1326704 '· 九、發明說明： 【發明所屬之技術領域】 類化合物螢光材料ABP04:M及其 本發明係關於一種鱗酸鹽 製備方法。 【先前技術】1326704 '· IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The compound-like fluorescent material ABP04:M and the present invention relate to a method for preparing a sulphate. [Prior Art]
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&ED)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’ t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i破損、可製紐積極小、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·交通號誌、汽車儀表板、液晶顯示板背光源、或筆記型電 腦顯示器，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 電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led，成本也相對提高β第三種 則是1996年日本曰亞化學公司（Nichia Chemical)發展出以氮化 銦鎵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 1326704 ν· ·With the evolution of civilization, human demand for lighting is increasing, and the demand for lighting quality is increasing. In recent decades, light-emitting diodes & ED) have gradually replaced traditional light sources, because light-emitting diodes (LEDs) have many advantages compared with conventional light sources: small size, good luminous efficiency, and longevity. Long, fast reaction speed, high reliability, no damage, can be made into small positive and small, and can be wound or arrayed components, and no pollution of toxic substances such as heat radiation and mercury. The range of applications currently included includes traffic signs, car dashboards, LCD backlights, or notebook-type displays, and can be used to create a variety of large components to provide indoor or outdoor large display screens and illumination. 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. In the second method, two LEDs of GaN and GaP are used to respectively control the current through the LED to emit blue and yellow-green light to be mixed to generate 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 LEDs will be used at the same time, and the cost is relatively increased. The third type is 1996. Nichia Chemical of Japan has developed a yttrium aluminum garnet type phosphor with an indium gallium nitride blue light emitting diode and a yellow light. It can also be 1326704 ν··
I \ • 為白光光源，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、及綠光兩種光色，所得之白光演色性較差。第四 種可產生白光之方法是由日本住友電工（Sumit〇m〇 Electrfc Industries,Ltd)在19"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，成本相對降低，但其缺點是發光效 率太低且哥命太短，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’BWaMPOACkEu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之梦酸鹽類化合物作為藍綠色勞 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-LED激發，可形 - 成白光。 【發明内容】I \ • is a white light source. Compared with the above two methods, the cost is low. However, due to the lack of red light and green light in the three primary colors, the resulting white light has poor color rendering. The fourth method for producing white light is the development of a white LED using ZnSe material by Sumit〇m〇Electrfc Industries, Ltd. in January 19, which can obtain white light without fluorescent substances, and the cost is relatively low. However, its shortcoming is that the luminous efficiency is too low and the life is too short, and further breakthroughs must be made in practical considerations. Therefore, in U.S. Patent No. 6,621,211, the chemical formula is (Sr'BWaMPOACkEu, a halophosphate compound as a blue fluorescent material, and a chemical formula of (Ba»Sr,Ca)2Si〇4:Eu As a blue-green light-emitting material, the salt compound can be excited by UV-LED to emit blue to blue-green light wavelength. It can be excited by UV-LED when mixed with suitable orange and red fluorescent materials. White light. [Summary content]
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加 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驗金屬和二價驗土金屬混合之碟 酸鹽類，再摻雜活性中心，所製成之化合物通式為AaBbP04:Mm， 其中，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M 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、K、Rb、及Cs之鹼金屬 元素，B包含單一或兩種以上選自Mg、Ca、Sr、及Ba之驗土元 /04 家及心稀土航素為Sl _ — _ :金屬元素可自金屬化合物或碳酸練得，例如。 鐘、或碰鐘。驗土元素可自金屬化合物或碳酸類=鍾=酸 硝酸鋰錢触。祕航麵自碰4 · 氧化銪或硝酸銪。 嫩物糊，例如： 本發明之另-目的係提供—種_柯主體金屬及 同發光中心之榮光粉體，可改變其發光範1於35()〜4(^ 長之光源照射下，可發出紫藍光到藍綠光之螢光。 / 依本發明之勞光材料具有光色純、熱穩定、及可調配不同主 體金屬來得到所需波絲園之螢光粉等優點。此外，本發明所 示之螢光㈣可多種合射法製得單相之螢光粉^例如： 固態反應法、郷法、或儒難槪等。縣發明之螢光材料 為新單相之螢光粉，製備方法_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榮 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。LiUi^POt作為本實施 例之螢光粉材料，其中X組成之範圍是〇<χ<1，本實施例中選擇 χ = 0.05 ’其製備方法包含下列各步驟： 首先依化學計量比分別取一含有鋰的第一反應物（如 1326704SUMMARY 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 compound having a higher luminous intensity. Fluorescent material. The reactant of the glare material comprises at least a disc salt of a monovalent metal and a bivalent soil-measuring metal, and is doped with an active center, and the compound is a compound of the formula AaBbP04:Mm, wherein A is a single or Two or more kinds are selected from metal elements having positive monovalent electrons, B is a single or two or more metal elements selected from positive divalent electrons, and M is a single or two or more elements selected from the group consisting of rare earths. The metal element having positive monovalent electrons includes one or two or more alkali metal elements selected from the group consisting of Li, Na, K, Rb, and Cs, and B contains one or more selected from the group consisting of Mg, Ca, Sr, and Ba. The soil tester/04 and the core rare earth element are Sl _ — _: The metal element can be obtained from a metal compound or carbonic acid, for example. Clock, or touch the clock. The soil test elements can be touched from metal compounds or carbonates = clock = acid lithium nitrate. The snorkeling surface touches 4 · yttrium oxide or yttrium nitrate. Tender paste, for example: Another object of the present invention is to provide a kind of _ ke body metal and glory powder of the same illuminating center, which can change its illuminating range 1 to 35 () ~ 4 (^ long light source irradiation, The violet light to the blue-green light is emitted. / The light-emitting material according to the present invention has the advantages of pure color, heat stability, and different main body metals to obtain the desired phosphor powder of the wave garden. The fluorescent light (four) shown in the invention can be obtained by a plurality of merging methods to obtain a single-phase fluorescent powder, for example: solid state reaction method, hydrazine method, or ruthenium ruthenium, etc. The fluorescent material of the invention is a new single-phase phosphor powder. The preparation method is rapid and easy to mass produce, and the obtained finished product has industrial application value. According to the foregoing advantages, if it can be mixed with a suitable orange and red glory material and excited by UV-LED, white light can be formed. In a preferred embodiment, a phosphate-based phosphor powder formulation and a preparation method will be described. LiUi^POt is used as the phosphor powder material of the present embodiment, wherein the range of X composition is 〇<χ<1, this embodiment In the example, choose χ = 0.05 'the preparation method includes the following A first reactant (e.g., 1,326,704 by first taking a stoichiometric ratio each containing lithium: the steps of
Li2C03)，含有銷的第二反應物(如Src〇3)，含有填酸之第 三反應物[如(NH4)2P04]，以及含有Ει!之第四反應物(如 Eu2〇3) ’使其形成之配方為LiSrixP〇4:EUx，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。 二、 以研缽研磨俾充分混合後，將混合物置於氧化鋁坩鍋中， 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。Li2C03), a second reactant containing a pin (such as Src〇3), a third reactant containing acid (such as (NH4)2P04], and a fourth reactant containing Ει! (such as Eu2〇3) The formulation thereof is LiSrixP〇4: EUx, wherein x = 0·05 °, and the synthesis method can utilize solid state reaction method, chemical synthesis method, such as citrate gel method, spray pyrolysis method and the like. 2. After thoroughly mixing with the mortar, the mixture is placed in an alumina crucible, and then the alumina crucible is placed in a square furnace, and heated in an air environment at 400 ° C to 650 ° C for 1 °. For 5 hours, in the present example, the mixture was sintered at 600 ° C for 3 hours, and then taken out and ground into a powder.
三、 接著將上述粉末置於氧化鋁坩鍋中’於7〇(Tc〜1400°C之 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fC/min之升溫速率加熱至 1300°C進行還原（reduction)反應，再持續恆溫處理3小 時。繼而，以5°C/min之降溫速率冷卻至室溫。還原燒結 後，以研蛛加以研磨，使其成為顆粒均勻之粉末，即得到 一磷酸鹽類化合物螢光粉(LiSi^PO^Euo.M；)。 在本實施例中，亦可選擇LiHJO4作為第一及第三反應物， 碳酸鏍(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LiHzPO4、S1CO3、Eu203可直接於 市售之商品取得。此外’反應物LiH2P〇4可以LiN〇3、U2C〇3 及(ΝΗ^ΗΡΟ4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咬心〇產 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 %、Ca、Ba代替時’也可以所選擇之代替元素:氧化物或鹽： 作為反應物❶反應物EwO3可以EU(N〇3)3 · 5H2〇作為替代原料， 1326704 #. · • · 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:Eu〇()5、 LiBa〇95P〇4:Eu〇05 及 LiBa〇.475Ca〇475P〇4:Eu0〇5 之製作與 LiCao^PO^Euo.o5類似，僅反應物之種類如實施例一中之含有鎢 • 的第二反應物，如SrC03改變為CaC03或Bac〇3。。3. The powder is then placed in an alumina crucible at '7 Torr (1 to 5 hours under a reducing atmosphere of Tc ~ 1400 ° C. This example is passed into h2/N2 (25% / 75%) The atmosphere was reduced, heated to 1300 ° C at a heating rate of fC/min to carry out a reduction reaction, and then kept under constant temperature for 3 hours. Then, it was cooled to room temperature at a cooling rate of 5 ° C / min. Grinding the spider to make it into a uniform powder, that is, obtaining a phosphate compound phosphor (LiSi^PO^Euo.M;). In this embodiment, LiHJO4 can also be selected as the first and third. The reactant, strontium carbonate (SrCCb) is used as the second reactant "eU2〇3" as the fourth reactant, and the above-mentioned weighed reactant is ground into a powder by grinding and uniformly mixed. For example, LiHzPO4, S1CO3, and Eu203 can be obtained directly from commercially available products. In addition, the reactant LiH2P〇4 can be replaced by LiN〇3, U2C〇3 and (ΝΗ^ΗΡΟ4; the reactant SrC〇3 can be strontium nitrate Sr(N〇3). ) 2, instead of using the metal strontium, the SrC〇3 bitter heart 制 produced by pre-oxidation treatment And further processing with other reactants in this embodiment. When Sr is replaced by other %, Ca, Ba, 'can also be substituted for the element: oxide or salt: as reactant ❶ reactant EwO3 can be EU (N〇3)3 · 5H2〇 as an alternative raw material, 1326704 #. · • · Or obtained by oxidation treatment of metal ruthenium. In addition, other formulations of the invention such as LiCa〇95p〇4:Eu〇()5, LiBa 〇95P〇4:Eu〇05 and LiBa〇.475Ca〇475P〇4:Eu0〇5 is produced similarly to LiCao^PO^Euo.o5, and only the type of the reactant is as in the first embodiment containing tungsten·the second The reactant, such as SrC03, is changed to CaC03 or Bac〇3.
依本發明實施例所製備之LiSri_xP〇4:EUx(x = 0.05)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锶磷酸鹽化合物(JCPDSn〇 : 14-〇2〇2) X光粉末繞射圖譜比較，可知本發明所揭示之填酸鹽類化合物榮 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。，γ =120。。 參考第二Α圖及第二Β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圓申虛線部分所示）， 則反應物經過處理(即經本實施例之第二步釋處理）所製備之螢 光粉發光強度可提升至121%(如第二b圖中直線部分所示由 8 1326704 . 此可知反應物經於空氣中低溫（600°C )處理，再於高溫（1300°C ) ’ 還原氣氛[H2/N2 (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LiCa^PC^EiUx = 0.05)及 LiSri_xP〇4:Eux(x = 0.05)之激發光譜(excitation)圖與放射光 譜(emission)圖。如圖所示，主體含鈣元素，其放射波長約在 475nm;主體含勰元素，其放射波長約在425nm〇不同金屬元素， 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》The LiSri_xP〇4: EUx (x = 0.05) sample prepared according to the examples of the present invention was identified by X-ray powder diffractometer, and the results were as shown in Fig. 1A. Comparing the sample prepared by the present invention with the standard lithium bismuth phosphate compound (JCPDSn〇: 14-〇2〇2) X-ray powder diffraction pattern, it can be seen that the sulphate of the acid-filling compound disclosed in the present invention is a single phase. 'Hexagonal structure, the lattice constant is a = b = 5. 002 (1) A, c = 8.209 (2) A; α = cold = 90. , γ = 120. . Referring to the second and second maps, 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 the fluorescent material is a fluorescent powder which is suitable for blue-violet light and emits 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 by the untreated reactant (ie, not treated in the second step of the embodiment) is 100% (as indicated by the dotted line in the second B circle), the reactant is processed (ie, The luminous intensity of the prepared phosphor powder can be increased to 121% by the second step of the present embodiment (as shown by the straight line in the second b diagram, 8 1326704. This shows that the reactants are subjected to low temperature in air (600°). C) treatment, and then at high temperature (1300 ° C) 'reduction atmosphere [H2 / N2 (25% / 75%)] treatment can obtain fluorescent powder with better luminous intensity. The third A and third B respectively It is an excitation spectrum and an emission spectrum of the fluorescent material LiCa^PC^EiUx = 0.05) and LiSri_xP〇4: Eux (x = 0.05). As shown in the figure, the main body contains calcium, and its emission wavelength is about 475 nm. The main body contains strontium element, and its emission wavelength is about 425 nm. Different metal elements have different excitation and emission intensities. In summary of the above spectral analysis, the present invention • changes the different host elements in the process' so that the luminescent 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 main -* body elements.
V - 將放射光譜之數據以1931年由國際照明委員會 (Commission International de l ’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 φ 標，標示於第四圖。圖中點a係第三B圖LiSri.xP〇4:EUx(x = 〇.05) 之放射光譜以程式轉換所得於色度座標模擬之位置(〇 l62i , 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榮光材料，其位置 '*帛乎到達純藍色的座標位置，顯示其色純度非常好，其他三點 ；(b，C ’d)分別為螢光材料Lic如撕⑽wcvEu〇I、 及 LiBa〇 ^Cao 475P〇4:Eu〇 〇5 之發光位置。 本申請案所列舉之各實施例僅為本發明之具體實施例，並非 9V - The data of the emission spectrum is converted into the chromaticity seat φ represented by each phosphor by the formula of the Chromaticity diagram established by the Commission International de l 'Eclairage ' CIE in 1931. The standard is shown in the fourth picture. In the figure, point a is the third B-picture LiSri.xP〇4: EUx (x = 〇.05). The emission spectrum is obtained by program conversion at the position of the chromaticity coordinate simulation (〇l62i, 0.0184), and the triangle symbol represents It is the theoretical white light position (〇31, 0.32). It can be seen from the position of the map that the glory material prepared according to the embodiment of the present invention has a position '* 到达 到达 到达 纯 纯 纯 , , , , , , , , , , , 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯 纯The light material Lic has a light-emitting position such as tear (10) wcvEu〇I, and LiBa〇^Cao 475P〇4:Eu〇〇5. The embodiments listed in the present application are merely specific embodiments of the present invention, and are not 9