TW201307530A - Aluminate phosphor - Google Patents
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- TW201307530A TW201307530A TW100128906A TW100128906A TW201307530A TW 201307530 A TW201307530 A TW 201307530A TW 100128906 A TW100128906 A TW 100128906A TW 100128906 A TW100128906 A TW 100128906A TW 201307530 A TW201307530 A TW 201307530A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 150000004645 aluminates Chemical class 0.000 title claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002602 lanthanoids Chemical group 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 238000010671 solid-state reaction Methods 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 2
- 239000011575 calcium Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 238000009877 rendering Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- -1 lanthanide metals Chemical class 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 3
- 235000013350 formula milk Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 235000020610 powder formula Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77064—Aluminosilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
Description
本發明關於一種螢光粉材料配方，尤指一種可改善其光學性質之以Si/O元素部分取代Al/F元素之鋁酸鹽類化合物螢光粉配方，，可被晶片波長為200~400 nm之紫外光激發，更可藉由Si/O部分取代Al/F元素進行結構微調，改變螢光粉體中鑭系金屬不同價數之存在比例，藉以調控其放光性質，深具應用潛力以及學術價值。The invention relates to a phosphor powder material formulation, in particular to an aluminate compound phosphor powder formula which can replace the Al/F element by Si/O element, which can improve its optical properties, and can be used with a wafer wavelength of 200-400. The ultraviolet light excitation of nm can further fine-tune the structure by replacing the Al/F element with Si/O, and change the proportion of different valence numbers of lanthanide metals in the phosphor powder, thereby regulating the light-emitting property and deep application potential. And academic value.
隨著文明之演進以及節能減碳之環保意識，目前各國正逐步地以發光二極體(Light Emitting Diode,LED)取代傳統光源，因發光二極體具有體積小、耗電量低(為白幟燈泡之十分之一、日光燈之二分之一)、壽命長、發光效率佳、操作反應速度快等優點，可解決傳統光源難以克服之問題，因此目前已應用在號誌燈、汽車光源、顯示器等元件，由於其符合現今強調之綠色環保概念，被譽為二十一世紀之「綠色照明光源」。With the evolution of civilization and the environmental awareness of energy saving and carbon reduction, countries are gradually replacing traditional light sources with Light Emitting Diodes (LEDs), which have small size and low power consumption (for white One-tenth of the bulb, one-half of the fluorescent lamp, long life, good luminous efficiency, fast response, etc., can solve the problem that traditional light sources are difficult to overcome, so it has been applied to the number of lights, car light source Components such as monitors are known as the "green lighting source" of the 21st century because they conform to the green concept of today's emphasis.
日本日亞(Nichia)化學公司於1996年提出藉由藍光LED激發鈰摻雜之釔鋁石榴石(Cerium-doped yttrium aluminum garnet；YAG:Ce)螢光粉產生黃色螢光，其與藍光混合後可產生冷白光，此為第一顆白光二極體，然而由於此白光缺乏紅光成分，故其演色性低，且此專利為日亞專利所限制。由於白光二極體須具全光譜波段放光才能達到高演色性以及理想色溫，除藍光二極體搭配YAG以及紅色螢光粉之外，亦有藍光二極體搭配綠色、紅色螢光粉以及UV-LED搭配藍綠紅三色螢光粉等混成白光方式，其中若要產生理想之色溫(暖白光)，UV-LED搭配三色螢光粉具有較佳之放光效率，故開發適合紫外光激發之藍色、綠色、紅色螢光粉為目前首要之研究課題。Japan's Nichia Chemical Co., Ltd. proposed in 1996 to generate yellow fluorescence by cerium-doped yttrium aluminum garnet (YAG:Ce) phosphor powder excited by blue LED, which is mixed with blue light. It can produce cool white light, which is the first white light diode. However, since this white light lacks red light component, its color rendering property is low, and this patent is limited by the Japanese patent. In addition to the blue light diode with YAG and red fluorescent powder, there are also blue light diodes with green and red fluorescent powder, as white light diodes must have full spectral band emission to achieve high color rendering and ideal color temperature. UV-LED is mixed with blue, green and red three-color fluorescent powder to form a white light method. In order to produce an ideal color temperature (warm white light), UV-LED with three-color fluorescent powder has better light-emitting efficiency, so it is suitable for ultraviolet light. The blue, green and red fluorescent powders that are stimulated are the primary research topics at present.
目前螢光粉相關之研究除新主體晶格之開發外，在一主體晶格中摻雜其他元素取代原本之主體晶格元素藉以改善發光性亦為常見之研究方向，例如Duan等人於2011年在Chemistry of material期刊上(Chemistry Materials,dx.doi.org/10.1021/cm103495j)發表Re2Si4N6C(RE=Lu,Y,Gd)系列螢光粉之研究，即使用RE/C取代原本於MRESi4N7中之M/N(M=Ba,Sr,Ca)，利用C元素之共價性以及其較剛性之鍵結特性藉以改善主體晶格的穩定性，故藉由不同元素之取代以調適螢光粉發光性質以及穩定性亦為目前主要之研究目標。At present, in addition to the development of new host lattices, it is also a common research direction to replace other primitive lattice elements in a host lattice to improve luminescence, such as Duan et al. Research on the Re 2 Si 4 N 6 C (RE=Lu, Y, Gd) series of phosphors published in the Journal of Chemistry of materials (Chemistry Materials, dx.doi.org/10.1021/cm103495j), using RE/C Substituting M/N (M=Ba, Sr, Ca) originally in MRESi 4 N 7 , using the covalent nature of C element and its more rigid bonding characteristics to improve the stability of the host lattice, so by different The substitution of elements to adjust the luminescent properties and stability of fluorescent powder is also the main research goal at present.
Yu等人於1997年在Cement and Concrete Research期刊上(Cement Concrete Res,1997,27,1439-1449)發表Ca12Al14O32F2的製備方式以及單晶結構，其結構以[AlO4]的四面體構成，其單位晶胞屬正方晶系，空間群為I43d，四面體之間以氧原子作為橋接，鈣原子與六個氧及一個氟原子配位，屬七配位，由於結構中形成之空缺格位由氟原子填補，此晶體相較於Ca12A7結構將更具穩定性，適合應用於螢光粉。Yu et al., 1997, in the journal Cement and Concrete Research (Cement Concrete Res, 1997, 27, 1439-1449), published the preparation of Ca 12 Al 14 O 32 F 2 and single crystal structure with [AlO 4 ] The tetrahedron is composed of a unit cell which belongs to the orthorhombic system and a space group of I43d. The tetrahedron is bridged by an oxygen atom, and the calcium atom is coordinated with six oxygen and one fluorine atom, which belongs to the seven-coordinated position. The formed vacancy is filled by fluorine atoms, which is more stable than the Ca 12 A 7 structure and is suitable for use in fluorescent powders.
本發明之一目的，旨在提供一種更具穩定性之螢光粉。It is an object of the present invention to provide a more stable phosphor.
本發明之次一目的，旨在提供一種可增進演色性之螢光粉。A second object of the present invention is to provide a phosphor which enhances color rendering.
本發明之另一目的，旨在提供一種簡化製程以及降低成本之螢光粉。Another object of the present invention is to provide a phosphor which simplifies the process and reduces the cost.
為達上述目的，本發明揭示之鋁酸鹽類化合物螢光粉，係在燒結溫度T及燒結壓力P之條件下以固態反應法合成，其配方為CaaSrbBacAldSieOfFgRh，其中10≦a+b+c+h≦12(0≦a＜12；0≦b＜12；0≦c＜12；0＜h≦1)、12＜d+e≦14(12≦d＜14；0＜e≦2)、30≦f≦34；、0＜g≦2，R為鑭系金屬類之元素，作為螢光粉之發光中心。其中，此固態反應法所使用的燒結溫度T為1000～1400℃，燒結壓力Y為0.1～0.9MPa。該螢光粉可被波長為200~400 nm之發光二極體激發，且其放射波長為400-700nm。其中，鑭系金屬元素R為Ce、Eu、Pr、Nd、Sm、Tb、Er、Yb、Dy其中之一者，以導致不同範圍之放光。In order to achieve the above object, the aluminate compound fluorescent powder disclosed by the present invention is synthesized by a solid state reaction method under the conditions of a sintering temperature T and a sintering pressure P, and the formulation thereof is Ca a Sr b Ba c Al d Si e O f F g R h , where 10≦a+b+c+h≦12(0≦a<12;0≦b<12;0≦c<12;0<h≦1),12<d+e≦ 14 (12≦d<14;0<e≦2),30≦f≦34; and 0<g≦2, R is an element of a lanthanide metal, and serves as a luminescent center of the phosphor powder. Among them, the sintering temperature T used in the solid state reaction method is 1000 to 1400 ° C, and the sintering pressure Y is 0.1 to 0.9 MPa. The phosphor powder can be excited by a light-emitting diode having a wavelength of 200 to 400 nm and has a radiation wavelength of 400 to 700 nm. Wherein, the lanthanide metal element R is one of Ce, Eu, Pr, Nd, Sm, Tb, Er, Yb, Dy to cause different ranges of light emission.
本發明所揭示之螢光粉，可藉由Si/O部分取代Al/F進行結構微調，透過放光中心配位環境之改變，調變鑭系金屬在晶格中不同價數之存在比例，進而控制其光學性質，且其放光範圍可同時涵蓋藍綠光以及紅光，搭配UV-LED合成白光可增進其演色性，使用較少種類之粉體亦可簡化製程以及降低成本，深具應用潛力及學術價值。The phosphor powder disclosed in the present invention can be finely tuned by substituting Si/O for Al/F, and the ratio of the different valences of the lanthanide metal in the crystal lattice can be modulated by the change of the coordination environment of the light-emitting center. In turn, its optical properties are controlled, and its light-emitting range can cover both blue-green and red light. The combination of UV-LED and white light can enhance its color rendering. Using fewer types of powder can simplify the process and reduce the cost. Application potential and academic value.
為使 貴審查委員能清楚了解本發明之內容，謹以下列說明搭配圖式，敬請參閱。In order for your review board to have a clear understanding of the contents of the present invention, please refer to the following description for matching drawings.
本發明之鋁酸鹽類化合物螢光粉係以固態反應法製備而成，其燒結溫度T為1000～1400℃，且燒結壓力P為0.1～0.9 MPa。以化學式CaaSrbBacAldSieOfFgRh表示，其中10≦a+b+c+h≦12(0≦a＜12；0≦b＜12；0≦c＜12；0＜h≦1)、12＜d+e≦14(12≦d＜14；0＜e≦2)、30≦f≦34；、0＜g≦2，其中R為鑭系金屬元素Ce、Eu、Pr、Nd、Sm、Tb、Er、Yb、Dy其中之一者。本發明較佳實施例(A)~(E)係為Ca11.9Al14-xSixO32+XF2-x:Eu0.1(x=0.1、0.2、0.3、0.5、0.6)樣品，配方如下表所示：The aluminate compound fluorescent powder of the present invention is prepared by a solid state reaction method, and has a sintering temperature T of 1000 to 1400 ° C and a sintering pressure P of 0.1 to 0.9 MPa. It is represented by the chemical formula Ca a Sr b Ba c Al d Si e O f F g R h , where 10≦a+b+c+h≦12(0≦a<12;0≦b<12;0≦c<12;0<h≦1),12<d+e≦14(12≦d<14;0<e≦2),30≦f≦34;,0<g≦2, where R is a lanthanide metal element Ce One of Eu, Pr, Nd, Sm, Tb, Er, Yb, Dy. Preferred embodiments (A) to (E) of the present invention are Ca 11.9 Al 14-x Si x O 32+X F 2-x :Eu 0.1 (x= 0.1, 0.2, 0.3, 0.5, 0.6 ) samples, formulations As shown in the following table:
請參閱第1圖，係為本發明較佳實施例(A)~(E)之X光粉末繞射圖譜。根據本發明實施例(A)~(E)所製備之Ca11.9Al14-xSixO32+XF2-x:Eu0.1(x=0.1、0.2、0.3、0.5、0.6)樣品，以X光粉末繞射圖譜鑑定其晶相純度，可發現本發明所合成之螢光粉為純相。Please refer to Fig. 1 for the X-ray powder diffraction pattern of the preferred embodiments (A) to (E) of the present invention. Samples of Ca 11.9 Al 14-x Si x O 32+X F 2-x :Eu 0.1 (x= 0.1, 0.2, 0.3, 0.5, 0.6 ) prepared according to the examples (A) to (E) of the present invention, The purity of the crystal phase was identified by X-ray powder diffraction pattern, and the phosphor powder synthesized by the present invention was found to be a pure phase.
請參閱第3A、3B圖所示之本發明較佳實施例(A)~(E)之激發光譜圖(一)、(二)。本發明實施例(A)~(E)所製備之Ca11.9Al14-xSixO32+XF2-x:Eu0.1(x=0.1、0.2、0.3、0.5、0.6)樣品，可被波長200～400nm之發光二極體所激發，尤隨著Si/O量之增加，波長250nm及325nm附近之光譜激發效果更加顯著。Please refer to the excitation spectra (1) and (2) of the preferred embodiments (A) to (E) of the present invention shown in Figs. 3A and 3B. The sample of Ca 11.9 Al 14-x Si x O 32+X F 2-x :Eu 0.1 (x= 0.1, 0.2, 0.3, 0.5, 0.6 ) prepared by the embodiments (A) to (E) of the present invention can be Excited by a light-emitting diode having a wavelength of 200 to 400 nm, the spectral excitation effect at wavelengths of 250 nm and 325 nm is more remarkable as the amount of Si/O increases.
請參考第2圖及第4圖所示之本發明較佳實施例(A)~(E)之放射光譜圖及色度座標圖。如圖中所現，可得知本發明實施例(A)~(E)所製備之Ca11.9Al14-xSixO32+XF2-x:Eu0.1(x=0.1、0.2、0.3、0.5、0.6)樣品，其放射波長為400～700 nm，且隨Si/O部分取代Al/F量之改變，結構微調可控制Eu2+/Eu3+之比例，進而調整藍綠光以及紅光範圍之放光強度，隨著Si/O微量增加而Al/F相應減少，藍綠光之強度呈現極大之增長，而紅光強度則相應削減。另，將其放射光譜數據以國際照明委員會制定之色度座標圖進行公式換算，得到各螢光粉之色度座標，分別標示於座標圖上，可窺知本較佳實施例合成之Ca11.9Al14-xSixO32+XF2-x:Eu0.1隨x值上升，可將放光由紅光範圍調適至藍光範圍。Please refer to the radiation spectrum diagram and the chromaticity coordinate diagram of the preferred embodiments (A) to (E) of the present invention shown in Figs. 2 and 4. As shown in the figure, it can be seen that Ca 11.9 Al 14-x Si x O 32+X F 2-x :Eu 0.1 (x= 0.1, 0.2, 0.3 ) prepared by the embodiments (A) to (E) of the present invention. , 0.5, 0.6) samples with a radiation wavelength of 400-700 nm, and the structure fine-tuning can control the ratio of Eu 2+ /Eu 3+ with the change of the Si/O partial substitution of Al/F, and then adjust the blue-green light and The intensity of the red light range increases with the increase of Si/O amount, and the intensity of blue-green light increases greatly, while the intensity of red light decreases accordingly. In addition, the radiation spectrum data is converted by the formula of the chromaticity coordinate map formulated by the International Commission on Illumination, and the chromaticity coordinates of each phosphor powder are obtained, which are respectively marked on the coordinate map, and the Ca 11.9 synthesized in the preferred embodiment can be seen. Al 14-x Si x O 32+X F 2-x :Eu 0.1 increases with the value of x, and the light emission can be adjusted from the red light range to the blue light range.
據此，本發明所揭示之螢光粉，可藉由Si/O部分取代Al/F進行結構微調，透過放光中心配位環境之改變，調變鑭系金屬在晶格中不同價數之存在比例，進而控制其光學性質，且其放光範圍可同時涵蓋藍綠光以及紅光，搭配UV-LED合成白光可增進其演色性，且本較佳實施例之鋁酸鹽類化合物螢光粉Ca11.9Al14-xSixO32+XF2-x:Eu0.1，其使用之原料涵蓋CaCO3、Al2O3、SiO2、CaF2、Eu2O3，依配方稱取適當原料於研缽均勻混合研磨後，置於1250℃下、氫(5%)-氮(95%)氣氛下燒結6小時，即可得產物。製作過程簡單，利於大量生產，使用較少種類之粉體亦可簡化製程以及降低成本，深具應用潛力及學術價值。Accordingly, the phosphor powder disclosed in the present invention can be finely tuned by substituting Si/O for Al/F, and the valence of the lanthanide metal in the crystal lattice can be modulated by the change of the coordination environment of the light-emitting center. There is a ratio, which in turn controls its optical properties, and its light-emitting range can cover both blue-green light and red light. Synthesizing white light with UV-LED can enhance its color rendering, and the aluminate compound of the preferred embodiment is fluorescent. Powder Ca 11.9 Al 14-x Si x O 32+X F 2-x :Eu 0.1, the raw materials used thereof cover CaCO 3 , Al 2 O 3 , SiO 2 , CaF 2 , Eu 2 O 3 , according to the formula The raw materials were uniformly mixed and ground in a mortar, and then sintered at 1250 ° C under a hydrogen (5%)-nitrogen (95%) atmosphere for 6 hours to obtain a product. The production process is simple, which is conducive to mass production. The use of less kinds of powders can simplify the process and reduce the cost, and has potential application and academic value.
本申請案所列舉之各實施例僅為本發明之較佳具體實施例，並非用以限制本發明之範圍。任何人在不超脫本發明之精神範圍所作之修飾或變更皆應涵蓋於本發明之專利範圍內。The embodiments of the present invention are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Modifications or variations made by any person without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
第1圖，係為本發明較佳實施例(A)～(E)其X光粉末之繞射圖譜。Figure 1 is a diffraction pattern of the X-ray powder of the preferred embodiments (A) to (E) of the present invention.
第2圖，係為本發明較佳實施例(A)～(E)之放射光譜圖。Fig. 2 is a radiation spectrum diagram of preferred embodiments (A) to (E) of the present invention.
第3A圖，係為本發明較佳實施例(A)～(E)之激發光譜圖(一)。Fig. 3A is an excitation spectrum diagram (I) of preferred embodiments (A) to (E) of the present invention.
第3B圖，係為本發明較佳實施例(A)～(E)之激發光譜圖(二)。Fig. 3B is an excitation spectrum diagram (2) of preferred embodiments (A) to (E) of the present invention.
第4圖，係為本發明較佳實施例(A)～(E)之色度座標圖。Fig. 4 is a chromaticity coordinate diagram of preferred embodiments (A) to (E) of the present invention.
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| TW100128906A TWI432555B (en) | 2011-08-12 | 2011-08-12 | Aluminate phosphor |
| CN2011102894378A CN102925145A (en) | 2011-08-12 | 2011-09-27 | aluminate compound fluorescent powder |
| JP2011246358A JP5563542B2 (en) | 2011-08-12 | 2011-11-10 | Aluminate compound phosphor |
| KR1020110130741A KR101331302B1 (en) | 2011-08-12 | 2011-12-08 | Aluminate compound phosphor |
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| CN107987828A (en) * | 2017-12-29 | 2018-05-04 | 河北工业大学 | A kind of mayenite structure fluorescent powder of LED white light emissions |
| CN112225450B (en) * | 2020-09-23 | 2022-10-28 | 中国计量大学 | Lanthanide-doped wide-color-gamut fluorescent glass and preparation method thereof |
| CN115491196B (en) * | 2022-11-21 | 2023-03-24 | 四川世纪和光科技发展有限公司 | Red light fluorescent composition, red light fluorescent film and red light LED light source |
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| NL7504440A (en) * | 1975-04-15 | 1976-10-19 | Philips Nv | LUMINESCENT SCREEN. |
| NL7903102A (en) * | 1979-04-20 | 1980-10-22 | Philips Nv | LUMINESCENT FABRIC WITH NATURAL ALKALINE SILICATE ALUMINATE GRID. |
| US7351281B2 (en) * | 2001-09-26 | 2008-04-01 | Doxa Aktiebolag | Powdered material and ceramic material manufactured therefrom |
| US7575697B2 (en) * | 2004-08-04 | 2009-08-18 | Intematix Corporation | Silicate-based green phosphors |
| MX2007012960A (en) * | 2005-04-20 | 2008-03-24 | Etech Ag | Novel materials used for emitting light. |
| CN101208407A (en) * | 2005-04-20 | 2008-06-25 | 易特斯股份公司 | Novel materials used for emitting light |
| JP4931176B2 (en) * | 2005-09-14 | 2012-05-16 | 株式会社アルバック | Phosphor, method for manufacturing the same, and light emitting device |
| KR101497104B1 (en) * | 2006-10-03 | 2015-02-27 | 라이트스케이프 머티어리얼스, 인코포레이티드 | Metal silicate halide phosphors and led lighting devices using the same |
| TWI359857B (en) * | 2006-12-25 | 2012-03-11 | Ind Tech Res Inst | White light illumination device |
| TW201005075A (en) * | 2008-07-24 | 2010-02-01 | Univ Nat Chiao Tung | White-emitting phosphors and lighting apparatus thereof |
| KR20100070731A (en) | 2008-12-18 | 2010-06-28 | 삼성전자주식회사 | Halosilicate phosphors and white light emitting devices including same |
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