TWI383034B - Two-phase silicate-based yellow phosphor - Google Patents

Two-phase silicate-based yellow phosphor Download PDF

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TWI383034B
TWI383034B TW95138585A TW95138585A TWI383034B TW I383034 B TWI383034 B TW I383034B TW 95138585 A TW95138585 A TW 95138585A TW 95138585 A TW95138585 A TW 95138585A TW I383034 B TWI383034 B TW I383034B
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phosphor
phase
composition
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TW200728434A (en
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Yi-Qun Li
Yi Dong
Shifan Cheng
Dejie Tao
Ning Wang
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Intematix Corp
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Description

二相以矽酸鹽為主的黃色磷光體Two-phase yellow phosphor based on citrate

本發明實施例總體係關於一種二相以矽酸鹽為主的光致發光材料。更具體而言,本發明實施例係關於包含兩個以矽酸鹽為主之相之發黃光磷光體,該磷光體在高亮度白光LED照明系統、LCD顯示面板、電漿顯示面板及黃光照明系統中皆有應用。The total system of the present invention relates to a two-phase bismuth silicate-based photoluminescent material. More specifically, embodiments of the present invention relate to a yellow-emitting phosphor comprising two bismuth-based phases, the phosphor in a high-brightness white LED illumination system, an LCD display panel, a plasma display panel, and a yellow There are applications in light lighting systems.

白光LED在業內已為人習知,且相對而言其係近期之創新。直至開發出可在電磁波譜之藍光/紫外光區域發光之LED,才使製作基於LED之白光照明源成為可能。在經濟上,白光LED具有替代白熾光源(燈泡)之潛力,尤其當生產成本降低及技術進一步發展時。具體而言,據信白光LED在使用壽命、堅固性及效率方面皆有優於白熾燈泡之潛力。舉例而言,預計基於LED之白光照明源可滿足運行壽命為100,000小時及效率為80至90%之工業標準。高亮度LED業已對諸如交通燈信號等領域形成實質影響,替代了白熾燈,且因此無需驚訝不久其將滿足家庭及商業以及其他日常應用領域中的普遍照明要求。White LEDs are well known in the industry and relatively recent innovations. Until the development of LEDs that emit light in the blue/ultraviolet region of the electromagnetic spectrum, it is possible to make LED-based white light sources. Economically, white LEDs have the potential to replace incandescent light sources (bulbs), especially when production costs are reduced and technology is further developed. In particular, it is believed that white LEDs have the potential to outperform incandescent bulbs in terms of lifetime, robustness and efficiency. For example, LED-based white light illumination sources are expected to meet industry standards of 100,000 hours of operating life and 80 to 90% efficiency. High-brightness LEDs have had a substantial impact on areas such as traffic light signals, replacing incandescent lamps, and so it is not surprising that they will soon meet the general lighting requirements in home and business and other everyday applications.

現有若干製造基於發光磷光體之白光照明系統之通用方法。至今,多數白光LED市售產品皆依據圖1所示方法製造,其中來自一輻射源之光線對白光照明之顏色輸出產生影響。參見圖1之系統10,一輻射源11(其可係一LED)發出位於電磁波譜可見部分之光線12、15。光線12及15係相同光線,但出於例示之目的而顯示為兩個分開的光束。自輻射源11發射的一部分光線,即光線12激發一磷光體13,該磷光體係一可自輻射源11吸收能量後發射光線14之光致發光材料。光線14可係一位於光譜黃光區域之實質單色光線,或其可係一綠光與紅光、綠光與黃光、或黃光與紅光等之組合。輻射源11亦發出不被磷光體13吸收的可見光中之藍光;其係圖1中所示的可見藍光15。可見藍光15與黃光14混合以提供該圖中所示之所期望之白光照明16。There are several general methods for fabricating white light illumination systems based on luminescent phosphors. To date, most white LED commercial products have been manufactured according to the method shown in Figure 1, in which light from a source of light has an effect on the color output of white light illumination. Referring to system 10 of Figure 1, a radiation source 11 (which can be an LED) emits light rays 12, 15 located in the visible portion of the electromagnetic spectrum. Light rays 12 and 15 are the same light, but are shown as two separate beams for illustrative purposes. A portion of the light emitted from the radiation source 11, i.e., the light 12, excites a phosphor 13 which, upon absorption of energy from the radiation source 11, emits the photoluminescent material of the light 14. The light 14 can be a substantially monochromatic light in the yellow region of the spectrum, or it can be a combination of green and red, green and yellow, or yellow and red. The radiation source 11 also emits blue light in visible light that is not absorbed by the phosphor 13; it is the visible blue light 15 shown in FIG. It can be seen that the blue light 15 is mixed with the yellow light 14 to provide the desired white light illumination 16 as shown in the figure.

或者,已有一更新方法係使用發出紫外(UV)光之非可見光輻射源。此概念繪示於圖1B中,該圖闡明一包括輻射源之照明系統,該輻射源發出非可見光使得來自該輻射源之光線實質不對由該照明系統所產生之光線產生影響。參照圖1B,自輻射源21發出實質不可見光線,呈光線22、23形式。光線22與光線23特徵相同,但使用兩個不同的參考數字來說明以下這一點:光線22可用於激發一磷光體,例如磷光體24或25,但自輻射源21發出之光23不撞擊磷光體,不對來自該(等)磷光體之色彩輸出28產生影響,此乃因人眼實質看不見光線23。Alternatively, an updated method has used a source of non-visible radiation that emits ultraviolet (UV) light. This concept is illustrated in Figure 1B, which illustrates an illumination system that includes a source of radiation that emits non-visible light such that light from the source of radiation does not substantially affect the light produced by the illumination system. Referring to FIG. 1B, a substantially invisible line is emitted from the radiation source 21 in the form of rays 22, 23. Light 22 is of the same characteristic as light 23, but uses two different reference numerals to illustrate the point that light 22 can be used to excite a phosphor, such as phosphor 24 or 25, but light 23 from radiation source 21 does not strike phosphorescence. The body does not affect the color output 28 from the (etc.) phosphor, because the light 23 is invisible to the human eye.

需要優於先前技術之以矽酸鹽為主的黃色磷光體之改良,其中該改良至少部分表現為藍色光激發光線轉化成來自該磷光體之期望黃光輸出之轉化效率與先前技術相等或大於其。亦期望該磷光體具有高達200℃之溫度穩定性及增強的演色性。而且,對提高製造產率而言關鍵是提供一在約400奈米至約480奈米之波長範圍內具有寬廣且一致的激發效率之黃色磷光體。具有整體高性能及低成本之所期望之黃色磷光體可同一藍光LED一起使用從而產生高亮度白光,其色彩輸出不隨溫度改變且其色彩混合可產生所期望之一致的色溫及演色性指數。There is a need for an improvement over the prior art citrate-based yellow phosphor, wherein the improvement is at least partially manifested by the conversion efficiency of the blue photoexcitation light into a desired yellow light output from the phosphor that is equal to or greater than the prior art. its. It is also desirable for the phosphor to have temperature stability up to 200 ° C and enhanced color rendering. Moreover, it is critical to increase manufacturing yield to provide a yellow phosphor having broad and consistent excitation efficiencies in the wavelength range from about 400 nanometers to about 480 nanometers. The desired yellow phosphor with overall high performance and low cost can be used with the same blue LED to produce high brightness white light, the color output does not change with temperature and its color mixing produces the desired consistent color temperature and color rendering index.

本發明實施例係關於在其組合物中具有兩個不同相之黃色磷光體,該等相通常由式(M1)2 SiO4 及(M2)3 SiO5 表示,其中M1及M2各自可係一鹼土金屬。當本發明磷光體受到一可發射介於約220奈米至約530奈米間輻射之輻射源激發時,其具有一波長介於約555奈米至約580奈米間之峰值發射強度。本發明黃色磷光體經構造以吸收UV至波長小於約530奈米之可見光線,且可由具有介於約360奈米與約520奈米間大範圍波長之光線以大約一致發射強度激發。The present invention relates to a yellow phosphor having two different phases in its composition, which are generally represented by the formula (M1) 2 SiO 4 and (M2) 3 SiO 5 , wherein each of M1 and M2 can be rare earth metal. When the phosphor of the present invention is excited by a radiation source that emits radiation between about 220 nanometers and about 530 nanometers, it has a peak emission intensity at a wavelength between about 555 nanometers and about 580 nanometers. The yellow phosphor of the present invention is configured to absorb UV light to visible light having a wavelength of less than about 530 nm and can be excited by approximately uniform emission intensity from light having a wide range of wavelengths between about 360 nm and about 520 nm.

具體而言,本發明黃色磷光體包括一呈化學計算關係之二相以矽酸鹽為主的具有至少一種二價鹼土金屬元素M1或M2(其係Mg、Ca、Ba或Zn)之化合物,該化學計算關係通常由式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D表示,其中M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬。該式中間之圓點表明該化合物中SiO4 及SiO5 部分於該材料中形成兩個不同相。a、x、y、z及u之值符合下列關係:0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;及2.6u3.3。銪(Eu)及陰離子D之量各自介於約0.001至約0.5之間。該陰離子D係選自由F、Cl、Br、S及N組成之群,且其專門替代該二相磷光體之二相中任一相之晶格中的氧陰離子。該等磷光體經構造以發射峰值發射波長介於約555奈米與580奈米間之可見光。Specifically, the yellow phosphor of the present invention comprises a compound having a stoichiometric relationship of two phases, preferably a phthalate, having at least one divalent alkaline earth metal element M1 or M2 (which is Mg, Ca, Ba or Zn). The stoichiometric relationship is generally represented by the formula a[Sr x (M1) 1 - x ] z SiO 4 ●(1-a)[Sr y (M2) 1 - y ] u SiO 5 :Eu 2 + D, where M1 and M2 is at least one divalent metal selected from the group consisting of Ba, Mg, Ca, and Zn. The dot in the middle of the formula indicates that the SiO 4 and SiO 5 moieties in the compound form two distinct phases in the material. The values of a, x, y, z, and u are in the following relationship: 0.6 a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5; and 2.6 u 3.3. The amounts of ruthenium (Eu) and anion D are each between about 0.001 and about 0.5. The anion D is selected from the group consisting of F, Cl, Br, S, and N, and it specifically replaces the oxygen anion in the crystal lattice of any of the two phases of the two-phase phosphor. The phosphors are configured to emit visible light having a peak emission wavelength between about 555 nm and 580 nm.

本發明另一實施例中,黃色磷光體可用於白光LED中。此一白光照明系統包括一經構造可發射波長大於約280奈米之輻射之輻射源;及一二相以矽酸鹽為主的黃色磷光體,該磷光體經構造可吸收來自該輻射源之輻射的至少一部分並發射具有波長介於550奈米至約580奈米間之峰值強度的光線。該黃色磷光體具有式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D,其中M1、M2、x、y、z及u係如上定義。In another embodiment of the invention, a yellow phosphor can be used in a white LED. The white light illumination system includes a radiation source configured to emit radiation having a wavelength greater than about 280 nm; and a two-phase yellow phosphor dominated by niobate, the phosphor configured to absorb radiation from the radiation source At least a portion of the light is emitted with a peak intensity having a wavelength between 550 nm and about 580 nm. The yellow phosphor has the formula a[Sr x (M1) 1 - x ] z SiO 4 ● (1-a) [Sr y (M2) 1 - y ] u SiO 5 :Eu 2 + D, where M1, M2 x, y, z, and u are as defined above.

合成本發明黃色磷光體之方法包括溶膠-凝膠方法、固體反應方法及共沉澱方法。該等方法通常包括將該等金屬及類金屬鹽溶於一以水為主之溶液中,並使所有組份一起沉澱。該沉澱可包括於原子水平混合之該等金屬之羥基化物及羧酸鹽之溶液。該溶液可包括一可替代晶格點上之氧之鹵素摻雜劑。The method of synthesizing the yellow phosphor of the present invention includes a sol-gel method, a solid reaction method, and a coprecipitation method. Such methods generally involve dissolving the metal and metalloid salts in a water-based solution and allowing all components to precipitate together. The precipitate may comprise a solution of a hydroxylate and a carboxylate of the metals mixed at the atomic level. The solution can include a halogen dopant that can replace the oxygen on the lattice points.

一實例性共沉澱方法包括:a)將Sr(NO3 )3 、(M1)(NO3 )2 及(M2)(NO3 )2 溶於水中;b)將Eu2 O3 溶於硝酸中;c)將SrF2 溶於硝酸中;d)混合由步驟a)、b)及c)所產生之溶液;e)將(CH3 O)4 Si加至步驟d)所產生之溶液中,且隨後將一酸加至該混合物中以引發沉澱;f)將步驟e)之混合物之pH值調節至約9;g)對步驟f)之反應產物加以乾燥,且隨後煆燒該反應產物以分解沉澱物;及h)在還原氣氛下燒結步驟g)之沉澱物。An exemplary coprecipitation method comprises: a) dissolving Sr(NO 3 ) 3 , (M1)(NO 3 ) 2 and (M2)(NO 3 ) 2 in water; b) dissolving Eu 2 O 3 in nitric acid ; c) dissolving SrF 2 in nitric acid; d) mixing the solution produced by steps a), b) and c); e) adding (CH 3 O) 4 Si to the solution produced in step d), And then adding an acid to the mixture to initiate precipitation; f) adjusting the pH of the mixture of step e) to about 9; g) drying the reaction product of step f), and then calcining the reaction product Decomposing the precipitate; and h) sintering the precipitate of step g) under a reducing atmosphere.

激發光譜顯示當本發明黃色磷光體在介於約200至540奈米之波長下受到激發時可有效發射螢光。本發明黃色磷光體提供具有優於先前技術磷光體之處之發射特性,該等優點包括更高發光效率及更佳溫度穩定性二者,以及在較大激發波長範圍內之發射一致性。該等激發波長介於約400奈米至約500奈米之間。The excitation spectrum shows that the yellow phosphor of the present invention can effectively emit fluorescence when excited at a wavelength of between about 200 and 540 nm. The yellow phosphors of the present invention provide emission characteristics superior to those of prior art phosphors, including both higher luminous efficiency and better temperature stability, as well as emission uniformity over a larger range of excitation wavelengths. The excitation wavelengths are between about 400 nanometers and about 500 nanometers.

本說明書中論述改變主晶格中鹼土金屬與矽之比率之影響、鹼土金屬之種類、Eu活化劑含量之影響及鹵素摻雜劑之作用。In this specification, the effect of changing the ratio of alkaline earth metal to cerium in the host lattice, the type of alkaline earth metal, the content of Eu activator, and the role of the halogen dopant are discussed.

本發明新穎磷光體包含以二相矽酸鹽為主之化合物。其可用於許多應用領域,包括白光LED系統、黃色照明系統及色彩顯示面板之組件,包括用於電漿顯示面板之RGB(紅、綠、藍)背後照明系統之組件。本發明磷光體在於較高接合溫度下作業之高功率LED封裝中具有特殊應用。The novel phosphor of the present invention comprises a compound based on a dibasic citrate. It can be used in many applications, including components for white LED systems, yellow lighting systems, and color display panels, including components for RGB (red, green, blue) backlight systems for plasma display panels. The phosphors of the present invention have particular applications in high power LED packages that operate at higher junction temperatures.

本發明二相以矽酸鹽為主的磷光體之多種實施例將以下列次序加以闡述:首先,對該等二相以矽酸鹽為主的新穎組合物進行概述,然後詳細闡述該矽酸鹽主晶格之結晶性質,改變晶格中鹼土金屬與矽的相對量之影響,及改變不同鹼土金屬之相對量之影響。然後論述在組合物的至少一相中之活化劑二價銪(Eu2 ),並揭示含有元素F、Cl、Br、S及N中的一種或多種之摻雜劑D。尤其重要的是至少某些摻雜劑原子位於矽酸鹽主晶之氧原子晶格點處這一事實。The various embodiments of the two-phase citrate-based phosphor of the present invention will be illustrated in the following order: First, an overview of the two-phase citrate-based novel composition will be outlined, followed by a detailed description of the citric acid. The crystalline nature of the salt host lattice changes the effect of the relative amounts of alkaline earth metals and strontium in the lattice and the relative amounts of different alkaline earth metals. The activator divalent europium (Eu 2 + ) in at least one phase of the composition is then discussed and a dopant D comprising one or more of the elements F, Cl, Br, S and N is disclosed. Of particular importance is the fact that at least some of the dopant atoms are located at the lattice point of the oxygen atom of the ceric acid host crystal.

再論述提供本發明二相以矽酸鹽為主的系統之優點,該等優點包括(但不限於)可用於該二(或更多)相磷光體之多種激發能量,該二(或更多)相磷光體之增強的溫度穩定性及此一二(或更多)相磷光體系統可提供之合意之發射光譜。Further discussing the advantages of providing a two-phase bismuthate-based system of the present invention, including but not limited to a plurality of excitation energies available for the two (or more) phase phosphors, the two (or more) The enhanced temperature stability of the phase phosphor and the desired emission spectrum of the one or two (or more) phase phosphor systems.

最後將涵蓋該二相磷光體系統在白光LED及彩色顯示面板中之應用,包括可用激發源之類型,及一可與本發明二相系統共同使用之已知的其他磷光體之實例。Finally, the application of the two-phase phosphor system in white LEDs and color display panels will be covered, including the types of excitation sources available, and examples of other known phosphors that can be used with the two-phase system of the present invention.

本發明實施例之新穎的多相以矽酸鹽為主的磷光體系統Novel multi-phase citrate-based phosphor system in accordance with an embodiment of the present invention

本發明實施例之新穎磷光體組合物於該組合物內具有至少兩個以矽酸鹽為主之相,其中第一相可具有實質與(M1)2 SiO4 相同之晶體結構,且第二相可具有實質與(M2)3 SiO5 相同之晶體結構。熟習此項技術者應瞭解該等兩個矽酸鹽之相係實例性的;本發明實施例亦涵蓋許多其他相,且彼此共同起作用之不同矽酸鹽相之相對量界定該等新穎屬性。The novel phosphor composition of the embodiments of the present invention has at least two phases based on citrate in the composition, wherein the first phase may have the same crystal structure as (M1) 2 SiO 4 and the second The phase may have the same crystal structure as (M2) 3 SiO 5 . Those skilled in the art will appreciate that the two citrate phases are exemplary; the present invention also encompasses many other phases, and the relative amounts of different citrate phases that work together define these novel attributes. .

本文中M1及M2各自通常係一鹼土金屬,但M1、M2亦可係其他元素。因此本文將M1、M2各自定義為係選自由Sr、Ba、Mg、Ca及Zn組成之群。該組合物中至少一相含有於或等於約0.0001重量%之水平之Mg。In this context, M1 and M2 are each usually an alkaline earth metal, but M1 and M2 may also be other elements. Therefore, each of M1 and M2 is defined herein as being selected from the group consisting of Sr, Ba, Mg, Ca, and Zn. At least one phase of the composition contains Mg at a level of or equal to about 0.0001% by weight.

本發明磷光體組合物可由二價銪(Eu2 )激活,然而熟習此項技術者亦應瞭解二價銪(Eu2 )並非係唯一的可用於激活磷光體組合物之活化劑。The phosphor composition of the present invention can be activated by divalent europium (Eu 2 + ), however, those skilled in the art will also appreciate that divalent europium (Eu 2 + ) is not the only activator that can be used to activate the phosphor composition.

該組合物之相中至少一相含有可係鹵素之摻雜劑D。當摻雜劑D係鹵素時,其可係F、Cl或Br中任一者。然而此並非指該摻雜劑D總必須係鹵素,或專門係鹵素;實際上,該摻雜劑D亦可包括元素S及N,且可係一鹵素與S及/或N之組合。在某些實施例中,至少某些納於該磷光體組合物之摻雜劑D原子位於該矽酸鹽主晶之氧原子晶格點上,其中再一次地該矽酸鹽主晶格包括(但不限於)諸如SiO4 、SiO5 、Si2 O5 、Si3 O8 、SiO4 、Si2 O7 及Si2 O8 等結構,其中替代矽之鹼土金屬之量取決於其化合價。At least one of the phases of the composition contains a halogen-free dopant D. When the dopant D is halogen, it may be any of F, Cl or Br. However, this does not mean that the dopant D must be halogen or special halogen; in fact, the dopant D may also include the elements S and N, and may be a combination of a halogen and S and/or N. In certain embodiments, at least some of the dopant D atoms of the phosphor composition are located on the oxygen atom lattice point of the bismuth silicate main crystal, wherein again the citrate host lattice comprises (but not limited to) structures such as SiO 4 , SiO 5 , Si 2 O 5 , Si 3 O 8 , SiO 4 , Si 2 O 7 and Si 2 O 8 , wherein the amount of the alkaline earth metal instead of lanthanum depends on the valence thereof.

在本發明一實施例中,本發明一新穎二相磷光體通常可描述為式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D,其中該式SiO4 部分與該式SiO5 部分之間之符號意欲用於表示分開相。該式係例示性,因為可能已選擇任何兩個矽酸鹽相。在以上所顯示之實例性表達式中M1及M2各自係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬。In an embodiment of the invention, a novel two-phase phosphor of the invention can generally be described as a formula a[Sr x (M1) 1 - x ] z SiO 4 ● (1-a) [Sr y (M2) 1 - y u SiO 5 :Eu 2 + D, wherein the symbol between the SiO 4 moiety and the SiO 5 moiety of the formula is intended to indicate a separate phase. This formula is exemplary since any two citrate phases may have been selected. In the exemplary expressions shown above, each of M1 and M2 is at least one divalent metal selected from the group consisting of Ba, Mg, Ca, and Zn.

無論其矽酸鹽結構如何,本發明實施例之該等磷光體在其化學式中不一定必須係化學計量,意指該化合物之式中各種元素間不一定必須是一整數值關係。舉例而言,式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D中x、y及z值可符合下列關係,其中0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;及2.6u3.3。Regardless of its citrate structure, the phosphors of the embodiments of the present invention do not necessarily have to be stoichiometric in their chemical formulas, meaning that the various elements of the formula of the compound do not necessarily have to be an integer value relationship. For example, the formula a[Sr x (M1) 1 - x ] z SiO 4 ●(1-a)[Sr y (M2) 1 - y ] u SiO 5 :Eu 2 + D in x, y and z values Can meet the following relationship, of which 0.6 a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5; and 2.6 u 3.3.

本發明二相材料可藉由兩種途徑合成:(1)將兩個矽酸鹽相之合意組合物中原材料組份前體加以混合並藉由液相反應或固相反應處理前體並燒結;(2)獨立處理二相材料並藉由機械混合對最終二相材料加以混合。The two-phase material of the present invention can be synthesized by two routes: (1) mixing the raw material component precursors in the desired composition of the two citrate phases and treating the precursor by a liquid phase reaction or a solid phase reaction and sintering (2) independently processing the two-phase material and mixing the final two-phase material by mechanical mixing.

如G.Blasse等人在Philips Research Reports第23卷,第1冊,第1至120頁所教示,經銪激活之磷光體中之主晶格可屬於系統Me2 SiO4 ,其中Me係Sr或Ba,在此情況下該磷光體具有K2 SO4 樣或Me3 SiO5 晶體結構,其中Me係Ca、Sr或Ba中任一者,其中該磷光體具有晶體結構(或與該晶體結構相關)Cs3 CoCl5 。圖2A所顯示之實例性x-射線衍射圖表明本發明磷光體之主晶格亦呈晶體狀。As taught by G. Blasse et al. in Philips Research Reports, Vol. 23, Volume 1, pages 1 to 120, the host lattice in a ruthenium-activated phosphor may belong to the system Me 2 SiO 4 , where Me is Sr or Ba, in this case the phosphor has a K 2 SO 4 -like or Me 3 SiO 5 crystal structure, wherein Me is any one of Ca, Sr or Ba, wherein the phosphor has a crystal structure (or is associated with the crystal structure) ) Cs 3 CoCl 5 . The exemplary x-ray diffraction pattern shown in Figure 2A shows that the host lattice of the phosphor of the present invention is also crystalline.

參考圖2A,其顯示(M2)3 SiO5 型化合物、含有M3 SiO5 及M2 SiO4 型化合物之二相組合物及(M1)2 SiO4 型化合物之x-射線衍射圖案間之對比。(M2)3 SiO5 型化合物之x-射線衍射圖案顯示為圖2A中之最上面的曲線,且實際測得之化合物係Sr3 Eu0 . 6 Si1 . 0 2 O5 F0 . 1 3 。(M1)2 SiO4 型化合物係圖2中之最下面的曲線,實際化合物係(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2Referring to FIG. 2A, there is shown a comparison between the (M2) 3 SiO 5 type compound, the two-phase composition containing the M 3 SiO 5 and the M 2 SiO 4 type compound, and the x-ray diffraction pattern of the (M1) 2 SiO 4 type compound. . X- ray diffraction pattern (M2) 3 SiO 5 as a compound of the display in the top curve of FIG. 2A, and the actual measured Sr-based compound of 3 Eu 0. 6 Si 1. 0 2 O 5 F 0. 1 3 . (M1) 2 SiO 4 type compound is the lowermost curve in Fig. 2, the actual compound system (Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 .

圖2A之中間曲線係二相以矽酸鹽為主的材料之x-射線衍射圖案,該材料之一般性質可由式(M1)2 SiO4 ●(M2)3 SiO5 代表,其中圓點指示該材料二相之區分。更具體而言,該二相磷光體可由式a(Srx M11 x )z SiO4 ●(1-a)(Sry M21 y )u SiO5 :Eu2 D代表,其中在此情況下該實例性磷光體係0.72[(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2 ]●0.28(Sr3 Eu0 . 6 Si1 . 0 2 O5 F0 . 1 3 )。當然,熟習此項技術者應瞭解在此情況下該術語意指a=0.72;(1-a)=0.28;M1包括所有鹼土金屬Sr、Ba及 Mg三者,而M2僅係Sr,且摻雜劑D係氟。The middle curve of Fig. 2A is an x-ray diffraction pattern of a two-phase citrate-based material whose general properties can be represented by the formula (M1) 2 SiO 4 ● (M2) 3 SiO 5 , wherein dots indicate The distinction between two phases of material. More specifically, the two-phase phosphor may be represented by the formula a(Sr x M1 1 - x ) z SiO 4 ●(1-a)(Sr y M2 1 - y ) u SiO 5 :Eu 2 + D, wherein In this case, the example phosphorescent system is 0.72 [(Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 ] ● 0.28 ( Sr 3 Eu 0 . 6 Si 1 . 0 2 O 5 F 0 . 1 3 ). Of course, those skilled in the art should understand that in this case the term means a=0.72; (1-a)=0.28; M1 includes all alkaline earth metals Sr, Ba and Mg, while M2 is only Sr and is doped. The impurity D is fluorine.

圖2A中三個x-射線衍射(XRD)圖案之比較表明三個試樣皆係晶體狀。雖然不希望受限於任何特殊理論,但據信(M1)2 SiO4 可顯示與矽酸鍶Sr2 SiO4 之結構(正交晶體結構,空間群Pnma)一致之峰,且(M2)3 SiO5 可顯示與另一矽酸鍶Sr3 SiO5 (四邊形晶體結構,空間群P4/ncc)結構一致之峰。由於在實際磷光體中鋇及/或鎂替代鍶,因而本發明二相磷光體之峰位置可沿2θ軸略微移動或不移動。A comparison of the three x-ray diffraction (XRD) patterns in Figure 2A indicates that all three samples are crystalline. Although not wishing to be bound by any particular theory, it is believed that (M1) 2 SiO 4 can exhibit a peak consistent with the structure of the strontium ruthenate Sr 2 SiO 4 (orthogonal crystal structure, space group Pnma), and (M2) 3 SiO 5 can show a peak consistent with the structure of another strontium ruthenate Sr 3 SiO 5 (quadrilateral crystal structure, space group P4/ncc). The peak position of the biphasic phosphor of the present invention may be slightly shifted or not moved along the 2θ axis due to the substitution of yttrium and/or magnesium in the actual phosphor.

圖2B顯示藉由下列兩種不同方法合成之實例性二相磷光體之x-射線衍射圖案:1)在一方法中,分別將該等相中的每一相共沉澱、煆燒及燒結且於兩相中每一相皆經充分處理後才加以混合;及2)將二相同時以液相合成,並一起經共沉澱、煆燒及燒結。圖2B中藉由方法1)製備之試樣標識為「分開燒結後加以機械混合」,而藉由方法2)製備之試樣標識為「同時沉澱」。2B shows an x-ray diffraction pattern of an exemplary two-phase phosphor synthesized by two different methods: 1) in one method, each phase in the respective phases is coprecipitated, calcined, and sintered, respectively. After each phase of the two phases is sufficiently treated, it is mixed; and 2) the two are synthesized in the liquid phase at the same time, and co-precipitated, calcined and sintered together. The sample prepared by the method 1) in Fig. 2B is labeled as "mechanical mixing after separate sintering", and the sample prepared by the method 2) is identified as "simultaneous precipitation".

對於圖2B所示兩試樣而言,峰及其位置實質相同,因而表明該等兩相(M1)2 SiO4 及(M2)3 SiO5 係分別以液相形成。For the two samples shown in Fig. 2B, the peaks and their positions are substantially the same, thus indicating that the two-phase (M1) 2 SiO 4 and (M2) 3 SiO 5 systems are respectively formed in a liquid phase.

鹼土組份M1及M2在SiOAlkaline soil components M1 and M2 in SiO 44 及SiOAnd SiO 55 矽酸鹽相中之影響Effect in the citrate phase

以下部分將分別論述鹼土組份M1及M2在(M1)2 SiO4 及(M2)3 SiO5 矽酸鹽相中之影響。The following sections discuss the effects of alkaline earth components M1 and M2 in (M1) 2 SiO 4 and (M2) 3 SiO 5 citrate phases, respectively.

除了其他方法以外,還可藉由調節任何其他元素與鍶量之比率來控制(M1)2 SiO4 相之光學性質,則其中M1係鍶(Sr)加另一鹼土元素例如鎂(Mg)、鈣(Ca)、鋇(Ba)或過渡金屬元素例如鋅(Zn)或其任一組合或任何多種組合。實施本發明概念實施例之一實例性數據組曾闡明於美國專利申請案第11/269,953號,該申請案於2005年11月8日提出申請且名稱為「Silicate-based green phosphors」,其全文以引用方式併入本文。Among other methods, the optical properties of the (M1) 2 SiO 4 phase can be controlled by adjusting the ratio of any other element to the amount of lanthanum, wherein the M1 system 锶 (Sr) plus another alkaline earth element such as magnesium (Mg), Calcium (Ca), barium (Ba) or a transition metal element such as zinc (Zn) or any combination thereof or any combination thereof. An exemplary data set for practicing an embodiment of the inventive concept is set forth in U.S. Patent Application Serial No. 11/269,953, filed on Nov. 8, 2005, entitled "Silicate-based green phosphors" Incorporated herein by reference.

三種綠色磷光體(其中具有式(Sr0 . 2 Ba0 . 8 )2 SiO4 :Eu2 F者在約522奈米下發光;(Sr0 . 3 Ba0 . 7 )2 SiO4 :Eu2 F在約525奈米下發光;且(Sr0 . 4 Ba0 . 6 )2 SiO4 :Eu2 F在約532奈米下發光)之發射光譜於美國專利申請案第11/269,953號中與更多在光譜黃光區域發光之磷光體之發射光譜進行比較,該以矽酸鹽為主的黃色磷光體具有式(Sr0 . 7 Ba0 . 3 )2 SiO4 :Eu2 F。該黃色磷光體在約540奈米下發光。用一在約450奈米下發光之藍光LED激發該等磷光體。Three kinds of green phosphor (having the formula (Sr 0 2 Ba 0 8) 2 SiO 4: Eu 2 + F by emitting at about 522 nanometers; (Sr 0 3 Ba 0 7 ) 2 SiO 4:.... Eu 2 + F emission at about 525 nm; and (Sr 0 4 Ba 0 6. .) 2 SiO 4: Eu 2 + F at about 532 nm at an emission) of the emission spectrum of U.S. Patent application No. 11 in / 269,953 Compared with the emission spectrum of more phosphors emitting light in the yellow region of the spectrum, the yellow phosphor based on citrate has the formula (Sr 0 . 7 Ba 0 . 3 ) 2 SiO 4 :Eu 2 + F. The yellow phosphor illuminates at about 540 nm. The phosphors are excited with a blue LED that emits light at about 450 nm.

本發明之發明者已在先前研究中揭示(Sr1 x Bax )2 SiO4 磷光體系統中出現峰值發射之波長位置自500奈米下之綠色(此時x=1,換言之,此時所含鹼金屬係100% Ba)變成在580奈米下之黃色(此時x=0(100% Sr))。當Ba自0至約90%不斷增加時,同一光源在450奈米下之轉變效率亦顯示一不斷增長。當Ba與Sr比率係0.3至0.7時所獲得之峰值發射波長545奈米接近YAG:Ce峰值發射波長。The inventors of the present invention have revealed in previous studies that the wavelength position at which the peak emission occurs in the (Sr 1 - x Ba x ) 2 SiO 4 phosphor system is from green at 500 nm (in this case, x = 1, in other words, at this time) The alkali metal system contained 100% Ba) became yellow at 580 nm (in this case, x = 0 (100% Sr)). When Ba increases from 0 to about 90%, the conversion efficiency of the same light source at 450 nm also shows a continuous increase. The peak emission wavelength of 545 nm obtained when the ratio of Ba to Sr is 0.3 to 0.7 is close to the YAG:Ce peak emission wavelength.

同樣四種磷光體(Sr0 . 2 Ba0 . 8 )2 SiO4 :Eu2 F、(Sr0 . 3 Ba0 . 7 )2 SiO4 :Eu2 F、(Sr0 . 4 Ba0 . 6 )2 SiO4 :Eu2 F及(Sr0 . 7 Ba0 . 3 )2 SiO4 :Eu2 F之激發光譜族顯示於美國專利申請案第11/269,953號中。熟習此項技術者應瞭解一「激發光譜」實際係一發射光譜,其中所發射出的光線強度作為激發輻射波長之函數進行量測。換言之,選擇在一特定波長下量測自磷光體發射之光線,且該波長係引入經掃描磷光體之輻射之波長。在此系列實驗中所選擇之波長係當該磷光體在450奈米下受到激發時出現最強發射之波長。The same four kinds of phosphors (Sr 0 . 2 Ba 0 . 8 ) 2 SiO 4 :Eu 2 + F, (Sr 0 . 3 Ba 0 . 7 ) 2 SiO 4 :Eu 2 + F, (Sr 0 . 4 Ba 0 . 6) 2 SiO 4: Eu 2 + F and (Sr 0 7 Ba 0 3) 2 SiO 4:.. Eu 2 + F group of the excitation spectrum is shown in U.S. Patent application No. 11 / 269,953. Those skilled in the art will appreciate that an "excitation spectrum" is actually an emission spectrum in which the intensity of the emitted light is measured as a function of the wavelength of the excitation radiation. In other words, the light emitted from the phosphor is measured at a particular wavelength and the wavelength is the wavelength of the radiation that is introduced into the scanned phosphor. The wavelength selected in this series of experiments is the wavelength at which the phosphor emits the strongest emission when excited at 450 nm.

在美國專利申請案第11/269,953號之特定實例中,實驗中所用檢測器經設定以量測由(Sr0 . 2 Ba0 . 8 )2 SiO4 :Eu2 F磷光體所發射出的522奈米光線之強度,此乃因當(Sr0 . 2 Ba0 . 8 )2 SiO4 :Eu2 F磷光體在450奈米下受到激發時,522奈米係出現最強發射之波長。將檢測器設定至522奈米後,使激發輻射波長自約300奈米掃描至約560奈米並記錄522奈米處之發射。同樣,該檢測器經設定以分別量測(Sr0 . 3 Ba0 . 7 )2 SiO4 :Eu2 F、(Sr0 . 4 Ba0 . 6 )2 SiO4 :Eu2 F及(Sr0 . 7 Ba0 . 3 )2 SiO4 :Eu2 F磷光體之525奈米、532奈米及540奈米光線之強度,並對於各試樣使激發輻射之波長自約300奈米掃描至約560奈米。In a specific example of U.S. Patent Application Serial No. 11/269,953, the detector used in the experiment is set to measure the emission of (Sr 0 . 2 Ba 0 . 8 ) 2 SiO 4 :Eu 2 + F phosphor. The intensity of the 522 nm light is due to the strongest emission wavelength of the 522 nm when the (Sr 0 . 2 Ba 0 . 8 ) 2 SiO 4 :Eu 2 + F phosphor is excited at 450 nm. After the detector was set to 522 nm, the excitation radiation wavelength was scanned from about 300 nm to about 560 nm and the emission at 522 nm was recorded. Also, the detector is set to each measurement (Sr 0 3 Ba 0 7. .) 2 SiO 4: Eu 2 + F, (Sr 0 4 Ba 0 6..) 2 SiO 4: Eu 2 + F and ( Sr 0 . 7 Ba 0 . 3 ) 2 SiO 4 :Eu 2 + F phosphor 525 nm, 532 nm and 540 nm light intensity, and for each sample the excitation radiation wavelength from about 300 nm Scan to about 560 nm.

在該實例中之數據顯示此三種在522奈米、525奈米及532奈米下發射之綠色磷光體當激發輻射波長小於約420奈米時更加響應激發輻射。在約420與460奈米之間,522及525奈米綠色磷光體曲線降至532奈米綠色磷光體及540黃色磷光體二者之下。該等四種磷光體皆不會響應於波長大於約500至520奈米之激發輻射。The data in this example shows that the three green phosphors emitted at 522 nm, 525 nm, and 532 nm are more responsive to excitation radiation when the excitation radiation wavelength is less than about 420 nm. Between about 420 and 460 nm, the 522 and 525 nm green phosphor curves fall below both the 532 nm green phosphor and the 540 yellow phosphor. None of the four phosphors are responsive to excitation radiation having a wavelength greater than about 500 to 520 nm.

簡言之,其將顯示相對於單相系統在兩相系統中對於激發可以獲得意外結果。In short, it will show that unexpected results can be obtained for excitation in a two-phase system relative to a single-phase system.

不同於Ba之元素可用於替代矽酸鹽基質中之Sr;該等可供選擇的元素包括Ca及Mg。在以Sr-Ba為主的矽酸鹽磷光體系統中以鈣替代鋇或鍶通常已顯示當鈣替代水平小於40%時可降低單相(M1)2 SiO4 系統之發射強度,並將發射移至更長波長下。(參見美國專利申請案第11/269,953號)。在以Sr-Ba為主之矽酸鹽磷光體中大量鎂替代鋇或鍶通常會降低發射強度,並將發射移至更短波長下。然而,少量鎂替代鋇或鍶(例如,小於10%)可增強發射強度,並將發射移至更長波長下。Elements other than Ba can be used to replace Sr in the citrate matrix; these alternative elements include Ca and Mg. The replacement of barium or strontium with calcium in a sulphate phosphor system based on Sr-Ba has generally been shown to reduce the emission intensity of the single phase (M1) 2 SiO 4 system when the calcium substitution level is less than 40% and will emit Move to a longer wavelength. (See U.S. Patent Application Serial No. 11/269,953). The substitution of large amounts of magnesium for strontium or barium in Sr-Ba-based phthalate phosphors generally reduces the emission intensity and shifts the emission to shorter wavelengths. However, a small amount of magnesium instead of ruthenium or osmium (eg, less than 10%) enhances the emission intensity and shifts the emission to longer wavelengths.

少量Mg添加至(M1)2 SiO4 以矽酸鹽為主的綠色磷光體中之效果亦顯示於美國專利申請案第11/269,953號中。其中揭示測得之磷光體(Sr0 . 0 5 7 Ba0 . 4 Mg0 . 0 2 5 )2 SiO4 :Eu2 F及(Sr0 . 0 5 7 Ba0 . 4 Mg0 . 0 2 5 )2 SiO4 :Eu2 F在450奈米激發下之發射光譜並與實質不含Mg之磷光體之發射進行對比。不含Mg之「對照」磷光體由式(Sr0 . 6 Ba0 . 4 )2 SiO4 :Eu2 F代表。選擇此系列組合物之目的在於表明下列之效果:Mg首先替代Sr,使Ba含量實質不變,然後Mg替代Ba,使Sr含量實質不變。The effect of a small amount of Mg added to the (M1) 2 SiO 4 green phosphate-based phosphor is also shown in U.S. Patent Application Serial No. 11/269,953. The measured phosphor (Sr 0 . 0 5 7 Ba 0 . 4 Mg 0 . 0 2 5 ) 2 SiO 4 :Eu 2 + F and (Sr 0 . 0 5 7 Ba 0 . 4 Mg 0 . 0 2 5 ) The emission spectrum of 2 SiO 4 :Eu 2 + F at 450 nm excitation and compared with the emission of substantially Mg-free phosphor. The Mg-free "control" by the formula (Sr 0 6 Ba 0 4. .) 2 SiO 4 phosphor: Eu 2 + F representative. The purpose of selecting this series of compositions is to show the following effects: Mg first replaces Sr, so that the Ba content is substantially unchanged, and then Mg replaces Ba, so that the Sr content is substantially unchanged.

添加Mg可提高發射強度。觀察所有三種磷光體在約540奈米下之峰值發射強度,三者中具有最低發射強度之磷光體係對照磷光體即(Sr0 . 6 Ba0 . 4 )2 SiO4 :Eu2 F。Mg替代Ba之磷光體展示出之發射強度較對照磷光體增加約6至7%,且Mg替代Sr之磷光體展示出之發射強度較對照磷光體提高約10%。亦可觀察到納入Mg將出現峰值發射之波長移至更長波長(即略微靠近黃色並遠離綠色),且當Mg替代Ba時而不是Mg替代Sr時該效果更明顯。Adding Mg increases the emission intensity. All three phosphors were observed a peak emission intensity at approximately 540 nm, has the three lowest emission intensity of the phosphorescence phosphor i.e. control (Sr 0 6 Ba 0 4. .) 2 SiO 4: Eu 2 + F. The phosphor of Mg instead of Ba exhibits an emission intensity that is about 6 to 7% higher than that of the control phosphor, and the phosphor of Mg instead of Sr exhibits an emission intensity that is about 10% higher than that of the control phosphor. It can also be observed that the inclusion of Mg shifts the wavelength at which the peak emission occurs to a longer wavelength (ie, slightly closer to yellow and away from green), and this effect is more pronounced when Mg replaces Ba instead of Mg instead of Sr.

須重申的是該等結果係在單相即(M1)2 SiO4 系統中觀察到。It must be reiterated that these results were observed in the single phase, ie (M1) 2 SiO 4 system.

可對單相(M2)3 SiO5 系統進行類似光學觀察並與單相(M1)2 SiO4 觀察結果進行對比。該等已論述於2005年10月25日提出申請之美國專利申請案第11/258,679號中,該申請案之名稱為「Silicate-based orange phosphors」,其全文以引用方式併入本文,其報道了單個相Sr3 SiO5 、(Ba0 . 1 Sr0 . 9 )3 SiO5 及(Ba0 . 0 7 5 Mg0 . 0 2 5 Sr0 . 9 )3 SiO5 之發射光譜。展示出最大發射強度之磷光體係磷光體(Ba0 . 1 Sr0 . 9 )3 SiO5 及(Sr0 . 9 7 Eu0 . 0 3 )3 SiO5 :F。該等磷光體表明,不僅所繪示之五種磷光體之最高強度發射而且該曲線圖中之某些最長之峰值發射波長(介於約585至600奈米之間)皆完全位於電磁波譜之橙色區域內。在本發明實例性磷光體中,顯示最短波長發射之磷光體係(Ba0 . 0 7 5 Mg0 . 0 2 5 Sr0 . 9 Eu0 . 0 3 )3 SiO5 :F,其峰波長發射略小於580奈米。A similar optical observation can be made for the single phase (M2) 3 SiO 5 system and compared with the single phase (M1) 2 SiO 4 observation. U.S. Patent Application Serial No. 11/258,679, filed on Oct. 25, 2005, which is incorporated herein by reference in its entirety in The emission spectra of a single phase of Sr 3 SiO 5 , (Ba 0 . 1 Sr 0 . 9 ) 3 SiO 5 and (Ba 0 . 0 7 5 Mg 0 . 0 2 5 Sr 0 . 9 ) 3 SiO 5 . Phosphorescent phosphor exhibiting maximum emission intensity (Ba 0 . 1 Sr 0 . 9 ) 3 SiO 5 and (Sr 0 . 9 7 Eu 0 . 0 3 ) 3 SiO 5 :F. The phosphors show that not only the highest intensity emission of the five phosphors depicted but also some of the longest peak emission wavelengths (between about 585 and 600 nm) in the graph are completely in the electromagnetic spectrum. Within the orange area. In the exemplary phosphor of the present invention, the phosphorescent system exhibiting the shortest wavelength emission (Ba 0 . 0 7 5 Mg 0 . 0 2 5 Sr 0 . 9 Eu 0 . 0 3 ) 3 SiO 5 :F, the peak wavelength emission is slightly Less than 580 nm.

改變一系列具有式(Sr0 . 9 7 Eu0 . 0 3 )y SiO5 之實例性磷光體中Sr(或Ba、Ca等)與Si含量之比率之實例亦顯示於美國專利申請案第11/258,679號中。所顯示數據表明發射強度最大值出現於當Sr與Si之比率係約3.1時,其中強度次大值出現在比率係約2.8時。曲線圖上的點欲表明在單相系統中不一定必須嚴格遵循(M2)3 SiO5 之化學計量(同樣,M2係Sr、Ba、Ca、Eu等之量),其中鹼土金屬或其他元素M與矽之比率固定為約3.0之值。實際上出於增強發射強度之目的相對於慣用值改變此比率具有優勢。A series of changes having the formula (Sr 0. 9 7 Eu 0 . 0 3) y SiO examples of phosphors described in Example 5 Sr (or Ba, Ca, etc.) the ratio of the Si content is also shown in U.S. Patent Application No. 11 /258,679. The data shown indicates that the maximum emission intensity occurs when the ratio of Sr to Si is about 3.1, with the second largest intensity appearing at a ratio of about 2.8. The points on the graph indicate that it is not necessary to strictly follow the stoichiometry of (M2) 3 SiO 5 in a single-phase system (again, the amount of M2 series Sr, Ba, Ca, Eu, etc.), among which alkaline earth metals or other elements M The ratio to 矽 is fixed at a value of about 3.0. It is actually advantageous to vary this ratio relative to the usual value for the purpose of enhancing the emission intensity.

改變美國專利申請案第11/258,679號中(M2)3 SiO5 橙色磷光體中鹼土金屬性質(意指同一性)及含量對發射強度峰值及發射波長二者皆有影響。在彼專利申請案中,(Mx Sr1 x )2 . 9 1 Eu0 . 0 9 SiO5 系列中鹼土金屬M係選自由鎂(Mg)、鍶(Sr)、鈣(Ca)及鋇(Ba)組成之群。Altering the (M2) 3 SiO 5 orange phosphor in the U.S. Patent Application Serial No. 11/258,679, the alkaline earth metal properties (meaning identity) and the content have an effect on both the emission intensity peak and the emission wavelength. In his patent application, the (M x Sr 1 - x ) 2 . 9 1 Eu 0 . 0 9 SiO 5 series of alkaline earth metal M is selected from the group consisting of magnesium (Mg), strontium (Sr), calcium (Ca) and strontium. (Ba) The group consisting of.

美國專利申請案第11/258,679號亦表明納有兩種不同鹼土金屬Ca及Mg之效果,其中顯示一系列具有式(Cax Sr1 x )2 . 9 1 Eu0 . 0 9 SiO5 之磷光體之發射光譜數據,該等試樣具有等於0.0、0.5及1.0之x值。亦顯示校正x=1及x=0.5之結果以使所有三個峰皆具有與x=0之組合物峰大體相同之高度的數據。在彼系列中,具有Ca與Sr中間比率之組合物(換言之,該組合物中Ca及Sr之量實質相同)顯示在約605至610奈米處之最長的峰值發射波長。該情況較該系列其他兩位成員之情況更靠近紅色,並遠離黃色。主要含鈣之組合物(x=1)顯示在約510奈米處的最短峰值發射波長,其係一靠近黃色之綠色端之顏色。全部含有鍶且不含鈣之組合物在該分佈的中間,其中峰值發射波長在約590奈米處。U.S. Patent Application No. 11 / 258,679 also have the effect of two different tables Minna alkaline earth metals of Mg and Ca, which shows a series of formulas.. - 2 9 1 Eu 0 0 9 SiO 5 of (Ca x Sr 1 x) The emission spectrum data of the phosphors having x values equal to 0.0, 0.5, and 1.0. The results of correcting x = 1 and x = 0.5 are also shown such that all three peaks have data at substantially the same height as the peak of the composition of x = 0. In the series, compositions having an intermediate ratio of Ca to Sr (in other words, the amounts of Ca and Sr in the composition are substantially the same) show the longest peak emission wavelength at about 605 to 610 nm. This situation is closer to red than the other two members of the series and away from yellow. The predominantly calcium containing composition (x = 1) shows the shortest peak emission wavelength at about 510 nm, which is a color near the green end of the yellow. All compositions containing barium and no calcium were in the middle of the distribution with a peak emission wavelength at about 590 nm.

再參考美國專利申請案第11/258,679號,其發現組合物(Mgx Sr1 x )2 , 9 1 Eu0 . 0 9 SiO5 中鎂替代鍶可降低發射強度並將峰值發射波長移至更短波長處。對其中磷光體在403奈米處以及在450奈米處受到激發之情形而言皆有如上情況。對此兩種激發波長而言,完全含有鍶作為鹼土金屬組份(x=0)之組合物皆在最長波長處發射,且該發射亦發生於約590奈米處。少量鎂替代鍶(x=0.2)可明顯降低發射強度,但不會實質改變發射波長。Referring again to U.S. Patent Application Serial No. 11/258,679, it is found that the substitution of magnesium in the composition (Mg x Sr 1 - x ) 2 , 9 1 Eu 0 . 0 9 SiO 5 reduces the emission intensity and shifts the peak emission wavelength to Shorter wavelengths. The same is true for the case where the phosphor is excited at 403 nm and at 450 nm. For both excitation wavelengths, the composition containing ruthenium as the alkaline earth metal component (x = 0) was emitted at the longest wavelength, and the emission also occurred at about 590 nm. A small amount of magnesium instead of strontium (x = 0.2) can significantly reduce the emission intensity, but does not substantially change the emission wavelength.

更多之鎂替代鍶至最初水平x=0.30,然後進一步降低至x=0.35之水平會提高發射強度,雖然未完全恢復至鎂含量為零時所顯示之強度。在該系列鎂替代鍶之該點(x=3.5之水平)處,可觀察到該系列中次高發射強度。自該濃度起,進一步由鎂替代鍶(分別至x=0.4及x=0.5)會使強度降低,起初僅係小程度地,隨後相當顯著。該等組合物(x=0.3、0.35及0.4,x=0.5)之峰值發射波長介於約530至560奈米之間。More magnesium substitutions to the initial level x = 0.30, and then further reduction to the level of x = 0.35 will increase the emission intensity, although not fully restored to the intensity shown by the magnesium content of zero. At this point in the series of magnesium substitutions (at the level of x = 3.5), the second highest emission intensity in the series was observed. From this concentration, further replacement of strontium by magnesium (to x = 0.4 and x = 0.5, respectively) results in a decrease in strength, initially only to a small extent, and then quite significant. The peak emission wavelengths of the compositions (x = 0.3, 0.35 and 0.4, x = 0.5) are between about 530 and 560 nm.

單相系統中Eu活化劑含量之影響Effect of Eu activator content in single-phase systems

據報道組合物Me3 SiO5 中最適宜活化劑濃度係銪相對於鹼土金屬Me(其中Me係Ca、Sr及Ba;參見G.Blasse等人在Philips Research Reports,第23卷,第1冊,1968中之文章)為數個原子百分比,本文亦報道類似結果。美國專利申請案第11/258,679號已報道改變單相以矽酸鹽為主的組合物(由式(Sr1 x Eux )3 SiO5 代表)中銪活化劑含量之效果。已發現Eu濃度為約0.02之組合物之發射強度最大,同時次發射強度組合物係x=0.03者。It is reported that the optimum activator concentration in the composition Me 3 SiO 5 is relative to the alkaline earth metal Me (where Me is Ca, Sr and Ba; see G. Blasse et al. in Philips Research Reports, Vol. 23, Volume 1, The article in 1968) is a few atomic percentages, and similar results are reported in this paper. The effect of changing the content of the ruthenium activator in a single phase bismuthate-based composition (represented by the formula (Sr 1 - x Eu x ) 3 SiO 5 ) has been reported in U.S. Patent Application Serial No. 11/258,679. Compositions having an Eu concentration of about 0.02 have been found to have the highest emission intensity, while the secondary emission intensity composition is x = 0.03.

通常由式[Srx (M1)1 x ]2 SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D代表之本發明二相以矽酸鹽為主的組合物中,每一相中銪活化劑水平並未指定,但通常可介於約0.01至約0.1之間,其中Eu2 替代該二相組合物中之M1及M2。The two phases of the present invention are generally represented by the formula [Sr x (M1) 1 - x ] 2 SiO 4 ● (1-a) [Sr y (M2) 1 - y ] u SiO 5 : Eu 2 + D based composition, each phase europium activator level is not specified, but usually can be between about 0.01 to about 0.1, wherein Eu 2 + Alternatively the two-phase composition of M1 and M2.

摻雜劑陰離子D之作用The role of dopant anion D

現論述將摻雜劑陰離子D納入本發明二相組合物中之效果,其中D在式[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D之量並未特別指定。在此實施例中,該組合物之相中至少一相含有選自由F、Cl、Br、S及N組成之群之摻雜劑D,其中至少某些摻雜劑原子位於該矽酸鹽主晶之氧原子晶格點處。The effect of incorporating the dopant anion D into the biphasic composition of the present invention is now discussed, wherein D is in the formula [Sr x (M1) 1 - x ] z SiO 4 ● (1-a) [Sr y (M2) 1 - y ] u SiO 5 : The amount of Eu 2 + D is not specifically specified. In this embodiment, at least one of the phases of the composition contains a dopant D selected from the group consisting of F, Cl, Br, S, and N, wherein at least some of the dopant atoms are located in the bismuth citrate The oxygen atom of the crystal is at the lattice point.

美國專利申請案第11/258,679號給出氟(F)在單相系統中之作用之一實例,其顯示磷光體(Sr0 . 9 7 Eu0 . 0 3 )3 SiO5 F6 z 發射強度作為氟(F)濃度之函數之曲線圖。Z介於0至約0.1之間。此處,顯示(M2)3 SiO5 型單相矽酸鹽為主的系統中介於約0.03至0.06間之F濃度使發射強度實質增強。U.S. Patent Application No. 11 / 258,679 is given fluorine (F) acting in the one instance a single-phase system, its display phosphor (Sr 0. 9 7 Eu 0 . 0 3) 3 SiO 5 F 6 z emission intensity A graph as a function of fluorine (F) concentration. Z is between 0 and about 0.1. Here, it is shown that the F concentration of between about 0.03 and 0.06 in the (M2) 3 SiO 5 type single phase citrate-based system substantially enhances the emission intensity.

本發明二相實施例中,鹵素例如氟可以NH4 F摻雜劑形式加至二相中任一相中。本發明已發現當NH4 F摻雜劑之量極小(約1%)時,峰值發射之位置位於較短波長處,且當加入更多NH4 F時,波長隨摻雜劑量增加而增加。摻雜有Eu之磷光體之所以能發光係由於該化合物中存在Eu2 ,Eu2 經歷自4f6 5d1 至4f7 之電子躍遷。發射帶波長位置主要取決於基質之材料或晶體結構,在光譜之近UV至紅色區域間變化。此種依賴可解釋為係由晶體場5d能級之分裂導致。隨晶體場強度增加,發射帶移至更長波長處。表示電子-電子斥力之晶體參數(換言之,Eu2 陽離子與周圍陰離子間之距離,及與遠處陽離子及陰離子之平均距離)對5d-4f躍遷之發光峰值能量影響最大。Two-phase embodiment of the invention, can be a halogen such as fluorine dopant in the form of NH 4 F was added to any one phase or two phases. The present inventors have found that when the amount of NH 4 F dopant is extremely small (about 1%), the position of the peak emission is at a shorter wavelength, and when more NH 4 F is added, the wavelength increases as the doping amount increases. The phosphor doped with Eu is capable of emitting light due to the presence of Eu 2 + in the compound, and Eu 2 + undergoes an electronic transition from 4f 6 5d 1 to 4f 7 . The position of the emission band wavelength depends mainly on the material or crystal structure of the substrate, varying between the UV and red regions of the spectrum. This dependence can be explained by the splitting of the 5d energy level of the crystal field. As the crystal field strength increases, the emission band moves to longer wavelengths. The crystal parameter representing the electron-electron repulsion (in other words, the distance between the Eu 2 + cation and the surrounding anion, and the average distance from the distant cation and anion) has the greatest influence on the luminescence peak energy of the 5d-4f transition.

當有少量NH4 F存在時,氟陰離子摻雜劑主要在燒結處理期間起熔劑作用。通常,熔劑以下兩種方式之一改進燒結處理:第一種係用液相燒結機理促進晶體成長,第二種係自晶粒吸收並收集雜質並提高經燒結材料之相純度。在本發明一實施例中,主磷光體係(Sr1 x Bax )3 SiO5 。Sr及Ba二者皆係極大之陽離子。可能會存在可被認為係雜質之較小陽離子(例如)Mg及Ca。因此,進一步純化主晶格會產生更完美的對稱晶格及陽離子與陰離子間之更大距離,從而削弱晶體場強度。此係少量NH4 F摻雜會將發射峰移至較短波長處之原因。發射強度隨少量F摻雜增加有利於產生缺陷更少而品質更高之晶體。When a small amount of NH 4 F is present, the fluoride anion dopant acts primarily as a flux during the sintering process. Generally, the flux improves the sintering process in one of two ways: the first uses a liquid phase sintering mechanism to promote crystal growth, and the second absorbs and collects impurities from the grains and increases the phase purity of the sintered material. In an embodiment of the invention, the primary phosphorescent system (Sr 1 - x Ba x ) 3 SiO 5 . Both Sr and Ba are extremely cations. There may be smaller cations such as Mg and Ca which may be considered to be impurities. Therefore, further purification of the host lattice results in a more perfect symmetrical lattice and a greater distance between the cation and the anion, thereby weakening the crystal field strength. This is why a small amount of NH 4 F doping will shift the emission peak to a shorter wavelength. The increase in emission intensity with a small amount of F doping is advantageous in producing crystals with fewer defects and higher quality.

當NH4 F之量更進一步增加時,某些F-陰離子會替代O2 -陰離子,並被納入該晶格中。會產生陽離子空位以維持電荷中性。由於陽離子位置之空缺會減小陽離子與陰離子間之平均距離,因而該晶體場強度會增加。因此,當NH4 F含量增加時,由於陽離子空位數目增加從而使發射曲線之峰會移至更長波長處。該發射波長直接與基態與激發態間之能隙相關,而能隙僅由晶體場強度決定。發射波長隨氟及氯增加之結果強有力地證明氟或氯極可能替代氧位被納入主晶格。另一方面,如預期一樣,添加磷酸根離子不會實質改變發射波長。此再次證明磷酸根用作陽離子,不會替代氧,並因而不容易納入晶格而改變基質材料之晶體場強度。基本由氧位組成之環繞Eu2 離子之晶體場情況尤其如此。藉由添加NH4 H2 PO4 獲得之發射強度的提高表明其使如上所述之熔劑起作用。When the amount of NH 4 F is further increased, some F-anions will replace the O 2 - anions and be incorporated into the crystal lattice. Cationic vacancies are created to maintain charge neutrality. Since the vacancy of the cation position reduces the average distance between the cation and the anion, the crystal field strength increases. Therefore, as the NH 4 F content increases, the peak of the emission curve shifts to a longer wavelength due to an increase in the number of cation vacancies. The emission wavelength is directly related to the energy gap between the ground state and the excited state, and the energy gap is determined only by the crystal field strength. As a result of the increase in emission wavelength with fluorine and chlorine, it is strongly demonstrated that fluorine or chlorine is likely to be substituted for the oxygen site to be incorporated into the host lattice. On the other hand, as expected, the addition of phosphate ions does not substantially change the emission wavelength. This again demonstrates that phosphate acts as a cation, does not replace oxygen, and thus does not readily incorporate a crystal lattice to alter the crystal field strength of the matrix material. This is especially the case for crystal fields that surround the Eu 2 + ions, which consist essentially of oxygen sites. An increase in the emission intensity obtained by the addition of NH 4 H 2 PO 4 indicates that it acts on the flux as described above.

二相以矽酸鹽為主的系統之光學性質Optical properties of two-phase citrate-based systems

實例性二相以矽酸鹽為主的磷光體系統之光學性質顯示於圖3至6。圖3係與單相磷光體對比著顯示之二相系統之激發光譜,且圖4係同樣的兩種化合物之發射光譜。圖5A係在三種不同激發波長下二相系統之發射光譜,且表1係圖5A之二相磷光體系統之CIE坐標及Ra之圖表。圖6顯示定義為發射強度作為溫度之函數之溫度穩定性。各圖將依次論述。The optical properties of an exemplary two-phase citrate-based phosphor system are shown in Figures 3-6. Figure 3 is an excitation spectrum of a two-phase system shown in comparison with a single-phase phosphor, and Figure 4 is an emission spectrum of the same two compounds. Figure 5A is an emission spectrum of a two-phase system at three different excitation wavelengths, and Table 1 is a graph of CIE coordinates and Ra of the two-phase phosphor system of Figure 5A. Figure 6 shows the temperature stability defined as the emission intensity as a function of temperature. The figures will be discussed in turn.

圖3係一實例性二相矽酸鹽磷光體之激發光譜,該二相磷光體通常由式a(Srx M11-x )z SiO4 ●(1-a)(Sry M21-y )u SiO5 :Eu2+ D代表,且特定磷光體係0.72[(Sr1.025 Ba0.925 Mg0.05 )Eu0.06 Si1.03 O4 F0.12 ]●0.28(Sr3 Eu0.6 Si1.02 O5 F0.13 )。所顯示的用於對比者係單相磷光體(Sr1.025 Ba0.925 Mg0.05 )Eu0.06 Si1.03 O4 F0.12Figure 3 is an excitation spectrum of an exemplary two phase bismuth silicate phosphor, which is typically of the formula a(Sr x M1 1-x ) z SiO 4 ●(1-a)(Sr y M2 1-y u SiO 5 :Eu 2+ D represents a specific phosphorescent system 0.72 [(Sr 1.025 Ba 0.925 Mg 0.05 )Eu 0.06 Si 1.03 O 4 F 0.12 ]●0.28 (Sr 3 Eu 0.6 Si 1.02 O 5 F 0.13 ). The comparison is shown for the comparative system single phase phosphor (Sr 1.025 Ba 0.925 Mg 0.05 ) Eu 0.06 Si 1.03 O 4 F 0.12 .

圖3中出乎意料的是係其中二相系統之發射強度在極長激發波長範圍內保持恆定的特別方式。該二相化合物顯示在大於約140奈米之激發波長範圍內發射強度以不超過約10%變化。在某些實施例中,在140奈米激發波長範圍內,激發波長以不超過約5%變化。在此情況,140奈米激發波長範圍係自約380至約520奈米。Unexpectedly in Figure 3 is a particular way in which the emission intensity of a two phase system remains constant over a very long excitation wavelength range. The biphasic compound exhibits an emission intensity that varies by no more than about 10% over an excitation wavelength range greater than about 140 nm. In certain embodiments, the excitation wavelength varies by no more than about 5% over a range of excitation wavelengths of 140 nm. In this case, the 140 nm excitation wavelength range is from about 380 to about 520 nm.

出於對比之目的,通常由(M1)2 SiO4 代表且具體而言該化合物係(Sr1.025 Ba0.925 Mg0.05 )Eu0.06 Si1.03 O4 F0.12 之單相系統在此相同的360至520波長範圍內顯示發光幾乎降低100%。For comparison purposes, a single-phase system typically represented by (M1) 2 SiO 4 and in particular the compound (Sr 1.025 Ba 0.925 Mg 0.05 )Eu 0.06 Si 1.03 O 4 F 0.12 is here at the same 360 to 520 wavelength The range shows that the luminescence is reduced by almost 100%.

具有此一水平曲線之一優勢在於二相磷光體系統可由多種激發源激發,且仍發射恆定量之光。此使得光學工程師在使用本發明二相以矽酸鹽為主的化合物時在選擇輻射源及設計整個系統時自由度特別大。One advantage of having such a horizontal curve is that the two-phase phosphor system can be excited by a variety of excitation sources and still emit a constant amount of light. This allows the optical engineer to have a particularly high degree of freedom in selecting the radiation source and designing the entire system when using the two-phase bismuthate-based compound of the present invention.

當然,在其他實施例中,可能不需要在如此寬廣之激發波長範圍內之恆定發射;換言之,僅需要提供一在約80奈米之更窄範圍內(大約例如自380至460奈米)之恆定發射。圖3顯示本發明二相以矽酸鹽為主的化合物0.72[(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2 ]●0.28(Sr3 Eu0 . 6 Si1 . 0 2 O5 F0 . 1 3 )在此80奈米激發範圍內依舊顯示小於約10(或甚至5)%之變化,但(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2 單相磷光體顯示約50%之降低。Of course, in other embodiments, constant emission over such a wide range of excitation wavelengths may not be required; in other words, it is only necessary to provide a narrower range of about 80 nm (about, for example, from 380 to 460 nm). Constant emission. Figure 3 shows a compound of the present invention having a bismuth hydride as a two-phase compound 0.72 [(Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 ]●0.28(Sr 3 Eu 0 . 6 Si 1 . 0 2 O 5 F 0 . 1 3 ) still exhibits less than about 10 (or even 5)% variation in this 80 nm excitation range, but Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 The single-phase phosphor shows a decrease of about 50%.

單相以矽酸鹽為主的化合物與二相以矽酸鹽為主的系統之發射光譜之對比顯示於圖4。再次實例性(M1)2 SiO4 磷光體係(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2 ,且實例性(M1)2 SiO4 ●M(2)3 SiO5 二相系統係0.72[(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0 . 0 6 Si1 . 0 3 O4 F0 . 1 2 ]●0.28(Sr3 Eu0 . 6 Si1 . 0 2 O5 F0 . 1 3 )。單相磷光體及二相系統二者之激發波長皆係約440奈米,且該數據已經校正以更容易地對比曲線寬度。圖4顯示該二相系統具有較該單相系統寬之發射範圍。A comparison of the emission spectra of a single-phase bismuthate-based compound with a two-phase citrate-based system is shown in FIG. Illustrative (M1) 2 SiO 4 phosphorescent system again (Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 , and examples (M1) 2 SiO 4 ●M(2) 3 SiO 5 two-phase system is 0.72 [(Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0 . 0 6 Si 1 . 0 3 O 4 F 0 . 1 2 ] ● 0.28 (Sr 3 Eu 0 . 6 Si 1 . 0 2 O 5 F 0 . 1 3 ). Both the single-phase phosphor and the two-phase system have an excitation wavelength of about 440 nm, and the data has been corrected to more easily compare the width of the curve. Figure 4 shows that the two phase system has a wider emission range than the single phase system.

圖5A以不同方式顯示該二相系統實質不受激發波長影響。此處,該(M1)2 SiO4 ●M(2)3 SiO5 二相系統0.72[(Sr1 . 0 2 5 Ba0 . 9 2 5 Mg0 . 0 5 )Eu0.06 Si1.03 O4 F0.12 ]●0.28(Sr3 Eu0.6 Si1.02 O5 F0.13 )由峰值激發波長為447奈米、452.5奈米及460奈米之三種不同輻射源激發。圖5顯示在500與660奈米間之激發曲線大體相同,峰值發射強度及發生峰值發射之波長(約575奈米)二者皆大體相同。Figure 5A shows in a different manner that the two phase system is substantially unaffected by the excitation wavelength. Here, the (M1) 2 SiO 4 ●M(2) 3 SiO 5 two-phase system 0.72 [(Sr 1 . 0 2 5 Ba 0 . 9 2 5 Mg 0 . 0 5 )Eu 0.06 Si 1.03 O 4 F 0.12 ]●0.28 (Sr 3 Eu 0.6 Si 1.02 O 5 F 0.13 ) was excited by three different radiation sources with peak excitation wavelengths of 447 nm, 452.5 nm, and 460 nm. Figure 5 shows that the excitation curves between 500 and 660 nm are substantially the same, and the peak emission intensity and the wavelength at which the peak emission occurs (about 575 nm) are substantially the same.

表1給出發射曲線之定量評價。此處,由447.0奈米藍光晶片激發之曲線中CIE x及y坐標分別為0.311及0.304,Ra值為65.6。由452.5奈米藍光晶片激發之曲線中CIE x及y坐標分別為0.310及0.308,Ra值為68.5。由460.0奈米藍光晶片激發之曲線中CIE x及y坐標分別為0.308及0.304,Ra值為70.9。Table 1 gives a quantitative evaluation of the emission curve. Here, the CIE x and y coordinates in the curve excited by the 447.0 nm blue light wafer were 0.311 and 0.304, respectively, and the Ra value was 65.6. The CIE x and y coordinates in the curve excited by the 452.5 nm blue wafer were 0.310 and 0.308, respectively, and the Ra value was 68.5. The CIE x and y coordinates in the curve excited by the 460.0 nm blue wafer were 0.308 and 0.304, respectively, and the Ra value was 70.9.

溫度穩定性Temperature stability

本發明二相系統之又一出乎意料且有利之特徵係其在較大溫度範圍內顯著之溫度穩定性。圖6繪示的是由通式(M1)2 SiO4 ●M(2)3 SiO5 代表的二相以矽酸鹽為主的磷光體組合物之發射強度,該發射在介於20℃至180℃間之溫度範圍內量測並以該組合物或磷光體在室溫下(約20℃)所示強度為基準對任一特定溫度下的發射強度進行繪示之方式繪製曲線。所顯示的用於對比的是對單相磷光體(M1)2 SiO4 之類似量測及分析。該實例性單相磷光體係(Sr1.025 Ba0.925 Mg0.05 )Eu0 .06 Si1.03 O4 F0.12 ,且該實例性二相系統係0.72[(Sr1.025 Ba0.925 Mg0.05 )Eu0.06 Si1.03 O4 F0.12 ]●0.28(Sr3 Eu0.6 Si1.02 O5 F0.13 )。Yet another unexpected and advantageous feature of the two phase system of the present invention is its significant temperature stability over a wide temperature range. Figure 6 is a graph showing the emission intensity of a two-phase citrate-based phosphor composition represented by the general formula (M1) 2 SiO 4 ●M(2) 3 SiO 5 , which is emitted at 20 ° C to A curve is measured in the temperature range between 180 ° C and plotted against the intensity indicated by the composition or phosphor at room temperature (about 20 ° C) for the emission intensity at any particular temperature. Shown for comparison is a similar measurement and analysis of single phase phosphor (M1) 2 SiO 4 . The exemplary single phase phosphorescent system (Sr 1.025 Ba 0.925 Mg 0.05 )Eu 0 . 06 Si 1.03 O 4 F 0.12 , and the exemplary two-phase system is 0.72 [(Sr 1.025 Ba 0.925 Mg 0.05 )Eu 0.06 Si 1.03 O 4 F 0.12 ]●0.28 (Sr 3 Eu 0.6 Si 1.02 O 5 F 0.13 ).

結果顯示對本發明二相系統而言,該組合物可經構造以在高於約100℃之溫度下發光,光線強度等於或大於20℃時所發射出光線強度的約90%。在大於約120℃之溫度下,所發射光線強度等於或大於在20℃下所發射光線強度之約90%。同樣,在大於約140℃之溫度下,所發射光線強度等於或大於20℃下所發射光線強度之約80%;在高於約160℃之溫度下,所發射光線強度等於或大於20℃下所發射光線強度之約80%;且在大於約180℃之溫度下所發射光線強度等於或大於20℃下所發射光線強度之約70%。The results show that for the two phase system of the present invention, the composition can be configured to illuminate at a temperature above about 100 ° C, with a light intensity of about 90% of the intensity of the emitted light at or above 20 °C. At temperatures greater than about 120 ° C, the intensity of the emitted light is equal to or greater than about 90% of the intensity of the light emitted at 20 °C. Similarly, at a temperature greater than about 140 ° C, the intensity of the emitted light is equal to or greater than about 80% of the intensity of the emitted light at 20 ° C; at temperatures above about 160 ° C, the intensity of the emitted light is equal to or greater than 20 ° C. The intensity of the emitted light is about 80%; and the intensity of the emitted light at a temperature greater than about 180 ° C is equal to or greater than about 70% of the intensity of the emitted light at 20 ° C.

此係與單相系統進行比較,在單相系統中在100℃、120℃、140℃、160℃及180℃之溫度下,所發射光線強度分別係20℃下所發射光線強度之約80%、65%、55%、45%及30%。This system is compared with a single-phase system. In a single-phase system, the emitted light intensity is about 80% of the intensity of light emitted at 20 ° C at temperatures of 100 ° C, 120 ° C, 140 ° C, 160 ° C, and 180 ° C, respectively. , 65%, 55%, 45% and 30%.

明顯地,該二相系統可提供較單相系統更高之溫度穩定性。磷光體(及其係其中一部分之照明系統)熱穩定性之重要性對市場而言在於:一般照明及汽車應用通常要求作業溫度高於約100℃。此外,當至器件之輸入電流增大時,LED晶片表面之接面溫度隨之升高。藉由增大驅動電流可達成更高亮度,但LED封裝之熱量管理必須予以認真考慮。功率高於1W之LED之接面溫度規定為約120℃,且據信將來的應用將要求器件接面處的作業溫度應高達約200℃。Clearly, the two phase system provides higher temperature stability than single phase systems. The importance of thermal stability of phosphors (and their lighting systems) is important to the market: general lighting and automotive applications typically require operating temperatures above about 100 °C. In addition, as the input current to the device increases, the junction temperature of the surface of the LED wafer increases. Higher brightness can be achieved by increasing the drive current, but the thermal management of the LED package must be carefully considered. The junction temperature of LEDs with power above 1 W is specified to be about 120 ° C, and it is believed that future applications will require operating temperatures at device junctions of up to about 200 ° C.

白光照明之產生White light illumination

下文將論述可使用本發明二相黃色磷光體產生之白光照明。該部分首先闡述可用於激發本發明二相黃色磷光體之例示性藍光LED。圖3之激發光譜表明本發明黃色磷光體能吸收較大範圍波長之光線並可由該等光線激發,該等光線包括可見光之藍光部分。根據圖1之通用方案,來自本發明黃色磷光體之光線可與來自藍光LED之光線組合以製造白色照明。或者,來自本發明黃色磷光體(受到來自非可見光UV激發源之光線激發)之光線可與來自其他磷光體(例如藍色、綠色、橙色或紅色磷光體)組合。因此,白光之演色性可藉由於該系統中納入其他磷光體加以調節。White light illumination that can be produced using the two-phase yellow phosphor of the present invention will be discussed below. This section first sets forth an exemplary blue LED that can be used to excite the two-phase yellow phosphor of the present invention. The excitation spectrum of Figure 3 shows that the yellow phosphor of the present invention is capable of absorbing and stimulating light of a wide range of wavelengths, including the blue portion of visible light. According to the general scheme of Figure 1, light from the yellow phosphor of the present invention can be combined with light from a blue LED to produce white illumination. Alternatively, light from the yellow phosphor of the present invention (excited by light from a non-visible UV excitation source) can be combined with other phosphors (eg, blue, green, orange, or red phosphors). Therefore, the color rendering of white light can be adjusted by incorporating other phosphors into the system.

重要的是應注意用於向磷光體提供激發之藍光晶片(輻射源)之輸出波長之變化導致目前白光LED生產不能準確控制最終產品之CIE輸出。目前,藍光發射半導體晶片形式之激發源以2.5奈米增量在介於約445奈米至470奈米間分類。實質上當輻射源波長改變時所有現有黃色磷光體之發射強度皆有一定變化,即使此改變僅有約2.5奈米。當YAG材料受到約460奈米之輻射波長激發時,該材料具有發射最大值,且當激發波長變化至460奈米值之任一側時,發射效率皆會降低。如圖3所示,當激發波長自450奈米增加時,以矽酸鹽為主的單相磷光體發射效率急劇降低。It is important to note that variations in the output wavelength of the blue light wafer (radiation source) used to provide excitation to the phosphor result in current white LED production that does not accurately control the CIE output of the final product. Currently, excitation sources in the form of blue-emitting semiconductor wafers are classified in the range of about 445 nm to 470 nm in 2.5 nm increments. Essentially, the emission intensity of all existing yellow phosphors varies when the wavelength of the radiation source changes, even if the change is only about 2.5 nm. When the YAG material is excited by a radiation wavelength of about 460 nm, the material has an emission maximum, and when the excitation wavelength changes to either side of the 460 nm value, the emission efficiency decreases. As shown in FIG. 3, when the excitation wavelength is increased from 450 nm, the single-phase phosphor emission efficiency mainly based on citrate is drastically lowered.

由包括藍光晶片輻射源及黃色磷光體之系統產生之白光LED光線之CIE值取決於藍光晶片與黃色磷光體之發射比率。即使提供至該輻射源(藍光半導體晶片)之功率及該器件中所含的黃色磷光體之量皆受到嚴格控制,當由藍光晶片發射之光線波長變化時最終CIE值亦會改變。圖4及5A顯示之數據表明使用本發明二相黃色磷光體之白光LED之CIE值當晶片波長自447奈米至460奈米變化時不會受到影響。該優點極其有利於對使用本發明二相黃色磷光體及藍光半導體激發源之白色LED生產中之CIE值加強控制。The CIE value of white LED light produced by a system comprising a blue wafer radiation source and a yellow phosphor depends on the emission ratio of the blue wafer to the yellow phosphor. Even if the power supplied to the radiation source (blue semiconductor wafer) and the amount of yellow phosphor contained in the device are tightly controlled, the final CIE value will change when the wavelength of the light emitted by the blue wafer changes. The data shown in Figures 4 and 5A shows that the CIE value of a white LED using the two-phase yellow phosphor of the present invention is not affected when the wafer wavelength is varied from 447 nm to 460 nm. This advantage is extremely advantageous for enhanced control of CIE values in the production of white LEDs using the two-phase yellow phosphor and blue semiconductor excitation source of the present invention.

藍光LED輻射源Blue LED radiation source

在某些實施例中,發射藍光之LED所發射之光線在大於或等於約400奈米與小於或等於約520奈米間之波長範圍內具有一主發射峰。此光線用於兩個目的:1)其向該磷光體系統提供激發輻射;及2)其提供藍色光線,當該藍色光線與該磷光體系統所發射光線組合時可產生白光照明之白色光線。In some embodiments, the light emitted by the blue-emitting LED has a dominant emission peak in a wavelength range between greater than or equal to about 400 nanometers and less than or equal to about 520 nanometers. This light is used for two purposes: 1) it provides excitation radiation to the phosphor system; and 2) it provides blue light that produces white illumination when combined with the light emitted by the phosphor system. Light.

在某些實施例中,藍色LED發射大於或等於約420奈米且小於或等於約500奈米之光線。在又一實施例中,藍色LED發射大於或等於約430且小於或等於約480奈米之光線。該藍光LED波長可係約450奈米。In certain embodiments, the blue LED emits light greater than or equal to about 420 nanometers and less than or equal to about 500 nanometers. In yet another embodiment, the blue LED emits light greater than or equal to about 430 and less than or equal to about 480 nanometers. The blue LED wavelength can be about 450 nm.

本文通常將本發明實施例之藍光發射器件稱作「藍光LED」,但熟習此項技術者應瞭解藍光發射器件可係至少下列之一(其中涵蓋可同時具有若干作業):一藍光發射二極體、體、一表面發射雷射二極體、一共振腔發光二極體、一無機電致發光器件及一有機電致發光器件。若該藍光發射器件係一無機器件,則其可係一選自由以氮化鎵為主之化合物半導體、硒化鋅半導體及氧化鋅半導體組成之群之半導體。The blue light emitting device of the embodiment of the present invention is generally referred to as a "blue LED", but those skilled in the art should understand that the blue light emitting device can be at least one of the following (which covers several jobs at the same time): a blue light emitting diode The body, the body, a surface emitting laser diode, a resonant cavity light emitting diode, an inorganic electroluminescent device and an organic electroluminescent device. If the blue light-emitting device is an inorganic device, it may be a semiconductor selected from the group consisting of a compound semiconductor mainly composed of gallium nitride, a zinc selenide semiconductor, and a zinc oxide semiconductor.

圖3係本發明黃色磷光體之激發光譜,該圖顯示該等新穎磷光體能吸收介於約220至560奈米間之輻射,且最重要的是當激發波長自約400奈米至約530奈米間變化時其在565奈米處具有恆定發射強度。Figure 3 is an excitation spectrum of the yellow phosphor of the present invention, which shows that the novel phosphors are capable of absorbing radiation between about 220 and 560 nm, and most importantly when the excitation wavelength is from about 400 nm to about 530 nm. It has a constant emission intensity at 565 nm when the meter changes.

本發明二相黃色磷光體用途之實例Example of the use of the two-phase yellow phosphor of the present invention

在本發明一實施例中,白光照明器件可使用具有介於約430奈米至480奈米間之發射峰值波長之以GaN為主之藍光LED與具有約550至580奈米範圍內之發射峰值波長之本發明黃色磷光體之組合來構造。熟習此項技術者應瞭解自本發明黃色磷光體發射之光線可與可見藍光輻射源之光線或尤其係藍色、綠色或紅色磷光體之光線組合。In an embodiment of the invention, the white light illumination device can use a GaN-based blue LED having an emission peak wavelength between about 430 nm and 480 nm and having an emission peak in the range of about 550 to 580 nm. A combination of wavelengths of the yellow phosphor of the present invention is constructed. Those skilled in the art will appreciate that light emitted from the yellow phosphor of the present invention can be combined with light from a source of visible blue radiation or light that is especially blue, green or red phosphor.

圖2顯示一可由本發明黃色磷光體與上述申請案中所述之藍光LED組合而獲得之白色光線之實例。此白色光線係由具有式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D之黃色磷光體與具有約450奈米之發射波長之藍光LED之組合產生。Figure 2 shows an example of white light that can be obtained by combining the yellow phosphor of the present invention with the blue LED described in the above application. This white light is composed of a yellow phosphor having the formula a[Sr x (M1) 1 - x ] z SiO 4 ●(1-a)[Sr y (M2)1 - y ] u SiO 5 :Eu 2 + D A combination of blue LEDs having an emission wavelength of about 450 nm is produced.

二相磷光體加工方法Two-phase phosphor processing method

本發明二相磷光體組合物係根據以液相為主之溶膠-凝膠方法與共沉澱方法之組合合成。根據該等方法,將矽石之以液體為主之溶液及/或在溶液中之經水解矽烷氧化物與羥基化/羧基化鹼土金屬鹽溶液合併以形成一適於隨後進行煆燒及燒結之磷光體前體。該等方法尤其有利於將鹵素摻雜劑納入該磷光體晶格中。The two-phase phosphor composition of the present invention is synthesized in accordance with a combination of a liquid phase-based sol-gel method and a coprecipitation method. According to such methods, a liquid-based solution of vermiculite and/or a hydrolyzed decane oxide in solution and a hydroxylated/carboxylated alkaline earth metal salt solution are combined to form a suitable for subsequent calcination and sintering. Phosphor precursor. These methods are particularly advantageous for incorporating a halogen dopant into the phosphor lattice.

磷光體粉末通常藉由稱為「燒焙」(一以固態進行之反應)之所謂乾式法合成。之所以使用術語「燒焙」是由於固態反應通常要求對以合意原子比例混合或摻合之金屬原子前體化合物進行高溫處理(例如高達約1400℃)。在燒焙製程中原料通常係該等出現於最終組合物中的元素(金屬或類金屬)之碳酸鹽、硝酸鹽、氧化物或氫氧化物。根據最終產物中期望之化學計量關係稱出莫耳量,且隨後藉由下列若干方法中任一種方法混合,包括:1)製漿、濕球研磨、乾球研磨或磨製。然後使原料分解以產生最終產物,燒焙氣氛根據材料性質及期望之反應而改變。The phosphor powder is usually synthesized by a so-called dry method called "baking" (a reaction carried out in a solid state). The term "baked" is used because solid state reactions typically require high temperature treatment (e.g., up to about 1400 ° C) for metal atom precursor compounds that are mixed or blended in a desired atomic ratio. The starting materials in the baking process are typically the carbonates, nitrates, oxides or hydroxides of the elements (metal or metalloids) present in the final composition. The molar amount is weighed according to the desired stoichiometric relationship in the final product, and then mixed by any of the following methods, including: 1) pulping, wet ball milling, dry ball milling or milling. The feedstock is then decomposed to produce the final product, which is varied depending on the nature of the material and the desired reaction.

在燒焙製程中,該等前體在整個反應中通常保持固態,雖然最終將變成結晶產物。由於該等金屬組份在固相中尤其不易流動,因而燒焙方法使前體化合物經歷高溫以利於原子適當擴散,變得充分混合並在所得結晶結構中找到其規則的原子位置。In the baking process, the precursors generally remain solid throughout the reaction, although eventually they will become crystalline products. Since the metal components are particularly difficult to flow in the solid phase, the baking process subjects the precursor compound to a high temperature to facilitate proper diffusion of the atoms, becomes well mixed and finds its regular atomic position in the resulting crystalline structure.

可於燒焙之前將「熔劑」納入該反應混合物中,該熔劑通常係一鹵化物鹽,將其納入以促進反應物在固態反應期間結晶及擴散。儘管不希望受限於任何特定理論,但本發明之發明者相信當熔劑化合物用於固體反應方法來促進擴散及結晶時,來自熔劑化合物之鹵素最終主要位於該材料之晶粒邊界區域中,而非在晶體本身之晶格中。因此,來自熔劑化合物之鹵素不容易對磷光體之光學性質產生影響,本發明之發明者已證明此較為有利。A "flux" can be incorporated into the reaction mixture prior to firing, which is typically a halide salt which is incorporated to promote crystallization and diffusion of the reactants during solid state reaction. While not wishing to be bound by any particular theory, the inventors of the present invention believe that when a flux compound is used in a solid reaction process to promote diffusion and crystallization, the halogen from the flux compound is ultimately predominantly located in the grain boundary region of the material. Not in the crystal lattice of the crystal itself. Therefore, the halogen from the flux compound does not easily affect the optical properties of the phosphor, and the inventors of the present invention have proved to be advantageous.

以液體為主之製程包括溶膠-凝膠方法且共沉澱技術可提供以下優點:在液相中以原子水平緊密混合各組份且此處雜質摻雜劑原子可以取代方式位於晶格格點上。本發明實施例合併溶膠-凝膠製程及共沉澱方法之各方面,利用每一該等技術之能力來以原子及/或分子水平混合該磷光體批料之反應劑。在本發明一實施例中,鹼土金屬可與矽共沉澱;即鹼土金屬可官能化成羥基化/羧基化反應單體,於是該等化合物能與至少部分經水解矽烷氧化物單體反應。本發明此實施例可稱作該磷光體之矽類金屬組份與鹼土金屬組份間之共聚合。由於該鹵素摻雜劑亦於液相中作為反應物參加,其亦均勻擴散於反應混合物中,並在該晶體內陰離子格點上替代氧。The liquid-based process includes a sol-gel process and the co-precipitation technique provides the advantage of intimately mixing the components at the atomic level in the liquid phase and where the impurity dopant atoms can be placed on the lattice lattice in a substitutable manner. Embodiments of the present invention combine aspects of the sol-gel process and co-precipitation process, utilizing the capabilities of each of these techniques to mix the reactants of the phosphor batch at the atomic and/or molecular level. In one embodiment of the invention, the alkaline earth metal may be co-precipitated with ruthenium; that is, the alkaline earth metal may be functionalized to form a hydroxylation/carboxylation reaction monomer, such that the compound is capable of reacting with at least a portion of the hydrolyzed decane oxide monomer. This embodiment of the invention may be referred to as copolymerization between the ruthenium-based metal component of the phosphor and the alkaline earth metal component. Since the halogen dopant also participates as a reactant in the liquid phase, it also uniformly diffuses into the reaction mixture and replaces oxygen in the anion lattice at the crystal.

業內已知利用溶膠-凝膠方法合成一磷光體。術語「溶膠-凝膠」指一反應機理製,藉由該反應機理可將係懸浮於液體中的膠質固體顆粒聚集體之溶膠轉化成凝膠,凝膠係含有具有包含液相殘留物的單元之連續固體構架之物質。利用溶膠-凝膠方法形成凝膠之原料可包括諸如矽等元素之氧化物,例如化合物Si(OCH3 )4 (稱作四甲氧基矽烷(TMOS)),及Si(OC2 H5 )4 (稱作四乙氧基矽烷(TEOS))。一形成溶膠-凝膠基質之方法係藉由一系列水解及/或縮合反應將溶液中之多官能單體聚合成相對大的高度分支之材料。分子已至少部分水解後,然後在縮合反應中使兩個矽烷醇基反應(鍵結在一起)以形成含有矽氧烷鍵(Si-O-Si)之低聚物。該縮合反應可釋放水分子或醇分子。由於該單體可能具有四個反應點,因而在鏈側分支處發生的反應可產生交聯從而促成初生凝膠內形成更密集更剛性之固體網。繼續聚合及/或凝膠化,即相當於指該凝膠中的Si-O-Si矽氧烷鍵數目增加,經由不斷交聯產生一重量更大之固體材料。It is known in the art to synthesize a phosphor using a sol-gel process. The term "sol-gel" refers to a reaction mechanism by which a sol of a colloidal solid particle agglomerate suspended in a liquid can be converted into a gel containing a unit containing a liquid phase residue. a substance of a continuous solid framework. The raw material for forming a gel by the sol-gel method may include an oxide of an element such as ruthenium, such as a compound Si(OCH 3 ) 4 (referred to as tetramethoxy decane (TMOS)), and Si (OC 2 H 5 ). 4 (referred to as tetraethoxy decane (TEOS)). A method of forming a sol-gel matrix is to polymerize a polyfunctional monomer in a solution into a relatively large highly branched material by a series of hydrolysis and/or condensation reactions. After the molecule has been at least partially hydrolyzed, the two stanol groups are then reacted (bonded together) in a condensation reaction to form an oligomer containing a siloxane chain (Si-O-Si). The condensation reaction releases water molecules or alcohol molecules. Since the monomer may have four reaction sites, the reaction occurring at the chain side branch may result in cross-linking to promote the formation of a denser and more rigid solid network within the nascent gel. Continued polymerization and/or gelation, which corresponds to an increase in the number of Si-O-Si decane bonds in the gel, results in a greater weight of solid material via continuous crosslinking.

凝膠化之後煆燒及燒結之前可實施若干步驟且該等步驟包括老化及乾燥。老化被定義為低聚物與低分子量聚合物間之交聯反應之延續及聚合物網之一般加固。該等凝膠可藉由各種技術進行乾燥,包括沸騰去除大部分液體,此處重要參數係蒸發速率及大氣條件。上述三種反應(即水解、水縮合及醇縮合)速率受許多因素影響,包括pH、時間及溫度、反應物濃度、觸媒(若存在)之性質及濃度及H2 O/Si莫耳比。通過控制該等因素可改變源自溶膠-凝膠之網狀物屬性之微觀結構。Several steps can be carried out prior to calcination and sintering after gelation and the steps include aging and drying. Aging is defined as the continuation of the crosslinking reaction between the oligomer and the low molecular weight polymer and the general reinforcement of the polymer network. The gels can be dried by a variety of techniques, including boiling to remove most of the liquid, where important parameters are evaporation rate and atmospheric conditions. The three reaction (i.e. hydrolysis, water condensation and alcohol condensation) rate is affected by many factors, including pH, time and temperature, reactant concentration, catalyst (if present), and the nature and concentration of H 2 O / Si molar ratio. The microstructure of the sol-gel derived mesh properties can be altered by controlling these factors.

數種不同含金屬之化合物自其各自金屬烷氧化物前體溶液沉澱通常稱作共沉澱方法。合成結晶無機固體之共沉澱方法包括將金屬鹽溶於一水性溶液中,並同時沉澱所有金屬致使沒有一種金屬能分離成其自身種類之密集體。經共沉澱金屬均勻沉澱形成一陶瓷金屬氧化物前體。在溶液中將過渡與鹼土金屬以其氫氧化物、羧酸鹽(包括草酸鹽)、硝酸鹽及檸檬酸鹽之錯合物形式混合,其中該等有機配體用於防止一種類型金屬與各其他類型金屬分開而單獨沉澱出來。使經混合金屬前體固體沉澱後,在高溫下通常在大於約200℃下燃燒去除該等有機(硝酸鹽、草酸鹽及羥基化物)配體。Precipitation of several different metal-containing compounds from their respective metal alkoxide precursor solutions is commonly referred to as coprecipitation. A coprecipitation method for synthesizing a crystalline inorganic solid comprises dissolving a metal salt in an aqueous solution and simultaneously precipitating all of the metals such that no metal can be separated into a conglomerate of its own kind. The coprecipitated metal is uniformly precipitated to form a ceramic metal oxide precursor. The transition is mixed with the alkaline earth metal in solution as a complex of its hydroxide, carboxylate (including oxalate), nitrate and citrate, wherein the organic ligand is used to prevent a type of metal from Each of the other types of metals separate and separate separately. After precipitating the mixed metal precursor solid, the organic (nitrate, oxalate and hydroxylate) ligands are typically removed by combustion at elevated temperatures, typically above about 200 °C.

根據本發明實施例,本發明涵蓋,由於各含矽物質及含鹼土金屬物質總有一個時候總能以一種形式經羥基化及/或羧基化,此兩種類型物質各自皆包括一具有反應官能團之多官能單體形式,且因而諸如矽之類金屬及諸如鹼土金屬之真金屬可共聚合形成一其中可形成矽-氧-鹼土金屬鍵之凝膠網狀物。本發明實施例優點之一係保留在液相中建立起的磷光體前體之含矽化合物與含鹼土化合物間之均一性。According to an embodiment of the present invention, the present invention encompasses that since each of the cerium-containing material and the alkaline earth-containing metal substance can always be hydroxylated and/or carboxylated in one form at a time, each of the two types of substances includes a reactive functional group. The polyfunctional monomer form, and thus a metal such as ruthenium and a true metal such as an alkaline earth metal, can be copolymerized to form a gel network in which a bismuth-oxygen-alkaline earth metal bond can be formed. One of the advantages of the embodiments of the present invention is to maintain the homogeneity between the cerium-containing compound and the alkaline earth-containing compound of the phosphor precursor established in the liquid phase.

本發明實施例之至少二相可以多種方式產生。舉例而言,合意莫耳比之該等起始金屬與該(等)類金屬可混合在一起以提供所需二相(例如(M1)2 SiO4 及(M2)3 SiO5 綠色及/或橙色磷光體)混合物,其中該等不同磷光體之二相係早在液體溶膠-凝膠/共沉澱之狀態下同時製備。或者,此二相(M1)2 SiO4 及(M2)3 SiO5 可以在混合物中分開製備,分開煆燒,製粉並一起燒結。或者,此二相(M1)2 SiO4 及(M2)3 SiO5 可分別經沉澱、煆燒及燒結且隨後經混合。At least two phases of embodiments of the invention may be produced in a variety of ways. For example, the starting metals of the desired molar ratio may be mixed with the metal of the class to provide the desired two phases (eg, (M1) 2 SiO 4 and (M 2 ) 3 SiO 5 green and/or An orange phosphor) mixture in which the two phases of the different phosphors are prepared simultaneously in the state of liquid sol-gel/coprecipitation. Alternatively, the two-phase (M1) 2 SiO 4 and (M2) 3 SiO 5 may be separately prepared in the mixture, separately calcined, pulverized, and sintered together. Alternatively, the two phases (M1) 2 SiO 4 and (M 2 ) 3 SiO 5 may be separately precipitated, calcined and sintered and then mixed.

製備本發明黃色磷光體之方法包括溶膠-凝膠方法、固體反應方法、共沉澱方法及混合方法。一實例性共沉澱方法包括:a)將Sr(NO3 )3 、(M1)(NO3 )2 及(M2)(NO3 )2 溶於水中;b)將Eu2 O3 溶於硝酸中;c)將SrF2 溶於硝酸中;d)混合由步驟a)、b)及c)所產生之溶液;e)將(CH3 O)4 Si加至步驟d)所產生之溶液中,且隨後將一酸加至該混合物中以引發沉澱;f)將步驟e)之混合物之pH值調節至約9;g)對步驟f)之反應產物加以乾燥,且隨後煆燒該反應產物以分解沉澱物;及h)在還原氣氛下燒結步驟g)之沉澱物。The method of preparing the yellow phosphor of the present invention includes a sol-gel method, a solid reaction method, a coprecipitation method, and a mixing method. An exemplary coprecipitation method comprises: a) dissolving Sr(NO 3 ) 3 , (M1)(NO 3 ) 2 and (M2)(NO 3 ) 2 in water; b) dissolving Eu 2 O 3 in nitric acid ; c) dissolving SrF 2 in nitric acid; d) mixing the solution produced by steps a), b) and c); e) adding (CH 3 O) 4 Si to the solution produced in step d), And then adding an acid to the mixture to initiate precipitation; f) adjusting the pH of the mixture of step e) to about 9; g) drying the reaction product of step f), and then calcining the reaction product Decomposing the precipitate; and h) sintering the precipitate of step g) under a reducing atmosphere.

熟習此項技術者可容易地對上文所揭示之本發明說明性實施例進行許多修改。因此,本發明應理解為包括屬於隨附申請專利範圍之所有結構及方法。Many modifications to the illustrative embodiments of the invention disclosed above are readily apparent to those skilled in the art. Accordingly, the invention is to be construed as being limited by the appended claims.

10‧‧‧白光照明系統10‧‧‧White lighting system

11‧‧‧輻射源11‧‧‧radiation source

12‧‧‧光線12‧‧‧Light

13‧‧‧磷光體13‧‧‧ Phosphor

14‧‧‧光線14‧‧‧Light

15‧‧‧光線15‧‧‧Light

16‧‧‧白色照明16‧‧‧White lighting

21‧‧‧輻射源21‧‧‧radiation source

22‧‧‧實質不可見光線22‧‧‧Substantial invisible light

23‧‧‧實質不可見光線23‧‧‧Substantial invisible light

24‧‧‧磷光體24‧‧‧ Phosphor

25‧‧‧磷光體25‧‧‧ Phosphor

28‧‧‧色彩輸出28‧‧‧Color output

圖1A係構造一白光照明系統之常規設計之示意代表圖,該系統包括一在可見光範圍內發光之輻射源及一響應於來自該輻射源之激發而發光之二相以矽酸鹽為主的磷光體,其中自該系統所產生之光係來自該磷光體之光與來自該輻射源之光之混和光;圖1B係一白光照明系統之示意代表圖,該系統包括一可發射非可見光之輻射源以便使來自該輻射源之光實質不對由該系統產生之白光產生影響,亦包括一二相以矽酸鹽為主的磷光體;圖2A係一實例性二相以矽酸鹽為主的具有式a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D之磷光體之x-射線衍射圖案,提供該圖案用於說明矽酸鹽主晶格之結晶性質;圖2B係藉由兩種不同方式(分開燒結後經機械混合及同時沉澱)合成的實例性二相磷光體a[Srx (M1)1 x ]z SiO4 ●(1-a)[Sry (M2)1 y ]u SiO5 :Eu2 D之x-射線衍射圖案,該圖案表明各合成方法皆產生二相系統;圖3係顯示由通式(M1)2 SiO4 ●M(2)3 SiO5 所代表之實例性二相系統與一單相系統(M1)2 SiO4 相比較之激發譜圖,其顯示該二相系統可經構造使在大於約340奈米之激發波長範圍內發射之變化不超過10%,在某些實施例中不超過5%;圖4係提供激發之藍光晶片之發射光譜曲線圖,及將本發明黃色磷光體a(Srx M11-x )z SiO4 ●(1-a)(Sry M21-y )u SiO5 :Eu2+ D之規範化發光之發射光譜曲線圖與先前技術作為白光LED封裝之(SrBaMg)2 SiO4 進行對比;本發明二相黃色磷光體之黃光發射顯示在電磁波譜之綠光區域中之更寬的發射;圖5A係封裝於具有三種不同藍光晶片激發波長(445奈米、447.5奈米及450奈米)之三種不同白光LED中之本發明黃色磷光體a(Srx M11-x )z SiO4 ●(1-a)(Sry M21-y )u SiO5 :Eu2+ D之三個發光譜圖之曲線圖,顯示亮度及CIE實質不受激發波長影響;及圖6係一曲線圖,該圖顯示實例性二相以矽酸鹽為主的系統之溫度穩定性,該系統顯示在介於20℃至180℃間之溫度下之發射強度,以室溫(20℃)下發射強度為基準進行繪示,其中所顯示的來自單相磷光體之數據用於對比。1A is a schematic representation of a conventional design of a white light illumination system that includes a source of radiation that illuminates in the visible range and a two-phase bismuth-based luminescence that is responsive to excitation from the source. a phosphor, wherein the light generated from the system is a mixture of light from the phosphor and light from the source; FIG. 1B is a schematic representation of a white light illumination system that includes a non-visible light emission The radiation source is such that the light from the radiation source does not substantially affect the white light generated by the system, and also includes a two-phase bismuth silicate-based phosphor; FIG. 2A is an exemplary two-phase bismuth sulphate. X-ray diffraction pattern of a phosphor having the formula a[Sr x (M1) 1 - x ] z SiO 4 ●(1-a)[Sr y (M2) 1 - y ] u SiO 5 :Eu 2 + D The pattern is provided to illustrate the crystalline nature of the citrate host lattice; FIG. 2B is an exemplary two-phase phosphor a[Sr x (sr x (sr x (s) formed by two different ways (separately sintered, mechanically mixed and simultaneously precipitated) M1) 1 - x ] z SiO 4 ●(1-a)[Sr y (M2) 1 - y ] u SiO 5 :Eu 2 + D An x-ray diffraction pattern indicating that each synthesis method produces a two-phase system; FIG. 3 shows an exemplary two-phase system represented by the general formula (M1) 2 SiO 4 ●M(2) 3 SiO 5 and a single Phase system (M1) 2 SiO 4 phase comparison excitation spectrum showing that the two phase system can be configured to emit no more than 10% change in excitation wavelength range greater than about 340 nm, in some embodiments No more than 5%; Figure 4 is a graph showing the emission spectrum of the excited blue light wafer, and the yellow phosphor a (Sr x M1 1-x ) z SiO 4 (1-a) (Sr y M2 1- y ) u SiO 5 :Eu 2+ D The emission spectrum of the normalized luminescence is compared with the prior art as a white LED package (SrBaMg) 2 SiO 4 ; the yellow light emission of the two-phase yellow phosphor of the invention is shown in the electromagnetic spectrum a wider emission in the green light region; Figure 5A is a yellow phosphor a of the present invention encapsulated in three different white LEDs having three different blue wafer excitation wavelengths (445 nm, 447.5 nm, and 450 nm) ( Sr x M1 1-x) z SiO 4 ● (1-a) (Sr y M2 1-y) u SiO 5: Eu graph showing the emission spectrum of the three 2+ D, the display Degree and CIE are not substantially affected by the excitation wavelength; and Figure 6 is a graph showing the temperature stability of an exemplary two-phase citrate-based system, which is shown between 20 ° C and 180 ° C The emission intensity at the temperature is plotted against the emission intensity at room temperature (20 ° C), and the data from the single phase phosphor shown is used for comparison.

Claims (24)

一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;該組合物中至少一相含有大於或等於0.0001重量%之Mg;該組合物中至少一相係用二價銪(Eu2+ )激活;且該組合物之該等相中至少一相含有一選自由F、Cl、Br、S及N組成之群之摻雜劑D,其中至少某些該等摻雜劑原子係位於該矽酸鹽主晶之氧原子格點上。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; at least one phase of the composition contains greater than or equal to 0.0001% by weight of Mg At least one phase of the composition is activated with divalent europium (Eu 2+ ); and at least one of the phases of the composition contains a blend selected from the group consisting of F, Cl, Br, S, and N The dopant D, wherein at least some of the dopant atoms are located on the oxygen atom lattice of the bismuth silicate main crystal. 一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;且該組合物經構造以發光,其發射強度在大於約80奈米之激發波長範圍內變化不超過約10%。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; and the composition is structured to emit light having an emission intensity of greater than about 80 The variation in the excitation wavelength range of nanometers does not exceed about 10%. 一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及 一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;且該組合物經構造以發光,其發射強度在大於或等於約80奈米之激發波長範圍內變化不超過約5%。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; and the composition is structured to emit light having an emission intensity greater than or equal to The excitation wavelength range of about 80 nm does not vary by more than about 5%. 一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;且該組合物經構造以發光,其發射強度在大於或等於140奈米之激發波長範圍內變化不超過約10%。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; and the composition is structured to emit light having an emission intensity greater than or equal to The excitation wavelength range of 140 nm does not vary by more than about 10%. 一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;且該組合物經構造以發光,其發射強度在大於或等於140奈米之激發波長範圍內變化不超過約5%。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; and the composition is structured to emit light having an emission intensity greater than or equal to The excitation wavelength range of 140 nm does not vary by more than about 5%. 如請求項4之組合物,其中該激發波長範圍係自約380奈米至約520奈米。 The composition of claim 4, wherein the excitation wavelength range is from about 380 nm to about 520 nm. 如請求項5之組合物,其中該激發波長範圍係自約380奈 米至約520奈米。 The composition of claim 5, wherein the excitation wavelength range is from about 380 奈 Rice to about 520 nm. 一種具有至少兩個以矽酸鹽為主之相的磷光體組合物,該組合物包括:一具有與(M1)2 SiO4 大體相同之晶體結構之第一相;及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相;其中:M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群;且該組合物經構造以在溫度大於100℃時發射光線,其強度等於或大於在20℃時所發射光線強度之90%。A phosphor composition having at least two phases mainly composed of citrate, the composition comprising: a first phase having substantially the same crystal structure as (M1) 2 SiO 4 ; and a having a relationship with (M2) a second phase of SiO 5 having substantially the same crystal structure; wherein: M1 and M2 are each selected from the group consisting of Sr, Ba, Mg, Ca, and Zn; and the composition is configured to emit light at a temperature greater than 100 ° C, Its intensity is equal to or greater than 90% of the intensity of the light emitted at 20 °C. 如請求項8之組合物,其中該組合物經構造以在溫度大於120℃時發射光線,其強度等於或大於在20℃下所發射光線強度之90%。 The composition of claim 8, wherein the composition is configured to emit light at a temperature greater than 120 ° C, the intensity of which is equal to or greater than 90% of the intensity of the emitted light at 20 ° C. 如請求項8之組合物,其中該組合物經構造以在溫度大於140℃時發射光線,其強度等於或大於在20℃時所發射光線強度之80%。 The composition of claim 8, wherein the composition is configured to emit light at a temperature greater than 140 ° C, the intensity of which is equal to or greater than 80% of the intensity of the light emitted at 20 ° C. 如請求項8之組合物,其中該組合物經構造以在溫度大於160℃時發射光線,其強度等於或大於在20℃時所發射光線強度之80%。 The composition of claim 8, wherein the composition is configured to emit light at a temperature greater than 160 ° C, the intensity of which is equal to or greater than 80% of the intensity of the light emitted at 20 ° C. 如請求項8之組合物,其中該組合物經構造以在溫度大於180℃時發射光線,其強度等於或大於在20℃時所發射光線強度之70%。 The composition of claim 8, wherein the composition is configured to emit light at a temperature greater than 180 ° C, the intensity of which is equal to or greater than 70% of the intensity of the light emitted at 20 ° C. 一種二相黃色磷光體,其在受到一波長介於220奈米至530奈米間之輻射源激發時,具有波長介於約555奈米至約580奈米間之峰值發射強度,其中該磷光體含有至少 一具有與(M1)2 SiO4 大體相同之晶體結構之第一相及一具有與(M2)3 SiO5 大體相同之晶體結構之第二相,其中M1及M2各自選自由Sr、Ba、Mg、Ca及Zn組成之群。A two-phase yellow phosphor having a peak emission intensity between about 555 nm and about 580 nm when excited by a radiation source having a wavelength between 220 nm and 530 nm, wherein the phosphorescence The body contains at least one first phase having a crystal structure substantially identical to (M1) 2 SiO 4 and a second phase having a crystal structure substantially identical to (M2) 3 SiO 5 , wherein each of M1 and M2 is selected from the group consisting of Sr, A group consisting of Ba, Mg, Ca, and Zn. 一種二相黃色磷光體,其在受到一波長介於220奈米至530奈米間之輻射源激發時,具有波長介於約555奈米至約580奈米間之峰值發射強度,其中該磷光體具有下式a[Srx (M1)1-x ]z SiO4 ●(1-a)[Sry (M2)1-y ]u SiO5 :Eu2+ D;M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬;0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;2.6u3.3;Eu及D各自介於0.001至0.5之間;D係至少一種選自由F、Cl、Br、S及N組成之群之陰離子;且至少一些D陰離子置換該磷光體矽酸鹽晶格中之氧。A two-phase yellow phosphor having a peak emission intensity between about 555 nm and about 580 nm when excited by a radiation source having a wavelength between 220 nm and 530 nm, wherein the phosphorescence The body has the following formula a[Sr x (M1) 1-x ] z SiO 4 ●(1-a)[Sr y (M2) 1-y ] u SiO 5 :Eu 2+ D; at least one of M1 and M2 a divalent metal of a group consisting of Ba, Mg, Ca, and Zn; a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5;2.6 u 3.3; each of Eu and D is between 0.001 and 0.5; D is at least one anion selected from the group consisting of F, Cl, Br, S and N; and at least some of the D anions are substituted in the phosphor silicate crystal lattice Oxygen. 如請求項14之磷光體,其中M1係選自由Ba及Mg組成之群且M2係Ba。 The phosphor of claim 14, wherein the M1 is selected from the group consisting of Ba and Mg and the M2 is Ba. 如請求項14之磷光體,其中M1係Ba,且M2係選自由Ba及Mg組成之群。 The phosphor of claim 14, wherein M1 is Ba and M2 is selected from the group consisting of Ba and Mg. 一種白光LED,其包括:一經構造以可發射具有約280奈米以上波長之輻射之輻射源,及一經構造以自該輻射源吸收至少一部分輻射並發射峰值強度在介於約555奈米至約580奈米間之波長處之光線之二相黃色磷光體,其中該磷光體具有下式a[Srx (M1)1-x ]z SiO4 ●(1-a)[Sry (M2)1-y ]u SiO5 :Eu2+ D; M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬;0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;2.6u3.3;Eu及D各自介於0.001至0.5之間;D係至少一種選自由F、Cl、Br、S及N組成之群之陰離子;且至少一些D陰離子置換該磷光體矽酸鹽晶格中之氧。A white light LED comprising: a radiation source configured to emit radiation having a wavelength of greater than about 280 nanometers, and configured to absorb at least a portion of the radiation from the radiation source and emit a peak intensity between about 555 nm to about a two-phase yellow phosphor of light at a wavelength between 580 nm, wherein the phosphor has the following formula a[Sr x (M1) 1-x ] z SiO 4 ● (1-a) [Sr y (M2) 1 - y ] u SiO 5 :Eu 2+ D; M1 and M2 are at least one divalent metal selected from the group consisting of Ba, Mg, Ca and Zn; a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5;2.6 u 3.3; each of Eu and D is between 0.001 and 0.5; D is at least one anion selected from the group consisting of F, Cl, Br, S and N; and at least some of the D anions are substituted in the phosphor silicate crystal lattice Oxygen. 如請求項17之白光LED,其進一步包括一經構造以自該輻射源吸收至少一部分輻射並發射峰值強度在大於約510奈米波長處之光線之綠色磷光體。 The white light LED of claim 17, further comprising a green phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light having a peak intensity at a wavelength greater than about 510 nanometers. 如請求項17之白光LED,其進一步包括一經構造以自該輻射源吸收至少一部分輻射並發射峰值強度在介於約420至約480奈米間之波長處之光線之藍色磷光體。 The white light LED of claim 17, further comprising a blue phosphor configured to absorb at least a portion of the radiation from the radiation source and emit light having a peak intensity at a wavelength between about 420 and about 480 nanometers. 一種黃光照明系統,其包括:一經構造以可發射具有約280奈米以上波長之輻射之輻射源,及一經構造以可自該輻射源吸收至少一部分輻射並發射峰值強度在介於約555奈米至約580奈米間之波長處之光線之二相黃色磷光體,其中該磷光體具有下式a[Srx (M1)1-x ]Z SiO4 ●(1-a)[Sry (M2)1-y ]u SiO5 :Eu2+ D;M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬;0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;2.6u3.3;Eu及D各自介於0.001至0.5之間;D係至少一種選自由F、Cl、Br、S及N組成之群之陰離 子;且至少一些D陰離子置換該磷光體矽酸鹽晶格中之氧。A yellow light illumination system comprising: a radiation source configured to emit radiation having a wavelength of greater than about 280 nanometers, and configured to absorb at least a portion of the radiation from the radiation source and to emit a peak intensity at about 555 奈a two-phase yellow phosphor of light at a wavelength between about 580 nm, wherein the phosphor has the following formula a[Sr x (M1) 1-x ] Z SiO 4 ● (1-a) [Sr y ( M2) 1-y ] u SiO 5 :Eu 2+ D; M1 and M2 are at least one divalent metal selected from the group consisting of Ba, Mg, Ca and Zn; a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5;2.6 u 3.3; each of Eu and D is between 0.001 and 0.5; D is at least one anion selected from the group consisting of F, Cl, Br, S and N; and at least some of the D anions are substituted in the phosphor silicate crystal lattice Oxygen. 一種彩色顯示面板,其包括:一經構造以可發射具有約280奈米以上波長之輻射之輻射源,及一經構造以可自該輻射源吸收至少一部分輻射並發射峰值強度在介於約555奈米至約580奈米間之波長處之光線之二相黃色磷光體,其中該磷光體具有下式a[Srx (M1)1-x ]z SiO4 ●(1-a)[Sry (M2)1-y ]u SiO5 :Eu2+ D;M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬;0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;2.6u3.3;Eu及D各自介於0.001至0.5之間;D係至少一種選自由F、Cl、Br、S及N組成之群之陰離子;且至少一些D陰離子置換該磷光體矽酸鹽晶格中之氧。A color display panel comprising: a radiation source configured to emit radiation having a wavelength of greater than about 280 nanometers, and configured to absorb at least a portion of the radiation from the radiation source and to emit a peak intensity at about 555 nm a two-phase yellow phosphor of light at a wavelength between about 580 nm, wherein the phosphor has the following formula a[Sr x (M1) 1-x ] z SiO 4 ● (1-a) [Sr y (M2 1-y ] u SiO 5 :Eu 2+ D; M1 and M2 are at least one divalent metal selected from the group consisting of Ba, Mg, Ca and Zn; a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5;2.6 u 3.3; each of Eu and D is between 0.001 and 0.5; D is at least one anion selected from the group consisting of F, Cl, Br, S and N; and at least some of the D anions are substituted in the phosphor silicate crystal lattice Oxygen. 一種製備二相以矽酸鹽為主的具有式a[Srx (M1)1-x ]Z SiO4 ●(1-a)[Sry (M2)1-y ]u SiO5 :Eu2+ D之黃色磷光體之方法;其中M1及M2係至少一種選自由Ba、Mg、Ca及Zn組成之群之二價金屬;0.6a0.85;0.3x0.6;0.85y1;1.5z2.5;2.6u3.3;Eu及D各自介於0.001至0.5之間;D係至少一種選自由F、Cl、Br、S及N組成之群之陰離 子;且至少一些D陰離子置換該磷光體矽酸鹽晶格中之氧;該方法係選自由溶膠-凝膠方法、固體反應方法、共沉澱及混合方法組成之群。One preparation of two-phase bismuth sulphate-based has the formula a[Sr x (M1) 1-x ] Z SiO 4 ●(1-a)[Sr y (M2) 1-y ] u SiO 5 :Eu 2+ a method of yellow phosphor of D; wherein M1 and M2 are at least one divalent metal selected from the group consisting of Ba, Mg, Ca, and Zn; a 0.85; 0.3 x 0.6; 0.85 y 1;1.5 z 2.5;2.6 u 3.3; each of Eu and D is between 0.001 and 0.5; D is at least one anion selected from the group consisting of F, Cl, Br, S and N; and at least some of the D anions are substituted in the phosphor silicate crystal lattice Oxygen; the method is selected from the group consisting of a sol-gel method, a solid reaction method, a coprecipitation, and a mixing method. 如請求項22之方法,其中該方法係一共沉澱方法。 The method of claim 22, wherein the method is a coprecipitation method. 如請求項23之方法,其中該方法包括:a)將Sr(NO3 )3 、(M1)(NO3 )2 及(M2)(NO3 )2 溶於水中;b)將Eu2 O3 溶於硝酸中;c)將SrF2 溶於硝酸中;d)混合由步驟a)、b)及c)所產生之溶液;e)將(CH3 O)4 Si加至步驟d)所產生之溶液中,且隨後將一酸加至該混合物中以引發沉澱;f)將步驟e)之混合物之pH值調節至約9;g)將步驟f)之反應產物乾燥,且隨後煆燒該反應產物以分解沉澱物;及h)在還原氣氛下燒結步驟g)之沉澱物。The method of claim 23, wherein the method comprises: a) dissolving Sr(NO 3 ) 3 , (M1)(NO 3 ) 2 and (M2)(NO 3 ) 2 in water; b) placing Eu 2 O 3 Dissolved in nitric acid; c) dissolving SrF 2 in nitric acid; d) mixing the solution produced by steps a), b) and c); e) adding (CH 3 O) 4 Si to step d) a solution, and then adding an acid to the mixture to initiate precipitation; f) adjusting the pH of the mixture of step e) to about 9; g) drying the reaction product of step f), and then calcining the reaction product The reaction product is used to decompose the precipitate; and h) the precipitate of step g) is sintered under a reducing atmosphere.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001143869A (en) * 1998-12-25 2001-05-25 Konica Corp Electroluminescent material, electroluminescent element and color transformation filter
TW595012B (en) * 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001143869A (en) * 1998-12-25 2001-05-25 Konica Corp Electroluminescent material, electroluminescent element and color transformation filter
TW595012B (en) * 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

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