thus also a light source, a composite ceramic according to the invention or after comprises composite ceramic produced by the process according to the invention.
- the light source may be of any type in which light from a primary light source is to be converted by a conversion phosphor. However, it is preferable that the light source is an LED.
- the primary light source can be a semiconductor chip, a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC, one on an organic light emitting Being a layer-based arrangement (OLED) or a plasma or discharge source, preferably a semiconductor chip, the person skilled in the art is aware of possible forms of such light sources.
- InAIGaN luminescent indium-aluminum-gallium nitride
- the composite ceramic used in the light source is preferably applied in the form of a homogeneous thin and non-porous plate directly to the surface of a primary light source shaped as a chip.
- This has the advantage that no location-dependent variation of the excitation and emission of the conversion phosphor takes place, as a result of which the light source equipped with it emits a homogeneous and color-constant light cone and has a high light output.
- the composite ceramic formed as a ceramic emission-converting molded body has a structured (eg pyramidal) surface on the side opposite a semiconductor chip.
- a structured (eg pyramidal) surface on the side opposite a semiconductor chip.
- the textured surface on the ceramic emission-converting Shaped body is preferably produced in that, for example, during isostatic pressing, the pressing tool has a structured pressing plate and thereby embosses a structure in the surface. Structured surfaces are desired when thin ceramic emission-converting moldings or platelets are to be produced.
- the pressing conditions are known to the person skilled in the art (see J. Kriegsmann, Technische keramische Werkstoffe, Chapter 4, Irishr dienst, 1998).
- Another subject of the invention is a lighting unit, in particular for the backlighting of display devices, which contains at least one light source according to the invention.
- Such lighting units are mainly used in display devices, in particular liquid crystal display devices (LC display), with a backlight. Therefore, such a display device is the subject of the present invention.
- LC display liquid crystal display devices
- the optical coupling between the emission-converting material (composite ceramic) and the primary light source (in particular semiconductor chip) preferably takes place by means of a light-conducting
- the primary light source is installed at a central location and to be optically coupled to the emission-converting material by means of light-conducting devices, such as, for example, photoconductive fibers. In this way, the lighting requirements adapted lights only
- ceramic shaped body is located.
- Example 1 shows the emission spectrum of a comparison material YAG: Ce and a composite ceramic consisting of Y 3 Al 5 0i 2 : Ce and Al 2 W 3 O 1 2 (3: 1), as prepared in Example 3a.
- the spectrum was recorded on an Edinburgh Instruments FL900 fluorescence spectrometer using an Xe medium pressure lamp (Osram) as the excitation source.
- Figure 2 shows the emission spectrum of a comparative material YAG: Ce and a composite ceramic consisting of Y 3 Al 5 O 2 : Ce and YAIW 3 O 12 (3: 1) as prepared in Example 3b.
- the spectrum was recorded on an Edinburgh Instruments FL900 fluorescence spectrometer using an Xe medium pressure lamp (Osram) as the excitation source.
- Example 1 Production of a composite ceramic, consisting of
- the powder components for the composite ceramics ie yttrium aluminate and aluminum tungstate, are prepared separately.
- the starting materials used are metal nitrates Y (NO 3 ) 3 , Al (NO 3 ) 3 , Ce (NO 3 ) 3 for the yttrium aluminate and Al (NO 3 ) 3 with WO 3 in ammonia for aluminum tungstate, which in each case lead to homogeneous solutions be mixed.
- the metal cations in the solutions are stabilized by the addition of a complexing agent (e.g., trisamine) and then evaporated to a solid residue. Further heating of the dry residue causes ignition and formation of a spongy precursor structure.
- a complexing agent e.g., trisamine
- the precursors are calcined at temperatures of 800 to 1000 ° C and converted to the compounds Y 3 -xCe x Al 5 0 12 and Al 2 W 3 0i2 in the form of soft agglomerates.
- the Al 2 W 3 0-i2 powder is coated in a wet-chemical way with Al 2 0 3 , wherein the coating process is realized by the hydrolysis of aluminum isopropylate in alcoholic medium with addition of ammonia as a catalyst in a mixing reactor.
- the two powders are mixed, wherein the volume fraction of the second component is in the range of 10 to 60% by volume and is determined taking into account the dilatometric measurements of the finished ceramics.
- the mixed powder is compressed in two stages uniaxially and isostatically in the form of thin slices, wherein the pressing pressure is in the range of 100 to 300 MPa.
- the subsequent sintering is realized in air as a multi-stage process, the temperatures being in the range of 000 ° C to 1600 ° C.
- the sintered ceramics are ground with a diamond suspension and cut to the excitation source adapted dimensions with a pico-laser.
- Example 2 Production of a composite ceramic, consisting of
- the powder components for the composite ceramics ie magnesium and silicon doped yttrium aluminate and yttrium aluminum tungstate, are prepared separately by a ceramic method.
- the metal oxides in the form of fine powders are mixed, calcined and synthesized at temperatures in the range from 800 ° C to 200 ° C.
- the YAIW 3 0 12 powder is wet-chemically coated with Al 2 O 3 , the coating process being carried out by the hydrolysis of aluminum isopropylate in an alcoholic medium with addition of ammonia as catalyst in a mixing reactor.
- the molding of the mixture was carried out by two-stage uniaxial and isostatic pressing in the form of thin slices, wherein the pressing pressure is in the range of 00 to 300 MPa.
- the subsequent sintering is realized in air as a multi-stage process, with the
- the sintered ceramics are ground with a diamond suspension and cut to the excitation source adapted dimensions with a pico-laser.
- Example 3 Concrete experimentation of the preparation of the composite ceramics from YAG: Ce and a tungstate (Example 3a: AI2W3O12; Example 3b: AIYW 3 0 12 ) Step 1.
- Al 2 W 3 O-i2 powder was prepared by a ceramic method, wherein the fine-grained oxides Al 2 O 3 and WO 3 mixed and in two stages, first at a temperature of 1000 ° C and then at 1100 ° C. were treated (with armörsem). 1.019 g (0.01 mol) of Al 2 O 3 (nano) was ground with 6.955 g (0.003 mol) of WO 3 with ethanol (Achatrmörser). The porridge was dried and in the
- AIYW 3 Oi 2 powder was prepared from the oxides Al 2 O 3 , WO 3 and Y 2 O 3 by a ceramic method, all oxide powders co-agglomerated and two-stage at temperatures 1000 ° C (6 h) and 1100 ° C (12 h) were treated in air. 0.5098 g (0.005 mol) of Al 2 O 3 (nanoscale) was ground with 6.955 g (0.003 mol) of WO 3 and 1.129 g (0.005 mol) of Y 2 O 3 in ethanol.
- the composite material is made of YAG: Ce and Al 2 O 3, and the YAG.Ce is prepared by the self-combustion method.
- the second component is nanopowder of Al2O3
- ceramics of YAG: Ce are produced with undoped YAG.
- the YAG: Ce powder is produced by a co-precision method, using as starting materials the metal nitrates
- the generated precipitate is converted to YAG: Ce by calcining at 800 ° C and sintering at 1000 ° C. After intensive grinding, the YAG.Ce becomes fine-grained and suitable for mixing with the similarly prepared YAG.
- the molding of the mixture was carried out by two-stage uniaxial and isostatic pressing in the form of thin slices, wherein the pressing pressure is in the range of 100 to 300 MPa.
- the subsequent sintering is realized in air as a multistage process with temperatures in the range of 1000 to 1600 ° C.
- the sintered ceramics are ground with a diamond suspension and cut to the excitation source adapted dimensions with a piko laser.
- Example 4 Production of LEDs with the composite ceramics of Examples 3a and 3b and Comparative Examples A and B.
- Example 4a Remote phosphor arrangement
- a wafer of diameter 5 mm and thickness 0.1 mm consisting of the composite ceramic according to the invention is applied to the SMD LED filled with liquid silicone OE 6550 (Dow Corning).
- the component is then stored in an oven at 150 ° C for 1 h, whereby the silicone hardens and bonds firmly to the LED and the ceramic plate.
- a ceramic phosphor plate with square dimensions of 1x1 mm and a thickness of 0.1 mm is with the help of a drop of silicone OE 6550 (Dow Corning) directly to the 1x1 mm LED chip of a SMD flipchip LED (chip peak wavelength 450 nm, operating current 350 mA).
- silicone OE 6550 Dow Corning
- Chip peak wavelength 450 nm, operating current 350 mA chip peak wavelength 450 nm, operating current 350 mA
- Examples 1, 2 and 3 are detectable by the permanent applications in light-emitting diodes.
- the material of the invention exhibits reduced cracking in use compared to prior art ceramics. Accordingly, the efficiency decreases less rapidly, and the ceramic can be used longer with good efficiency.
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| Application Number | Priority Date | Filing Date | Title |
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| EP13707280.7A EP2831016A1 (de) | 2012-03-29 | 2013-03-02 | Kompositkeramik, die einen konversionsleuchtstoff und ein mit einem negativen thermischen ausdehnungskoeffizienten material enthält |
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| EP12002303 | 2012-03-29 | ||
| EP13707280.7A EP2831016A1 (de) | 2012-03-29 | 2013-03-02 | Kompositkeramik, die einen konversionsleuchtstoff und ein mit einem negativen thermischen ausdehnungskoeffizienten material enthält |
| PCT/EP2013/000609 WO2013143645A1 (de) | 2012-03-29 | 2013-03-02 | Kompositkeramik, die einen konversionsleuchtstoff und ein mit einem negativen thermischen ausdehnungskoeffizienten material enthält |
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| EP (1) | EP2831016A1 (enExample) |
| JP (1) | JP6395701B2 (enExample) |
| KR (1) | KR20140148445A (enExample) |
| CN (2) | CN104220398B (enExample) |
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| DE102015102842A1 (de) * | 2015-02-27 | 2016-09-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Leuchtstoffkompositkeramik sowie Verfahren zu deren Herstellung |
| CN105199728B (zh) * | 2015-06-01 | 2017-03-22 | 井冈山大学 | 一种Eu3+和Mn2+共掺杂钨酸盐红色荧光材料 |
| CN108610023B (zh) * | 2016-12-09 | 2021-07-23 | 深圳光峰科技股份有限公司 | 陶瓷复合材料的制备方法、陶瓷复合材料及波长转换器 |
| US11014854B2 (en) | 2017-08-07 | 2021-05-25 | Consolidated Nuclear Security, LLC | Ceramic radiation detector device and method |
| CN109896843A (zh) * | 2017-12-07 | 2019-06-18 | 上海航空电器有限公司 | 用于激光照明的复相陶瓷阵列、制备方法及光源装置 |
| CN109896853B (zh) * | 2017-12-11 | 2022-07-15 | 上海航空电器有限公司 | 具有较低膨胀系数的陶瓷复合体、制备方法及光源装置 |
| CN110386822B (zh) * | 2018-04-19 | 2021-02-26 | 深圳光峰科技股份有限公司 | 一种复相荧光陶瓷及其制备方法 |
| CN112410623B (zh) * | 2019-08-21 | 2022-01-07 | 天津大学 | 一种高阻尼铝硅基复合材料及其制备方法 |
| CN111087173B (zh) * | 2019-12-30 | 2022-11-04 | 厦门天马微电子有限公司 | 一种负膨胀填料及其制备方法和应用 |
| CN112159220B (zh) * | 2020-09-24 | 2022-11-18 | 徐州凹凸光电科技有限公司 | 一种白光led/ld用高热稳定性高量子效率荧光陶瓷及其制备方法 |
| CN114843876B (zh) * | 2022-05-07 | 2025-08-19 | 江苏师范大学 | 一种基于能量传递的低阈值黄光固体激光器 |
| CN116004231A (zh) * | 2023-01-18 | 2023-04-25 | 海南大学 | 一种稀土掺杂的负热膨胀发光材料及其制备方法与应用 |
| CN116355613A (zh) * | 2023-03-31 | 2023-06-30 | 安徽工业大学 | 一种高灵敏度自激活荧光测温材料及其制备方法 |
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| US5919720A (en) | 1997-04-15 | 1999-07-06 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University | Materials with low or negative thermal expansion |
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| KR100764148B1 (ko) * | 2006-01-17 | 2007-10-05 | 루시미아 주식회사 | 시트상 형광체와 그 제조방법 및 이를 이용한 발광장치 |
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2013
- 2013-03-02 CN CN201380017859.7A patent/CN104220398B/zh not_active Expired - Fee Related
- 2013-03-02 CN CN201710538935.9A patent/CN107324795A/zh active Pending
- 2013-03-02 US US14/387,876 patent/US9567519B2/en not_active Expired - Fee Related
- 2013-03-02 WO PCT/EP2013/000609 patent/WO2013143645A1/de not_active Ceased
- 2013-03-02 KR KR1020147029949A patent/KR20140148445A/ko not_active Abandoned
- 2013-03-02 SG SG11201405877UA patent/SG11201405877UA/en unknown
- 2013-03-02 EP EP13707280.7A patent/EP2831016A1/de not_active Withdrawn
- 2013-03-02 JP JP2015502122A patent/JP6395701B2/ja not_active Expired - Fee Related
- 2013-03-28 TW TW102111261A patent/TWI594969B/zh not_active IP Right Cessation
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| J. S. O. EVANS ET AL: "Low-Temperature Oxygen Migration and Negative Thermal Expansion in ZrW 2 - x Mo x O 8", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 122, no. 36, 17 April 2000 (2000-04-17), US, pages 8694 - 8699, XP055424622, ISSN: 0002-7863, DOI: 10.1021/ja0013428 * |
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Also Published As
| Publication number | Publication date |
|---|---|
| US9567519B2 (en) | 2017-02-14 |
| CN104220398A (zh) | 2014-12-17 |
| SG11201405877UA (en) | 2014-11-27 |
| JP2015514144A (ja) | 2015-05-18 |
| TW201348175A (zh) | 2013-12-01 |
| CN104220398B (zh) | 2017-07-28 |
| JP6395701B2 (ja) | 2018-09-26 |
| CN107324795A (zh) | 2017-11-07 |
| TWI594969B (zh) | 2017-08-11 |
| US20150041712A1 (en) | 2015-02-12 |
| KR20140148445A (ko) | 2014-12-31 |
| WO2013143645A1 (de) | 2013-10-03 |
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