1323277 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種螢光材料之製造方法，尤其關於一種氧氮 化合物螢光材料之製造方法。 » 【先前技術】 發光二極體(LED)之發光原理和結構與傳統光源並不相同， φ 且具有體積小、高可靠度等優點，在市場上的應用頗為廣泛。例 如，光學顯示裝置、雷射二極體、交通號誌、資料儲存襞置、通 訊裝置、照明裝置、醫療裝置、以及配合需求製成各種大型元件， 以應用於室内或室外大型顯示螢幕。 隨著白光LK)之出現，使得LK)應用領域跨足至照明光源 市場。白光LED之作法可為使用紅光、藍光與綠光三顆LED f 分別控制通過LED之電流再經過混光後以產生白光。另一種作 法係使用黃光與藍光二顆LED，控制通過led之電流再經過混 _ ^而產生白光。在上述之做法’若其巾-顆LED發生劣化，則 無法制所需之白光，且同時使用多個LED，成本也相對提高。 • I"6年日本日亞化學⑽物Chemical)在可發出460nm波 : 長光之InGaN藍光晶粒塗上一層以鈽為活化中心(activator)之纪1323277 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a fluorescent material, and more particularly to a method for producing an oxygen-nitrogen compound fluorescent material. » [Prior Art] The principle and structure of the light-emitting diode (LED) are not the same as those of the traditional light source. φ has the advantages of small size and high reliability, and is widely used in the market. For example, optical display devices, laser diodes, traffic signals, data storage devices, communication devices, lighting devices, medical devices, and various large components for use in large-scale indoor or outdoor display screens. With the advent of white light LK), the LK) application field has penetrated into the lighting source market. The white LED method can control the current passing through the LED and then mix the light to generate white light by using three LEDs f, red, blue and green. Another method uses two LEDs, yellow and blue, to control the current through the LED and then to produce white light. In the above-mentioned method, if the towel-LED is deteriorated, the required white light cannot be produced, and at the same time, a plurality of LEDs are used, and the cost is relatively increased. • I"6 years of Japanese Nichia (10) Chemical) in a 460nm wave: InGaN blue crystals of long light are coated with a layer of activator
鋁石榴石(yttrium aluminum garnet; YAG)螢光物質，利用藍光LED 照射，-榮光物質以產生與藍光互補之555細波長黃光，再將互 補之頁光、藍光予職合後得到自光。㈣此方法缺少三原色中 之紅光、及綠光兩種光色，故所得之白光，相較於以紅、綠、藍 6 13.23277 三原色所形成之白光，具有較差之演色性。 因此，美國專利第6649946號揭露一種以氮化物之化合物作 為紅色螢光材料’其化學式為M2Si5N8:Eu與MSi7N1G:Eu，可受 420-470nm之藍紫光激發，而發射出紅光。此紅色螢光材料與適 合之綠色螢光材料混合後，再與藍光發光二極體封裝，經藍光發 光二極體發出的部分藍光激發後，可分別產生紅光及綠光。紅 光、綠光、以及藍光發光二極體發出的藍光混合後形成之白光， 其演色性較佳。另外’美國專利申請案公開第20030168643號揭 露一種使用赛隆（sialon)之螢光材料，其化學式為The yttrium aluminum garnet (YAG) phosphor is irradiated with a blue LED, and the glory material is used to generate 555 fine-wavelength yellow light complementary to the blue light, and then the complementary page light and blue light are combined to obtain self-light. (4) This method lacks the red light and the green light in the three primary colors, so the white light obtained has a poorer color rendering than the white light formed by the three primary colors of red, green and blue 6 13.23277. Thus, U.S. Patent No. 6,649,946 discloses a compound of a nitride as a red fluorescent material, which has the chemical formula of M2Si5N8:Eu and MSi7N1G:Eu, which is excited by blue-violet light of 420-470 nm to emit red light. The red fluorescent material is mixed with the suitable green fluorescent material, and then encapsulated with the blue light emitting diode and excited by a part of the blue light emitted by the blue light emitting diode to generate red light and green light, respectively. The red light, the green light, and the white light formed by the blue light emitted by the blue light emitting diode are better in color rendering. Further, U.S. Patent Application Publication No. 20030168643 discloses a fluorescent material using sialon having a chemical formula of
MexSi12_(m+n)Al(m+n)OnN16.n:RelyRe2x，其中 Me 包含選自 Ca、Mg、 Y、以及不含La及Ce之鑭系金屬等材料，Rei包含選自Ce、Pr、 Eu、Tb、Yb、以及Er之材料，Re2是Dy，主要可被藍紫光激發 而產生橘黃光。此螢光粉經藍光發光二極體激發後產生之橘黃光 再與藍光混合所形成之白光，其色溫低於由藍光激發YAG螢光 粉後’經由混光所得到白光之色溫。但是，因該螢光粉是採高溫 (〜1700°C)ifj壓(10 atm)下合成’其合成過程之控制較困難。另^卜， 美國專利申請案公開第20050205845號揭露採用氮氧化合物之蟹 光材料，其化學式為MSi^N2以及MSi2-xAlx〇2+xN2x，並以Eu 作為活化中心’且添加少許Μη以改善放光強度。 【發明内容】 ，其特徵為 ，可有效提 本發明提供一種氧氮化合物螢光材料之製造方法 在氧氮化合物螢光材料製程中添加一鹼土族之說化物 高氧氮化合物螢光材料之發光強度。 7 13232.77 於一實施例中，本發明提供一種氧氮化合物螢光材料之製造 方法，其步驟包括：將含有Μ之一第一原料、含有Si之一第二 原料、含有Eu之一第三原料、含有Μη之一第四原料、以及一 鹼土族之氟化物混合成一混合物；以及將該混合物在一還原氣氛 令加熱形成一氧氮化合物，該氧氮化合物之通式為 Mi-x-ySi2N2〇2:EuxMny ’ 0<χ<1 ’ 〇<y<l，且 〇<x+y<l，其中 Μ 為 單一或兩種以上元素，選自於Sr、Ca、Ba、Mg、Zn、Mn、Y、 以及不包含Eu之稀土類元素。 【實施方式】 本發明所揭露之氧氮化合物螢光材料之製造方法可製造一 種能夠發出黃綠色螢光且結構空間群(space识〇叩)為p2i/m之營 光材料’其化學式為Mi-x-ySizNzO/EuxMiiy，其中 為其主體晶格結構(host)，Eu為活化中心，μ、Eu、及Μη之組 成中皆不可為0，亦即X及y分別介於〇及1之間，且X及丫之 和須小於1，較佳的範圍是0.01 < χ < 〇 2 ; 〇 〇1 $ y 〇 2。m為 單一或兩種以上元素，選自於Sr、Ca、Ba、Mg、ZnMnY: 以及不包含Eu之稀土類元素。 一 i2w2a2$UxMny 作為本 ’ y ~~ 〇.〇4 ’其製作方法如 於本發明之一實施例中，係以Sr 實施例之螢光粉材料，其中，x = 〇 〇4 下： 首先依化學計量比分別取含有Sr之第一原料，含有沿 原料，含有Eu之第三原料、以及含有洳之第四原料， 配方為SrNx_ySi2N2〇2:EuxMny之混合物，复中 ”彤烕 /、甲 x-0.〇4，y = 〇.〇4。 8 1323277 繼而’在前述混合物中添加含適當比例之鹼土族氟化物作為助溶 劑》由於此種氟化物熔點較低，可幫助先前添加之各原料於較低 之溫度進行共溶反應，使各原料在較低的反應溫度下即可炫融成 離子。將該混合物適度加熱，可使該氟化物成為液態，有利於原 料離子間之擴散，加速反應之進行以及產物之晶化以增進螢光材 料之發光效率。 上述鹼土族元素之莫耳濃度佔原料中M、Si、Eu、以及_之 總莫耳濃度比例為η，其中η的範圍介於0.003%至1 5%之間。於 本實施例中，選擇碳酸鋰(SrC〇3)作為第一原料，氮化矽（si3N4 ) 作為第二原料，氧化銪¢^03)作為第三原料，以及碳酸錳 _C〇3)作為第四原料，另外添加莫耳濃度比例η為3.67 X ΚΓ3% 之氣化鋇（BaF2)做為助賴’將上獅取之補及Bap2以研磨 方式研磨成粉末均勻混合。 接著將上述粉末置於坩鍋内，於设叫（2〇%/8〇%)之還原氣氛 申，以5C/mm之升溫速率加熱至14〇(rc進行還原（reducti〇n) 反應’持續加、溫1小時。再以rc/min之降溫速率冷卻至室溫，得 到化合物。將上述所得之化合物加入1〇%之1〇〇虹麟酸水溶液 中攪拌10分鐘後，再以細水重槪務2次^最後加以過 濾並烘乾，得到螢光材料。 上述之各原料，例如SrC〇3、或可用來替代SrC03之SrO、 1323277 sy^4 Eu2〇3、MncO3、以及助溶劑Bap2可直接於市售之商品取 得。其申，原料SrC〇3及SrO也可先以金屬锶經過氧化之前處理 後製得。同樣地’當以其他如Ca、Ba、Mg、Ζη、Μη、Y、以及 . 不包含Eu之稀土類元素替代Sr時，也可以所選擇之替代元素之 ’氧化物作為原料。此外，原料Si3N4可以Si在氮氣或氨氣氣氛中 '氮化製得;原料Eu2〇3可以EuN作為替代原料，或以金屬销經過氧 化或氮化處理製得;原料MnC〇3可以金屬錳經過氧化處理製得。 φ 助炫劑除本實施例選用之外，亦可以BeF2、MgF2、SrF2、以 及CaF2等原料替代。 除了上述於製程中添加BaF2助熔劑製得之螢光粉外，在此另 分別進行於螢光材料製程中添加lwt%SrF2、lwt%CaF2助熔劑， 以及未添加助熔劑等三組實驗，以比較本發明之添加助熔劑方法 與未添加助熔劑所製得之螢光材料間發光強度之差別。 •參考第一 A圖及第一 B圖’分別是螢光材料之激發(excitati〇n) 光譜與放射(emission)光譜圖。由此二圖譜可分別得知此螢光材料 適合被藍紫光激發，且激發後可發出黃綠光，並由此可知添加助 溶劑之螢光材料之發光強度高於未添加助炫劑之螢光材料之發光 強度。若以未添加助溶劑之螢光粉發光強度為100%，則添加助熔 劑BaF2、CaF2、以及SrF2所製得螢光材料之相對發光強度分別 為119%、127%、以及156%，其中又以添加srF2助熔劑之發光強 度最佳。 1323277 第- A ®及第二b ®分別膽程巾未添加助_及製程中添 加觀劑贴2所製得螢光材料私.92_2〇2伽〇〇祕〇〇4之掃猫式電 子顯微鏡(SEM)則。絲齡，未添加助_丨合紅粉體其顆 粒表面較為粗糙，而在本發明添加助熔劑之製程中，經助熔劑改 善其晶體形成過程，所形成之螢光材料粉體顆粒之表面平滑度較 佳，其顆粒呈較圓之球體，且其顆粒較大而分布較為均勻。综合 上述之光譜分析與掃瞄式電子顯微鏡照片之比較，可知本發明於 製程中添加助熔劑，能夠使螢光粉體之顆粒與表面形態改善，使 晶體之結晶性較佳，增強螢光粉體之發光強度。 第二圖中之點a係以添加助熔劑BaF2所製得螢光材料之發 射光譜，以CIE13.3 Colour Rendering色度座標分析軟體計算其於 色度座標圖之位置，由圖可得知依本發明所製得之螢光材料為適 合以藍紫光激發而放黃綠光之螢光粉。 參考第四圖，利用本發明之製造方法所製得之 ⑽4Μη〇.〇4螢光材料’在接受藍紫光⑼激發所放射 出之黃綠光(G)，再搭配CaS:Eu紅色螢光材料經藍紫光(Β)照射激 發後放射紅光(R)，再加上藍紫光(B)後，經混合R、g、B三色光 後’可得到一白光光譜，其色溫與演色性分別可高達8〇28 κ與幻。 於第五圖中點Α係第四圖之發射光譜以程式轉換所得於色度 座標模擬之位置(0.2879, 0.3260)，而三角形符號處所代表的是理論 上之白光位置(0.32, 0.31)，由圖譜位置可知依本發明所製得之榮光 11 1323277 材料搭配紅色螢光材料職紫光蹄後所得之自光非常接近理論 上之白光。 本發明所列舉之各實施例僅為用以說明本發明，並非用以限 制本發明之範圍。依本發明精神所作之修飾與變更皆不脫離本發 _ 明之申請專利範圍。 【圖式簡單說明】 第一 A圖係依本發明之添加助熔劑與習用未添加助溶劑螢光 • 粉製造方法所製得螢光粉之激發光譜圖。 第 B圖係依本發明之添加助熔劑與習用未添加助炫劑螢光 粉製造方法所製得螢光粉之放射光譜圖。 第一 A圖係依未添加助熔劑螢光粉製造方法所製得螢光粉之 掃瞄式電子顯微鏡相片。 第二B圖係依本發明之添加助熔劑螢光粉製造方法所製得發 光粉之掃瞄式電子顯微鏡相片。 _ 第二圖係以程式轉換將第一圖所示之發射光譜顯示於一色度 座標。 第四圖係依本發明之螢光粉搭配紅色螢光粉受藍紫光激發所 . 得之白光光譜。 _-第五圖係以程式轉換將第三圖所示之發射光譜顯示於一色度 . 座標。 12MexSi12_(m+n)Al(m+n)OnN16.n: RelyRe2x, wherein Me comprises a material selected from the group consisting of Ca, Mg, Y, and a lanthanide metal not containing La and Ce, and Rei comprises a selected from Ce, Pr, The material of Eu, Tb, Yb, and Er, Re2 is Dy, which is mainly excited by blue-violet light to produce orange light. The white light of the phosphor powder which is excited by the blue light emitting diode and then mixed with the blue light has a color temperature lower than the color temperature of the white light obtained by the light mixing after the YAG phosphor is excited by the blue light. However, since the phosphor powder is synthesized at a high temperature (~1700 ° C) ifj pressure (10 atm), the control of the synthesis process is difficult. U.S. Patent Application Publication No. 20050205845 discloses a nitroxide-based crab light material having the chemical formula of MSi^N2 and MSi2-xAlx〇2+xN2x, with Eu as the activation center' and adding a little Μη to improve Light intensity. SUMMARY OF THE INVENTION It is characterized in that the present invention can effectively provide a method for producing an oxygen-nitrogen compound fluorescent material by adding an alkali-alkali compound high-oxygen nitrogen compound fluorescent material to a oxynitride fluorescent material process. strength. 7 13232.77 In one embodiment, the present invention provides a method for producing an oxynitride fluorescent material, the method comprising: comprising a first raw material containing cerium, a second raw material containing Si, and a third raw material containing Eu And mixing a fourth raw material containing Μη and an alkaline earth fluoride into a mixture; and heating the mixture to form an oxynitride compound in a reducing atmosphere, the oxynitride compound having the formula Mi-x-ySi2N2〇 2: EuxMny ' 0<χ<1 ' 〇<y<l, and 〇<x+y<l, where Μ is a single or two or more elements selected from Sr, Ca, Ba, Mg, Zn, Mn, Y, and rare earth elements that do not contain Eu. [Embodiment] The method for producing an oxynitride phosphor material disclosed in the present invention can produce a camphorescent material capable of emitting yellow-green fluorescence and having a space group of spaces (p2i/m), which has a chemical formula of Mi. -x-ySizNzO/EuxMiiy, where is its host lattice structure, Eu is the activation center, and the composition of μ, Eu, and Μη cannot be 0, that is, X and y are between 〇 and 1 respectively. And the sum of X and 丫 must be less than 1, and the preferred range is 0.01 < χ < 〇 2 ; 〇〇 1 $ y 〇 2. m is a single or two or more elements selected from the group consisting of Sr, Ca, Ba, Mg, ZnMnY: and rare earth elements not containing Eu. An i2w2a2$UxMny as the 'y ~~ 〇.〇4' is produced in the embodiment of the present invention, and is a phosphor powder material of the Sr embodiment, wherein x = 〇〇4: first The stoichiometric ratio is taken as the first raw material containing Sr, and contains the third raw material containing Eu along the raw material, and the fourth raw material containing cerium, and the formula is a mixture of SrNx_ySi2N2〇2:EuxMny, and the complex is "彤烕/, Ax -0.〇4,y = 〇.〇4. 8 1323277 and then 'adding an appropriate proportion of alkaline earth fluoride as a co-solvent to the aforementioned mixture.》This fluoride has a lower melting point and can help the previously added raw materials. The co-solubilization reaction is carried out at a lower temperature, so that each raw material can be condensed into ions at a lower reaction temperature. The mixture is heated moderately to make the fluoride liquid, which is beneficial to the diffusion between the raw materials and the acceleration. The progress of the reaction and the crystallization of the product to improve the luminous efficiency of the fluorescent material. The molar concentration of the alkaline earth element in the raw material accounts for η of the total molar concentration of M, Si, Eu, and _ in the raw material, wherein the range of η From 0.003% to 1 5% In this embodiment, lithium carbonate (SrC〇3) is selected as the first raw material, tantalum nitride (si3N4) is used as the second raw material, yttrium oxide (03) is used as the third raw material, and manganese carbonate _C〇3 is selected. As a fourth raw material, a gasification enthalpy (BaF2) having a molar concentration ratio η of 3.67 X ΚΓ 3% is additionally added as a help for the lion's supplement and Bap2 to be ground into a powder and uniformly mixed. The powder is placed in a crucible, and is heated at a heating rate of 5 C/mm to 14 〇 (reducti〇n reaction) at a heating rate of 5 C/mm (continuous addition and temperature) at a reducing atmosphere of (2〇%/8〇%). After 1 hour, the mixture was cooled to room temperature at a cooling rate of rc/min to obtain a compound. The compound obtained above was added to a 1% aqueous solution of 1 〇〇 〇〇 酸 acid for 10 minutes, and then treated with fine water. Finally, it is filtered and dried to obtain a fluorescent material. The above various raw materials, such as SrC〇3, or SrO, 1323277 sy^4 Eu2〇3, MncO3, and cosolvent Bap2, which can be used to replace SrC03, can be directly used in the city. The products sold are obtained. The raw materials, SrC〇3 and SrO, can also be treated with metal ruthenium before oxidation. Similarly, when 'Sr is replaced by other rare earth elements such as Ca, Ba, Mg, Ζη, Μη, Y, and .. without Eu, the oxide of the alternative element may be selected as the raw material. In addition, the raw material Si3N4 can be made by nitriding Si in a nitrogen or ammonia atmosphere; the raw material Eu2〇3 can be made of EuN as an alternative raw material, or the metal pin can be obtained by oxidation or nitriding; the raw material MnC〇3 can be passed through the metal manganese. Oxidation treatment can be obtained. In addition to the selection of this embodiment, φ auxiliary agent can also be replaced by raw materials such as BeF2, MgF2, SrF2, and CaF2. In addition to the above-mentioned phosphor powder prepared by adding a BaF2 flux in the process, three sets of experiments, such as adding 1 wt% SrF2, 1 wt% CaF2 flux, and no flux added, were separately performed in the process of the phosphor material, respectively. The difference in luminous intensity between the method of adding a flux of the present invention and the phosphor material obtained by adding no flux is compared. • Refer to the first A diagram and the first B diagram ′ for the excitation material and the emission spectrum of the fluorescent material, respectively. Therefore, the two spectra can be separately found that the fluorescent material is suitable to be excited by blue-violet light, and can emit yellow-green light after excitation, and thus it can be seen that the fluorescent material with the addition of the auxiliary solvent has higher luminous intensity than the fluorescent material without the auxiliary agent. Luminous intensity. If the luminous intensity of the fluorescent powder without the addition of the co-solvent is 100%, the relative luminous intensities of the fluorescent materials prepared by adding the fluxing agents BaF2, CaF2, and SrF2 are respectively 119%, 127%, and 156%, of which The illuminating intensity of the srF2 flux is optimal. 1323277 The first - A ® and the second b ® respectively, the gallbladder towel is not added with aid _ and the process is added with the medicinal patch 2 to produce the fluorescent material private. 92_2 〇 2 〇〇 〇〇 〇〇 〇〇 4 (SEM). The age of the silk is not added, and the surface of the particles is relatively rough. In the process of adding the flux in the present invention, the flux is used to improve the crystal formation process, and the surface smoothness of the powder particles of the fluorescent material formed is improved. Preferably, the particles are relatively round spheres, and the particles are larger and more evenly distributed. By comparing the above-mentioned spectral analysis with the scanning electron micrograph, it can be seen that the flux added in the process of the present invention can improve the particle and surface morphology of the phosphor powder, and the crystallinity of the crystal is better, and the phosphor powder is enhanced. The luminous intensity of the body. The point a in the second figure is the emission spectrum of the fluorescent material prepared by adding the flux BaF2, and the position of the chromaticity coordinate diagram is calculated by the CIE 13.3 Colour Rendering chromaticity coordinate analysis software. The fluorescent material prepared by the invention is a fluorescent powder suitable for being excited by blue-violet light and emitting yellow-green light. Referring to the fourth figure, the (10)4Μη〇.〇4 fluorescent material prepared by the manufacturing method of the present invention is subjected to blue-green light (G) excited by blue-violet light (9), and then combined with CaS:Eu red fluorescent material through blue. After the excitation of violet light (Β), the red light (R) is emitted, and after blue-violet light (B), after mixing the three colors of R, g and B, a white light spectrum can be obtained, and the color temperature and color rendering can be as high as 8 respectively. 〇28 κ and illusion. In the fifth figure, the emission spectrum of the fourth figure is converted to the position of the chromaticity coordinate simulation (0.2879, 0.3260), and the triangular symbol represents the theoretical white light position (0.32, 0.31). At the map position, it can be seen that the glare 11 1323277 material prepared according to the invention is matched with the red fluorescent material and the self-light obtained from the purple hoof is very close to the theoretical white light. The examples of the invention are intended to be illustrative only and not to limit the scope of the invention. Modifications and variations made in accordance with the spirit of the present invention are not intended to fall within the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The first A diagram is an excitation spectrum of a phosphor powder prepared by adding a fluxing agent according to the present invention and a conventional method of adding a solvent-free fluorescent powder. Fig. B is a radiation spectrum diagram of the phosphor prepared by the method of producing a flux according to the present invention and a conventional method for producing a phosphor without a lubricant. The first A-picture is a scanning electron microscope photograph of the phosphor powder obtained by the method of manufacturing a flux-free phosphor powder. Fig. 2B is a scanning electron micrograph of the luminescent powder obtained by the method for producing a flux-refining powder according to the present invention. _ The second figure shows the emission spectrum shown in the first figure in a chromaticity coordinate by program conversion. The fourth figure is a white light spectrum obtained by the phosphor powder according to the present invention and the red phosphor powder excited by blue-violet light. _-The fifth picture shows the emission spectrum shown in the third figure in a chroma by program conversion. Coordinates. 12