1251248 五、發明說明（1) — 發明所屬之技術領域 本發明係關於一種混合式螢光體配方，尤其關於一種 可被藍光LED激發而產生白光之混合式螢光體配方，其中 包含一種_化矽酸鹽發綠光螢光體及一種含硫發紅光螢光 體。 先前技術 白光發光二極體（light emitting diodes; LEDs)為 目前LED市場最被看好之新興產品，其於照明市場的發展 潛力值得期待。其與白熾鎢絲燈泡及日光燈相比，led具 有體積小，發熱量低（無熱輻射）、耗電量低（低電壓、低 電流啟動）、壽命長（丨萬小時以上）、反應速度快（可高頻 操作）、環保（耐囊、耐衝擊不易破、廢棄物可回收、無污 ί、Γ-平：雷封裝/開發成輕薄短小產品等優點。其無白熾 看好於未來1〇年：廢棄物含汞等缺點，為被業界 品。隨著目前LED技術之\\代傳統照明n器具之—大潛力商 展，包括：指示燈、攜ίΐί，自光㈣之應用也逐漸開 及内裝燈。簡而言之，目式/電筒、LCD背光板、汽車儀板 源為當前之主要應用。別白光led乃以照明光源及背光 路*目：：tif要乃利用曰本曰亞公司所揭示之以藍光 發光二極體激發紀铭石抱 YAG:Ce，Gd)使其產生黃夫（yttriUm alUDlinate garnet; 混合配比，將可得白光1°Τϊί黃光與入射之藍光經適合之BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a hybrid phosphor formulation, and more particularly to a hybrid phosphor formulation that can be excited by a blue LED to produce white light, including a A citrate-emitting green phosphor and a sulfur-containing red-light phosphor. Prior Art White light emitting diodes (LEDs) are the most optimistic emerging products in the LED market, and their potential for development in the lighting market is worth looking forward to. Compared with incandescent tungsten bulbs and fluorescent lamps, LED has small volume, low heat generation (no heat radiation), low power consumption (low voltage, low current start), long life (more than 10,000 hours), fast response (High-frequency operation), environmental protection (resistant to bladder, impact resistance is not easy to break, waste can be recycled, no pollution, Γ-Ping: Lei package / development into a light and thin short product, etc. Its no incandescence is better than the next one year : Waste contains mercury and other shortcomings, and it is the product of the industry. With the current LED technology, the traditional potential of the traditional lighting n appliances, including: the indicator light, carrying ίΐ, the application of self-light (4) is gradually open Built-in light. In short, the eye/flashlight, LCD backlight, and car board source are the main applications at present. Don't use white light led illumination source and backlight. *: tif want to use 曰本曰亚The company reveals that the blue light emitting diode excites Ji Mingshi to hold YAG:Ce,Gd) to produce yellow yttriUm alUDlinate garnet; the mixing ratio will be suitable for white light 1°Τϊί yellow light and incident blue light.
Patent:TW383508)〇 ^ latent:5998925;ROC 裡渑合並非以傳統之紅綠藍（RGB)Patent: TW383508) 〇 ^ latent: 5998925; ROC 渑 merge with non-traditional red, green and blue (RGB)
1251248 五、發明說明（2) 之混光，故其演色性低（R a = 7 0〜8 5 )。最近美國l u m i 1 e d s公 司揭露以被藍光L E D激發而發綠光之S r G a 2 S 4 : E u 2 +與發紅 光之SrS:Eu2+，可形成RG B混光之白光。故其演色性較日 本日亞公司之白光高，約可達Ra二93(如JP特開 2002-60747; IEEE J. Selected Topics in Quantum Electronics 8，March/April 2002 )其所揭示之螢光粉皆 為稀土元素摻雜之硫化物。類似之研究成果，如韓國Huh 等人揭示以藍光激發發綠光之SrGa2S4 : Eu與發紅光之 ZnCdS: AgC卜而可經由RGB光色混合形成白光（如：J. Electrochem· Soc· 150， 2003， H57)1251248 V. Inventive Note (2) The light mixing is low, so the color rendering is low (R a = 7 0~8 5 ). Recently, the United States l u m i 1 e d s discloses that S r G a 2 S 4 : E u 2 + which emits green light by blue light L E D and SrS:Eu2+ which emits red light can form white light of RG B mixed light. Therefore, its color rendering is higher than that of Japan's Nichia Corporation, and it can reach Ra 2 93 (such as JP J. 2002-60747; IEEE J. Selected Topics in Quantum Electronics 8, March/April 2002). All are rare earth doped sulfides. Similar research results, such as Huh et al., Korea, have revealed that SrGa2S4: Eu, which emits green light with blue light, and ZnCdS: AgC, which emit red light, can form white light by RGB light color mixing (eg, J. Electrochem·Soc·150, 2003, H57)
Lumi leds公司與Huh等人所揭示被藍光激發之綠光或紅光 螢光粉組成中全部均含硫（S)，因硫離子（S2-)之共價性較 矽酸根離子（Si 04 2_)或鹵離子（X-，X=F，Cl，Br， I)等之 共價性強，其屬強鹼，故易與空氣中之水氣作用而被分 解，即失去螢光粉特性，進而使白光LED之壽命變短。 故如何發展可被藍光LED激發而產生綠光與紅光之化學穩 定螢光粉乃為重要之課題。 發明内容 本發明乃利用藍光LED激發不含硫之鹵化矽酸鹽之螢 光粉，使其產生綠光，並激發一含硫其表面可為覆蓋絕緣 體之螢光粉使其產生紅光，經此RGB混光，而可產生壽命 長之白光LED。 實施方式 本發明乃利用藍光LED( 430〜49 Onm)激發二種螢光粉使Lumi leds and Huh et al. disclose that all of the green-light or red-light phosphors excited by blue light contain sulfur (S), because the covalentity of sulfur ions (S2-) is more than that of citrate ions (Si 04 2_ Or a halogen ion (X-, X=F, Cl, Br, I), etc., which has a strong covalent property, and is a strong base, so it is easily decomposed by the action of water vapor in the air, that is, the characteristics of the fluorescent powder are lost. Further, the life of the white LED is shortened. Therefore, how to develop a chemically stable phosphor which can be excited by a blue LED to generate green light and red light is an important issue. SUMMARY OF THE INVENTION The present invention utilizes a blue LED to excite a phosphor powder containing no sulfur-containing halogenated niobate to generate green light, and to excite a sulfur-containing surface which can be a fluorescent powder covering the insulator to generate red light. This RGB is mixed to produce a white LED with a long life. Embodiments The present invention utilizes a blue LED (430~49 Onm) to excite two types of phosphor powder.
第5頁 1251248 五、發明說明（3) —-- 其分別產生綠紅光，其中一種乃鹵化矽酸鹽之螢光粉，使 其產生綠光。而另一種為表面包覆絕緣層之含硫螢光粉使 其產生紅光。此三種RGB色光混合將可調配成白光。本發 明之優點為其中被激發產生綠光之螢光粉，其不含硫離 子’而為含_化石夕酸鹽，其較硫離子而言共價性較差，故 可穩定存在於空氣環境中。而其中被激發產生紅光之含硫 離子螢光粉，因其表面亦可包覆於絕緣層中，故其可穩定 在空氣中。故本發明可改善習用Lumi leds公司等所揭示完 全以硫化物為綠光及紅光螢光粉較不穩定於空氣中之缺 點。此外本發明以藍光激發兩種螢光粉，使其分別發綠光 與紅光’故其演色性將較日亞公司所揭示之藍光LED與其 激發Y A G產生黃光所產生之白光為高。於是，本發明所提 出之螢光粉配方具新穎性與進步性，且可實際應用於製作 白光LED，故亦具產業應用性。 實例1 將具微米（// in)級粒徑之 Ca8Mg(Si04)4C12:Eu2 + ,Mn2 + 及SrS:Eu2+螢光粉與A B膠（e ρ ο X y之一種）分別以8%及1 1% 之比例均勻混合，將其封入含有46 0nm之氮化鎵LED晶粒之 杯（cup)内。經適當電流加入此成品内，可產生白光。經 此封裝後之發光二極體，其加入1 OmA之電流後，其所產生 之46 Onm波長之藍光，可有效激發 〇88^^(3丨04)4(：12』112 + (%112 + )螢光粉產生波長 5 0 711111之綠 光及SrS:Eu2+螢光粉產生波長620nm之紅光，經此RGB色光 混合可產生白光。Page 5 1251248 V. INSTRUCTIONS (3) —-- They produce green-red light, one of which is a phosphorous halide of bismuth hydride, which produces green light. The other is a sulfur-containing phosphor powder coated with an insulating layer to cause red light. These three RGB color mixing will be adjustable to white light. The invention has the advantages that the phosphor powder which is excited to generate green light does not contain sulfur ions and is a _ fossil acid salt, which is less covalent than the sulfur ion, so it can be stably present in the air environment. . The sulfur-containing phosphor powder which is excited to generate red light can be stabilized in the air because its surface can also be coated in the insulating layer. Therefore, the present invention can improve the disadvantages of the conventional Lumi leds company and the like that the sulfide is green and the red phosphor is less stable in the air. In addition, the present invention excites two types of phosphors in blue light to emit green and red light respectively, so that the color rendering property is higher than that of the blue LEDs revealed by Nichia and the yellow light generated by the excitation of Y A G . Therefore, the phosphor powder formulation proposed by the present invention is novel and progressive, and can be practically applied to the production of white LEDs, so it is also industrially applicable. Example 1 Ca8Mg(Si04)4C12:Eu2+, Mn2+ and SrS:Eu2+ phosphor powder with a micron (//in) particle size and AB gel (one of e ρ ο X y) were respectively 8% and 1 A 1% ratio was uniformly mixed and sealed in a cup containing 460 nm gallium nitride LED dies. White light can be produced by adding an appropriate current to the finished product. After the packaged LED, after adding a current of 1 OmA, the blue light of 46 Onm wavelength generated by the LED can effectively excite 〇88^^(3丨04)4(:12』112+ (%112) + ) Fluorescent powder produces green light with a wavelength of 5 0 711111 and SrS:Eu2+ fluorescent powder produces red light with a wavelength of 620 nm, which can produce white light by mixing RGB color light.
第6頁 1251248 五、發明說明（4) 實例2 除3^:£112+螢光體表面包覆2-1〇11111之8丨02絕緣層外， 其餘皆與實施例1同。測試結果其白光LED壽命約為實例1 白光L E D壽命長的1 0至2 0倍。 以上僅舉例說明本發明，對本發明所作之各種簡單變更， 例如以 CaS:Eu2+、 BaS:Eu2+、 （Sr，Ca)S:Eu2+、 (Sr，Ba，Ca)S:Eu2+、 （Ba，Ca)S:Eu2+、 ZnCdS:Ag、或 ZnCdS·· Ag，Cl取代SrS:Eu2+、或者以ZnO絕緣層取代si02絕 緣層，皆不脫離本發明之精神與範圍。Page 6 1251248 V. INSTRUCTIONS (4) Example 2 The same as Example 1 except that the surface of the phosphor is coated with the 8丨02 insulating layer of 2-1〇11111. The test results show that the white LED lifetime is about 10 to 20 times longer than the lifetime of the white light L E D of the example 1. The above is merely illustrative of the present invention, and various simple modifications made to the present invention, for example, CaS:Eu2+, BaS:Eu2+, (Sr,Ca)S:Eu2+, (Sr,Ba,Ca)S:Eu2+, (Ba,Ca) S: Eu2+, ZnCdS:Ag, or ZnCdS··Ag, Cl instead of SrS:Eu2+, or a ZnO insulating layer in place of the SiO 2 insulating layer, without departing from the spirit and scope of the invention.
第7頁 1251248 圖式簡單說明 圖一經藍光 LED激發 Ca8Mg(Si04)4C12:Eu2 +，Mn2+螢光 粉產生綠光及SrS:Eu2+螢光粉產生紅光之光譜圖。Page 7 1251248 Brief description of the diagram Figure 1 shows the spectrum of red light generated by Ca8Mg(Si04)4C12:Eu2 +, Mn2+ phosphor powder and SrS:Eu2+ phosphor powder.
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