200813190 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種磷酸鹽類化合物螢光材料Αβρ〇4:Μ及其 製備方法。 · ’、 【先前技術】 隨著文明演進，人類對於照明之需求日益增加，對照明品質 之要求也日益提高。近幾十年來，發光二極體(LED)逐漸取代傳 統光源，乃因發光二極體(LED)與傳統光源相較之下，具有許多 優勢，包括:體積小、發光效率佳、壽命長、操作反應速度極快、 可靠度高、不易破損、可製成體積極小、及可繞式或陣列式的元 件，且無熱輻射與無水銀等有毒物質的污染。目前已應用的範圍 包括·父通號諸、汽車儀表板、液晶顯示板背光源、或筆記型電 腦顯不器，且可配合需求製成各種大型元件，以供應室内或室外 大型顯示螢幕及照明。 隨著白光LED之問世，使LED之應用延伸至照明光源領 域。市面上之白光LED製備方法大致分為四種：第一種方法係 使用紅光、藍光、及綠光三顆LED，分別控制通過LED的電流， 再經過透鏡，將發出的光加以混合而產生白光。第二種方法係使 用GaN與GaP為材質的二顆LED，同樣地分別控制通過LED之 ，流而發出藍及黃綠光以混合產生白光。但這二種方法的缺點是 若這些同時使用的不同光色LED中之一發生故障，則將無法得 到正常的白光，且同時使用多個LHD，成本也相對提高。第三種 貝J疋1996年曰本曰亞化學公司（NichiaChemical)發展出以氮化 鋼錄藍光發光二極體配合發黃光之釔鋁石榴石型螢光粉亦可成 4 200813190 為-白光絲，與前述兩種方法相較，其成本較低，但因缺少三 原色中之紅光、輯錢種光色，所得之白光演色性較差。第四 種可產生自光之綠是由日本住友電卫（Sumit()m()㈣恤200813190 IX. Description of the Invention: [Technical Field] The present invention relates to a phosphate compound fluorescent material Αβρ〇4: ruthenium and a preparation method thereof. · ‘, [Prior Art] With the evolution of civilization, human demand for lighting is increasing, and the demand for lighting quality is increasing. In recent decades, LEDs have gradually replaced traditional light sources, because LEDs have many advantages over traditional light sources, including: small size, good luminous efficiency, and long life. The operation reaction speed is extremely fast, the reliability is high, the damage is not easy to be broken, the body can be made into a small body, and the material can be wound or arrayed, and there is no pollution of toxic substances such as heat radiation and mercury. The scope of application has been included in the father's number, car dashboard, LCD panel backlight, or notebook computer display, and can be made into various large components to meet the needs of large indoor display screens and lighting . With the advent of white LEDs, LED applications have been extended to the field of illumination sources. There are four methods for preparing white LEDs on the market: the first method uses three LEDs of red, blue, and green light to control the current through the LEDs, and then through the lens to mix the emitted light. White light. The second method uses two LEDs made of GaN and GaP, and similarly controls the flow of the LEDs to emit blue and yellow-green light to produce white light. The disadvantage of these two methods is that if one of the different light-colored LEDs used at the same time fails, normal white light will not be obtained, and multiple LHDs will be used at the same time, and the cost will be relatively increased. In the third case, in 1996, Nichia Chemical developed a yttrium aluminum garnet type phosphor with a nitrided steel blue light emitting diode and a yellow light. It can also be 4, 2008,190, for white light, Compared with the above two methods, the cost is low, but due to the lack of red light in the three primary colors, and the color of the light, the resulting white light has poor color rendering. The fourth kind of green light that can be produced by the Japanese Sumitomo Electric (Sumit () m () (four) shirt
Industries，Ltd)在1999年1月研發出使用ZnSe材料的白光LED， 無須螢光物質即可得到白光，成本姆降低，但其缺點是發光效 率太低且壽命太短，在實用層面的考量上仍需更進一步地突破。 因此，於美國專利第6,621，211號中，揭露化學式為 (Sr，Ba，Ca)5(P〇4)3Cl:Eu之鹵磷酸鹽類化合物作為藍色螢光材料\ 及化學式為(Ba，Sr，Ca)2Si〇4:Eu之石夕酸鹽類化合物作為藍綠色螢 光材料，可受UV-LED激發，發射出藍色光到藍綠色光範圍之波 長，與適合之橘黃色及紅色螢光材料混合經uv七ED激發，可形 成白光。 【發明内容】 本發明之一目的在於提供一種磷酸鹽類化合物螢光材料及 製備方法。在此磷酸鹽類化合物螢光材料製程中，先加溫處理該 螢光材料之反應物，再將處理後所得之混合物在一還原氣氛中^ 熱，形成具較高發光強度之一磷酸鹽類化合物螢光材料。其該榮 光材料之反應物至少包含一價鹼金屬和二價鹼土金屬混合之麟 酸鹽類，再摻雜活性中心，所製成之化合物通式為AaBbP〇Y:Mm， 其中0<a，b，m^l，A為單一或兩種以上選自帶正一價電子之金屬 元素，B為單一或兩種以上選自帶正二價電子之金屬元素，及μ 為單一或兩種以上選自稀土類之元素。前述帶正一價電子之金屬 元素包含單一或兩種以上選自Li、Na、Κ、Rb、及cs之驗金屬 元素，B包含單一或兩種以上選自Mg、Ca、Sr、及Ba之驗土元 5 200813190 素及 Zn，稀土類元素為 Se、Y、La、Ce、pr、Ndpm Sm、 ^，、刊吻❿^^謂構成之材辦群址。 驗金屬元素可自金屬化合物或碳_取得，例如：硝,_、碳酸 鐘、或鱗麵。驗土元素可自金屬化合喊碳酸類取得，例如： 硝酸鎮或碳_。前述航素選自齡屬氧化物或細，例如： 氧化銪或硝酸銪。 本發明之另一目的係提供一種利用不同主體金屬及摻雜不 同發光中心之螢光粉體，可改變其發光範圍。於35〇〜4〇〇11111波 長之光源照射下，可發出紫藍光到藍綠光之螢光。 依本發明之螢光材料具有光色純、熱穩定、及可調配不同主 體金屬來得到所需波長範圍之螢光粉等優點。此外，本發明所揭 不之螢光材料可利用多種合成方法製得單相之螢光粉末，例如： 固態反應法、凝膠法、或喷霧熱裂解法等。依本發明之螢光材料 為新單相之螢光粉，製備方法簡易迅速，易大量生產，所得成品 具產業應用價值。根據前述優點，若能與適合之橘黃色及紅色螢 光材料混合經UV_LED激發後，可形成白光。 【實施方式】 於本發明之一較佳實施例中，將說明磷酸鹽類螢光粉體配方 及製備方法。選擇LiSr^PC^Eux或Li(SrKxEux)P〇4作為本實施 例之螢光粉材料，其中X組成之範圍是0<χ<1，本實施例中選擇 χ = 0·05，其製備方法包含下歹ij各步驟： 一、首先依化學計量比分別取一含有鋰的第一反應物(如 6 200813190Industries, Ltd. developed a white LED using ZnSe material in January 1999. White light can be obtained without fluorescent substances, and the cost is reduced, but its disadvantage is that the luminous efficiency is too low and the life is too short. There is still a need for further breakthroughs. Therefore, in U.S. Patent No. 6,621,211, a halogenated phosphate compound of the formula (Sr, Ba, Ca) 5 (P〇4) 3Cl:Eu is disclosed as a blue fluorescent material and a chemical formula (Ba, Sr,Ca)2Si〇4: Eu silicate compound as a blue-green fluorescent material, which can be excited by UV-LED, emits blue to blue-green light wavelength, and is suitable for orange and red The light material mixture is excited by uv seven ED to form white light. SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphate compound fluorescent material and a method for producing the same. In the process of the phosphate compound fluorescent material, the reactant of the fluorescent material is first heated, and the mixture obtained after the treatment is heated in a reducing atmosphere to form a phosphate having a higher luminous intensity. Compound fluorescent material. The reactant of the glare material comprises at least a linalic acid salt of a monovalent alkali metal and a divalent alkaline earth metal, and is doped with an active center, and the compound has a formula of AaBbP〇Y:Mm, wherein 0 <a, b, m^l, A is a single or two or more metal elements selected from positive monovalent electrons, B is a single or two or more metal elements selected from positive divalent electrons, and μ is selected as a single or two or more From the elements of rare earths. The metal element having positive monovalent electrons includes one or two or more metal elements selected from the group consisting of Li, Na, yttrium, Rb, and cs, and B contains one or more selected from the group consisting of Mg, Ca, Sr, and Ba. Geotechnical Elements 5 200813190 Prime and Zn, rare earth elements are Se, Y, La, Ce, pr, Ndpm Sm, ^, and the magazines of the ❿^^^. The metal element can be obtained from a metal compound or carbon, such as: nitrate, _, carbonic acid, or scales. The soil test elements can be obtained from metallization and carbonation, for example: nitric acid town or carbon_. The foregoing element is selected from the group consisting of an oxide or a fine, such as: cerium oxide or cerium nitrate. Another object of the present invention is to provide a phosphor powder which utilizes different host metals and doped with different luminescent centers to change the range of illumination. Under the illumination of 35〇~4〇〇11111 wavelength source, it can emit violet blue to blue-green light. The phosphor material according to the present invention has the advantages of pure color, heat stability, and the ability to adjust different host metals to obtain phosphor powder of a desired wavelength range. Further, the fluorescent material disclosed in the present invention can be obtained by using a plurality of synthetic methods to obtain a single-phase fluorescent powder, for example, a solid state reaction method, a gel method, or a spray pyrolysis method. The fluorescent material according to the invention is a new single-phase fluorescent powder, and the preparation method is simple and rapid, and is easy to mass-produce, and the obtained finished product has industrial application value. According to the foregoing advantages, white light can be formed if it is excited by a UV-LED after being mixed with a suitable orange and red fluorescent material. [Embodiment] In a preferred embodiment of the present invention, a phosphate-based phosphor powder formulation and a preparation method will be described. LiSr^PC^Eux or Li(SrKxEux)P〇4 is selected as the phosphor powder material of the present embodiment, wherein the range of the X composition is 0 < χ < 1, in the present embodiment, χ = 0·05 is selected, and the preparation method thereof Including the steps of the lower jaw ij: First, first take a first reactant containing lithium according to the stoichiometric ratio (such as 6 200813190
LisCO3) ’含有鳃的第二反應物(如SrC〇3)，含有磷酸之第 三反應物[如(NH^PO4]、以及含有Ευ之第四反應物(如 Eu203)，使其形成之配方為xjSrkPCVEux，其中X = 0.05。其合成方法可利用固態反應法、化學合成法，如檸 檬酸鹽凝膠法、喷霧熱裂解法等。 丁 二、 以研钵研磨俾充分混合後，將混合物置於氧化銘掛鋼中， 再將氧化鋁坩鍋置入方形爐，於空氣環境下，先行以 400°C〜650°C下加熱1〜5小時，於本實施例中，混合物 於600 C下燒結3小時後，再取出並研磨成粉末。 三、 接著將上述粉末置於氧化鋁坩鍋中，於70(rc〜14〇(rC2 還原氣氛下加熱1〜5小時。本實施例是通入h2/N2 (25%/75%)之還原氣氛，以5°C/min之升溫速率加熱至 1300 C進行逛原（reduction)反應，再持續恒溫處理3小 時。繼而，以5°C/min之降溫速率冷卻至室溫。還原燒結 後，以研钵加以研磨，使其成為顆粒均勻之粉太，即^ -顧鹽類化合㈣鎌_α95Ρ〇4:Ε^!^ 在本實施例中，亦可選擇LiH2P〇4作為第一及第三反應物， 碳酸锶(SrCCb)作為第二反應物，氧化銪(EU2〇3)作為第四反應 物，將上述秤取之反應物以研磨方式研磨成粉末並均勻混合。 上述之各反應物，例如LiH2P〇4、SrC〇3、Eu203可直接於 市售之商品取得。此外’反應物LffiyPO#可以LiN03、L^CO 及邮4)册〇4代替；反應物SrC〇3可以硝酸鳃Sr(N〇3)2代替， 亦可直接使用金屬锶經過氧化前處理所製得之SrC〇3或Sr〇產 物，再與本實施例中其他反應物進行後續製程。當Sr以其他之 Mg、Ca、Ba代替時，也可以所選擇之代替元素之氧化物類 作為反應物。反應物Eu2〇3可以Eu(N〇3)3 · 5H20作為替代原料， 200813190 或是以金屬銪經過氧化處理製得。 此外，本發明其他配方如LiCa〇.95P〇4:Eu0.05、 ΕίΒ3〇95Ρ〇4··ΕΐΙ〇〇5 及 LiBa〇.475Ca〇.475P〇4:Eu〇.〇5 之製作與 LiCa〇.95P〇4rEU{)()5類似，僅反應物之種類如實施例一中之含有锶 的第二反應物，如SrC03改變為CaC03或BaC03。。 依本發明實施例所製備之LiSr^PO^Ei^x = 〇·〇5)樣品，以 X光粉末繞射儀鑑定其晶相純度，結果如第一 A圖所示。將依本 發明製得之樣品與標準鋰勰磷酸鹽化合物(JCPDSno : 14-0202) X光粉末繞射圖譜比較，可知本發明所揭示之磷酸鹽類化合物螢 光體為單一相，具六方晶系(hexagonal)之結構，其晶格常數為a =b=5· 002(1) A，c=8· 209(2) A ; α =冷=90。，r =120。。 參考第二A圖及第二B圖，分別是螢光材料LiSri_xP〇4:Eux(x = 0.05)之激發光譜(excitation)圖與放射光譜(emission)圖。由圖可 知’此螢光材料為適合藍紫光所激發並可發出藍光之螢光粉，並 可知反應物先經過處理所製備之螢光材料之發光強度較未經過 處理所製備之螢光材料之發光強度為高。前述之藍紫光波長可介 於350〜400nm之間，該藍紫光之光源可為紫外光發光二極體或 電漿。若以反應物未經處理(即未經本實施例之第二步驟處理）所 製備之螢光粉發光強度為100% (如第二B圖中虛線部分所示）， 則反應物經過處理(即經本實施例之第二步驟處理）所製備之螢 光粉發光強度可提升至121〇/〇(如第二B圖中直線部分所示）。由 200813190 此可知反應物經於空氣中低溫（60(TC )處理，再於高溫（1300°c ) 還原氣氛[决般2 (25%/75%)]處理可得具較佳發光強度之螢光粉。 第三A圖及第三B圖分別是螢光材料LiCaixP〇4:EUx(x = 0.05)及 LiSrkPO^Eu/x = 〇·〇5)之激發光譜(excitati〇n)圖與放射光 譜(emission)圖。如圖所示，主體含詞元素，其放射波長約在 475nm，主體含錯元素’其放射波長約在425nm。不同金屬元素， 其激發光及放光強度也不盡相同。綜合上述之光譜分析，本發明 於製程中改變不同主體元素，使得發光中心(Eu2+)受不同的晶格 場的影響，造成不同光色之產生。藉此，我們能藉由調配不同主 體元素間相對的含量，藉以製備符合需求的螢光粉。 將放射光譜之數據以1931年由國際照明委員會 (Commission International de 1 Eclairage ’ CIE)所制定之色度座標 圖(Chromaticity diagram)之公式換算成各螢光體所代表之色度座 標，標示於第四圖。圖中點a係第三B圖LiSrkPC^Eu/x = 0.05) 之放射光譜以程式轉換所得於色度座標模擬之位置(〇1621， 0.0184)，而三角形符號處所代表的是理論之白光位置(〇.31， 0.32)。由圖譜位置可知依本發明實施例製得之螢光材料，其位置 幾乎到達純藍色的座標位置，顯示其色純度非常好，其他三點 0> ’ c，d)分別為螢光材料 LiCa〇95p〇4:Eu〇〇5、UBa〇 95p〇4:Eu_、 及 ϋΒ3〇·475〇Β〇·475ρ〇4:Ευ〇.〇5 之發光位置。 本申凊案所列舉之各實施例僅為本發明之具體實施例，並非 200813190 用以限制本發明之範圍。依本發曰月之概念或精神所作之修改或變 更皆不脫離本發明之申請專利範爵。 【圖式簡單說明】 第-圖係依本發明之一實施例所製備之LiSrixP〇4:Eux(x = 0.05)樣品之X光粉末繞射圖譜。 第二_、依本剌之—實侧所_之LiS]^pQ4:EUx(x = 0.05)樣品之反應物，未經於空氣中低溫(6〇〇c>c)處理及經於空氣 中低溫(600°C)處理樣品之(A)光激發與⑻光發射之光譜圖。其中 虛線部分表示未經於空氣中低溫處理之樣品的光譜，直線部分表 示經於空氣中低溫處理之樣品的光譜。 第三圖係依本發明調配不同主體金屬所製得螢光粉之(A)光 激發與(B)光發射之光譜圖。 第四圖係將第三(B)圖之光放射光譜以程式轉換所得之CIE 色度座標圖。 【主要元件符號說明】 十、申請專利範圍： 1· 一種磷酸鹽類化合物螢光材料，該磷酸鹽類化合物之通式為 AaBbP04:Mm，其中〇<\ b，m5l，A為單一或兩種以上選自帶 正一價電子之金屬元素，B為單一或兩種以上選自帶正二價電 子之金屬元素，及Μ為單一或兩種以上選自稀土類之元素。LisCO3) 'Second reactant containing ruthenium (such as SrC〇3), a third reactant containing phosphoric acid [such as (NH^PO4), and a fourth reactant containing ruthenium (such as Eu203) to form a formulation It is xjSrkPCVEux, where X = 0.05. The synthesis method can be carried out by solid state reaction method, chemical synthesis method, such as citrate gel method, spray pyrolysis method, etc. Put it in the oxidized Ming steel, put the alumina crucible into the square furnace, and heat it at 400 ° C ~ 650 ° C for 1~5 hours in the air environment. In this example, the mixture is at 600 C. After sintering for 3 hours, it was taken out and ground into a powder. 3. The powder was placed in an alumina crucible and heated at 70 (rc~14 Torr (rC2 reducing atmosphere for 1 to 5 hours. This example is a pass). Into a reducing atmosphere of h2 / N2 (25% / 75%), heated to 1300 C at a heating rate of 5 ° C / min to carry out the reduction reaction, and then continue to constant temperature treatment for 3 hours. Then, at 5 ° C / The cooling rate of min is cooled to room temperature. After reduction sintering, it is ground in a mortar to make it uniform. Too, that is, ^ - salt compound (4) 镰 _α95 Ρ〇 4: Ε ^! ^ In this embodiment, LiH2P 〇 4 may also be selected as the first and third reactants, strontium carbonate (SrCCb) as the second reaction As a fourth reactant, cerium oxide (EU2〇3) is ground into a powder by grinding and uniformly mixed. The above-mentioned reactants such as LiH2P〇4, SrC〇3 and Eu203 can be directly used. It is obtained from commercially available products. In addition, 'reactant LffiyPO# can be replaced by LiN03, L^CO and post 4); the reactant SrC〇3 can be replaced by strontium nitrate Sr(N〇3)2, or metal can be used directly. The SrC〇3 or Sr〇 product obtained by pre-oxidation treatment is further processed with other reactants in this embodiment. When Sr is replaced by other Mg, Ca or Ba, the element may be replaced instead. The oxides are used as reactants. The reactant Eu2〇3 can be prepared by using Eu(N〇3)3 · 5H20 as an alternative raw material, 200813190 or by oxidation treatment of metal ruthenium. In addition, other formulations of the invention such as LiCa〇.95P 〇4: Eu0.05, ΕίΒ3〇95Ρ〇4··ΕΐΙ〇〇5 and LiBa〇.475Ca〇.475P〇4:Eu〇 The production of 〇5 is similar to that of LiCa〇.95P〇4rEU{)()5, and only the kind of the reactant is as the second reactant containing hydrazine in the first embodiment, such as SrC03 is changed to CaC03 or BaC03. The sample of LiSr^PO^Ei^x = 〇·〇5) prepared in the examples was identified by X-ray powder diffractometer, and the results were as shown in FIG. Comparing the sample prepared according to the present invention with the standard lithium bismuth phosphate compound (JCPDSno: 14-0202) X-ray powder diffraction pattern, it can be seen that the phosphate compound phosphor disclosed in the present invention is a single phase with hexagonal crystals. The structure of a hexagonal structure, whose lattice constant is a = b = 5 · 002 (1) A, c = 8 · 209 (2) A; α = cold = 90. , r = 120. . Referring to FIG. 2A and FIG. 2B, respectively, an excitation spectrum and an emission spectrum of the fluorescent material LiSri_xP〇4:Eux (x=0.05). It can be seen from the figure that 'this fluorescent material is a fluorescent powder which is suitable for blue-violet light and can emit blue light, and it can be known that the fluorescent material prepared by the treatment is processed to have a higher luminous intensity than that of the fluorescent material prepared without treatment. The luminous intensity is high. The blue-violet light wavelength may be between 350 and 400 nm, and the blue-violet light source may be an ultraviolet light-emitting diode or a plasma. If the luminescent intensity of the phosphor prepared without the reactants being treated (ie, not treated in the second step of this embodiment) is 100% (as indicated by the dashed line in Figure B), the reactants are processed (ie, The luminous intensity of the phosphor prepared by the second step of the present embodiment can be increased to 121 Å/〇 (as shown by the straight line in the second B diagram). From 200813190, it can be seen that the reactants are treated in a low temperature (60 (TC) treatment in air, and then at a high temperature (1300 ° C) reducing atmosphere [2% (25% / 75%)] to obtain a fire with better luminous intensity. Light powder. The third and third B graphs are the excitation spectra (excitati〇n) and emission of the fluorescent materials LiCaixP〇4: EUx (x = 0.05) and LiSrkPO^Eu/x = 〇·〇5, respectively. Emission map. As shown in the figure, the main body contains a word element having a radiation wavelength of about 475 nm, and the main body contains a wrong element, which emits at a wavelength of about 425 nm. Different metal elements have different excitation and emission intensities. In combination with the above spectral analysis, the present invention changes different host elements in the process, so that the illuminating center (Eu2+) is affected by different lattice fields, resulting in different light colors. In this way, we can prepare fluorescent powders that meet the needs by blending the relative contents of different host elements. The data of the emission spectrum is converted into the chromaticity coordinates represented by each phosphor by the formula of the Chromaticity diagram established by the Commission International de 1 Eclairage 'CIE in 1931, and is indicated in the first Four pictures. In the figure, the emission spectrum of point A is the third B diagram LiSrkPC^Eu/x = 0.05), which is converted by the program to the position of the chromaticity coordinate simulation (〇1621, 0.0184), and the triangle symbol represents the theoretical white light position ( 〇.31, 0.32). It can be seen from the position of the map that the phosphor material obtained according to the embodiment of the present invention has a position almost reaching the position of the pure blue coordinate, indicating that the color purity is very good, and the other three points 0 > 'c, d) are respectively the fluorescent material LiCa 〇95p〇4: Eu〇〇5, UBa〇95p〇4: Eu_, and ϋΒ3〇·475〇Β〇·475ρ〇4: Ευ〇.〇5 light-emitting position. The embodiments of the present invention are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention. Modifications or changes made in accordance with the concept or spirit of the present invention do not depart from the patent application of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is an X-ray powder diffraction pattern of a LiSrixP〇4:Eux (x=0.05) sample prepared according to an embodiment of the present invention. The second _, according to the — — - the real side of the LiS] ^ pQ4: EUx (x = 0.05) sample of the reactants, not treated in the air at low temperature (6 〇〇 c > c) and in the air Spectrograms of (A) photoexcitation and (8) light emission of the sample treated at low temperature (600 ° C). The dotted line indicates the spectrum of the sample that has not been subjected to low temperature treatment in air, and the straight line indicates the spectrum of the sample that has been subjected to low temperature treatment in air. The third figure is a spectrum of (A) photoexcitation and (B) light emission of phosphor powder prepared by mixing different host metals according to the present invention. The fourth figure is a CIE chromaticity coordinate map obtained by program-converting the light emission spectrum of the third (B) diagram. [Explanation of main component symbols] X. Patent application scope: 1. A phosphate compound fluorescent material, the general formula of which is AaBbP04:Mm, wherein 〇<\ b,m5l,A is single or two The above is selected from the group consisting of metal elements having positive monovalent electrons, and B is a single or two or more metal elements selected from the group consisting of positive divalent electrons, and lanthanum is a single or two or more elements selected from the group consisting of rare earths.