TWI594969B - 複合陶瓷 - Google Patents

複合陶瓷 Download PDF

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TWI594969B
TWI594969B TW102111261A TW102111261A TWI594969B TW I594969 B TWI594969 B TW I594969B TW 102111261 A TW102111261 A TW 102111261A TW 102111261 A TW102111261 A TW 102111261A TW I594969 B TWI594969 B TW I594969B
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Taiwan
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composite ceramic
conversion
conversion phosphor
thermal expansion
mixture
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TW102111261A
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TW201348175A (zh
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豪格 溫克勒
湯瑪斯 約舒泰
朱麗安 布落娃
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馬克專利公司
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Description

複合陶瓷
本發明係關於一種複合陶瓷及製造其之方法。而且，本發明亦係關於以根據本發明之複合陶瓷作為較佳而言白色光源中之發射轉換材料的用途，及一種光源、一種發光單元及一種顯示裝置。
先前技術揭示當其以藍光光譜區或紫外線區中之光激發時，可表現可見光之發射的各種化合物。該等所謂轉換磷光體呈粉末形式或作為陶瓷用於光源中。最為人所知的轉換磷光體為YAG：Ce(經鈰摻雜之釔鋁石榴石)或LuAG：Ce(經鈰摻雜之鎦鋁石榴石)，由於其經藍光激發而在黃光光譜區中之發射使得可產生白色光源。
若轉換磷光體係呈粉末形式應用，其具有來自光源發射之光的高反向散射的缺點，從而減少「封裝增益」(光源之可能的封裝密度)及因而降低效率。由於包括轉換磷光體之粉末的散射係數取決於顆粒大小，曾試圖藉由合成奈米顆粒而降低不合要求的散射效果。然而，呈奈米顆粒形式之摻雜稀土之轉換磷光體的應用通常導致因明顯的表面缺陷所引起的不良發光性及因小顆粒大小所引起的明顯的黏聚。儘管以粉末形式利用之某些轉換磷光體(諸如YAG：Ce或LuAG：Ce)因低的散射效果展示良好效率，然而，光量子產率仍能改進。
呈陶瓷形式之轉換磷光體適合例如將高能輻射(諸如x射線或γ輻射)轉換成可見光。該類型之閃爍陶瓷通常摻雜稀土及係由例如Lu2SiO5：Ce或Gd2O2S：Ce,Pr組成。然而，各種摻雜鈰之陶瓷亦可用作光源(諸如LED(發光裝置))中之轉換磷光體(WO 2007/107915)以實現 某種顏色分佈。陶瓷之應用通常比粉末情形下可產生更高的光量子產率，但是由於大量能量呈熱形式損失，由藍光至黃光的轉換效率通常仍舊極低。先前技術揭示特定而言摻雜稀土之YAG陶瓷以用於LED(WO 2008/012712)。特定而言，來自各種摻雜稀土之石榴石化合物的發射光(US 2010/0277673 A1)亦可用作LCD(液晶顯示器)的背光。曾試圖尋找作為固態光源之展現高光量子產率及高效率的發光陶瓷。由於大多數轉換磷光體(諸如YAG：Ce)具有低的導熱性，呈熱形式損失之能量無法輕易散逸。該熱應力產生陶瓷中之缺陷及斷裂的形成，甚至導致進一步降低導熱性及繼而大幅增加散射性。包括作為發射轉換材料之該類型之陶瓷的光源在使用期的過程中之效率會顯著降低。
需要除高光量子產率及高效率之外亦有利於光源之長壽命的轉換磷光體。
因此，本發明之目的在於提供用於光源之具有高效率及高光量子產率，及能夠製造具有長壽命的光源的發射轉換材料。
出人意料地發現，包括轉換磷光體及另一具有負熱膨脹係數之材料的複合陶瓷可提供所有該等優點。
術語「複合陶瓷」中之「複合」意在考慮其微結構具有至少兩種顆粒類型的情形。第一種顆粒類型係藉由轉換磷光體而形成及另一顆粒類型係藉由該另一材料而形成。通過具有負熱膨脹係數，文中之該另一材料意在補償轉換磷光體材料的熱膨脹。
在本申請案中，術語「轉換磷光體」用於表示吸收電磁光譜之某一波長區域、較佳而言藍光或紫外線區域、特定而言藍光光譜區之輻射，及發射電磁光譜之另一波長區域之可見光的材料。
本申請案之術語「發射轉換材料」意在用於表示包括至少一種轉換磷光體及視需要之另一材料、較佳而言具有負熱膨脹係數的材料的材料。
轉換磷光體較佳係含Ce、Eu及/或Mn之材料。含Ce、Eu及/或Mn之材料較佳係無機陶瓷材料，其中一些晶格位置尤其較佳地由Ce3+、Eu2+、Eu3+及/或Mn2+或Mn4+離子佔據。
含Ce、Eu及/或Mn之材料中之Ce、Eu及/或Mn的含量以在晶格位置置換含Ce、Eu及/或Mn之材料中之Ce、Eu及/或Mn的原子總數(即，例如佔YAG中之Y)計較佳在0.01至5原子%之範圍內，較佳在0.01至5原子%之範圍內，更佳而言0.05至3原子%。
根據本發明之較佳的含Ce、Eu及/或Mn的材料係其本身為熟習此項技術者知曉適於作為發光二極體之轉換磷光體者。該等特定而言為矽酸鹽類，諸如原矽酸鹽類、氧基原矽酸鹽類、二矽酸鹽類、賽倫陶瓷(sialon)、氮氧化矽(silicooxynitrides)、氮化矽(siliconitrides)、鋁酸鹽類、石榴石及其他三元及四元氧化物及氮化物。
含Ce、Eu及/或Mn之材料尤其較佳係含Ce、Eu及/或Mn之石榴石。根據本發明，石榴石較佳地表示具有形式E3G2(TO4)3之化學組成的岩石形成材料，其中E為由8個氧陰離子包圍之二或三價陽離子；G為由6個氧陰離子包圍之二、三或四價陽離子、較佳而言三價陽離子；T為由4個氧陰離子包圍之二或三價陽離子。
根據本發明，石榴石較佳係含Ce之石榴石。根據本發明，這較佳地表示其中一些陽離子E已經Ce3+離子置換的石榴石。簡而言之，含Ce之石榴石在該申請案中簡寫為E3G2(TO4)3：Ce。
E3G2(TO4)3：Ce中之E較佳係選自由Y、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu或其混合物組成之群。E3G2(TO4)3：Ce中之G及T彼此獨立地、較佳地選自由Al、Sc、Ga或其混合物組成之群。或者，G及 T亦可表示Mg/Si或Mg/Ge之組合或其混合物，其中Mg及四價元素Si或Ge則以相同莫耳比例存在。
「熱膨脹係數」用於表示敘述物質就其尺寸隨溫度變化而變化的表現的特徵量。導致此現象之作用為熱膨脹。熱膨脹取決於所用物質，即其為物質特異性材料常數。其度量單位為K-1。若其為正數，物質隨溫度提高而膨脹。若其為負量，物質之尺寸隨溫度提高而縮減。對許多物質而言，由於熱膨脹在所有溫度範圍內並非均一地發生，熱膨脹係數自身亦為溫度相依性，因其係針對某一參考溫度或某一溫度範圍引用。針對本發明之目的，以如下方式測定熱膨脹係數：由於熱膨脹係數α高度取決於陶瓷之微結構，複合物之α值必須藉助於膨脹計以實驗方式測定。利用推桿膨脹計，根據DIN 51045標準，測量複合陶瓷在熱作用下之長度的變化。存在於複合陶瓷中及根據本發明具有負熱膨脹係數之另一材料的熱膨脹係數亦可因此而測定。
在本發明中，另一材料之負熱膨脹係數在20℃至200℃之範圍內之溫度變化的情形下，較佳在1*10-6至12*10-6 K-1之範圍內，尤其較佳在3*10-6至10*10-6之範圍內。
根據本發明之複合材料中之具有負熱膨脹係數的另一材料較佳係鎢酸鹽或鉬酸鹽或其之混合氧化物。另一材料尤佳係選自由Al2W3O12、Y2W3O12、YAlW3O12、ZrW2O8、Al2Mo3O12、Y2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、Y2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、Y2MoW2O12、YAlMoW2O12或其混合物組成之群。
文中亦可較佳的是塗覆具有負熱膨脹係數的材料。適宜的塗料為例如無機氧化物，諸如氧化鋁或氧化矽。
轉換磷光體與另一材料之莫耳比較佳在1：0.5至10：1之範圍內，較佳而言1：1至5：1。精確的莫耳比特定而言取決於轉換磷光體與另一材 料之熱膨脹係數對彼此作用的方式。轉換磷光體一般具有正熱膨脹係數及因此隨溫度提高而膨脹。為了補償該膨脹，所用另一材料為具有負熱膨脹係數的材料。另一材料之膨脹係數應負至轉換磷光體之膨脹係數為正的程度。在該理想情形下，應以0.9：1至1：0.9之莫耳比應用兩種材料。兩種組分的莫耳比應彼此調節至轉換磷光體之正膨脹係數大於另一材料之負熱膨脹係數的模量的程度。換言之，複合陶瓷中之兩種組分的莫耳比應與其熱膨脹係數之模數的比大致成正比。
本發明亦係關於一種製造複合陶瓷、較佳而言根據本發明之複合陶瓷的方法，其包括下列步驟：a)提供轉換磷光體；b)提供具有負熱膨脹係數的材料；c)將在步驟a)及b)中提供之兩種組分混合以產生混合物；及d)燒結該混合物。
根據本發明，應以與就根據本發明之複合陶瓷而言完全相同的方式定義在步驟a)中提供的轉換磷光體。較佳地以粉末形式提供文中之轉換磷光體。文中之轉換磷光體粉末的平均顆粒大小較佳在0.1至1μm之範圍內。
在步驟b)中提供的具有負熱膨脹係數的材料於文中應以與複合陶瓷有關而定義之另一材料完全相同的方式定義。其較佳地同樣以粉末形式使用及其平均顆粒大小較佳在1至10μm之範圍內。
在根據本發明之方法的步驟c)中，將在步驟a)及b)中提供的材料彼此混合。可呈乾燥狀態或呈藉由添加溶劑之懸浮液的形式將該等粉末彼此混合。適宜的溶劑為慣用溶劑，例如乙醇或異丙醇。步驟c)中之混合較佳係在球磨機中進行。較佳係持續混合直到粉末之平均顆粒大小在0.1至1μm之範圍內。文中可有益地採用特定添加劑從而對抗黏聚物之形成。就氧化性粉末而言，通常使用所謂聚電解質類，例如 Darvan(Vanderbilt)、Dolapix(Zschimer & Schwertz)、KD1(Uniqema)。
混合之後，可進一步處理所得粉末混合物。較佳地以單軸及均壓之方式以兩個步驟將粉末混合物壓製呈薄圓盤之形式，其中該壓製壓力在100至300MPa之範圍內。
根據本發明，在適當溫度下進行步驟d)之燒結。若提供之步驟a)中之轉換磷光體不包括塗層，在低於具有負熱膨脹係數之材料的熔點的溫度下進行該燒結。已經發現，若燒結溫度為具有負熱膨脹係數之材料的熔化溫度之2/3至5/6，可達到良好的結果。若轉換磷光體攜帶在處理條件下穩定的惰性化塗層，本發明之該變形下之燒結亦可在熔化溫度或略高於其之區域中進行。燒結較佳係在800至1600℃之範圍內、更佳而言1000至1600℃的溫度下進行。燒結較佳係在燒結爐中進行。燒結較佳係在保護性氣體氛圍(N2或Ar)，或者在還原氛圍(諸如混合氣體(forming gas))下進行。
本發明另外係關於一種製造複合陶瓷、較佳而言根據本發明之複合陶瓷的方法，其包括下列步驟：a')以鋁氧化物塗覆轉換磷光體；b')將在步驟a')中獲得之經塗覆之轉換磷光體與含W或Mo之組分混合以產生混合物；及c')在1000至1600℃之範圍內、較佳而言在1400至1600℃之範圍內之溫度下燒結步驟b')中獲得之混合物。
根據本發明，應以與就根據本發明之複合陶瓷而言完全相同的方式定義在步驟a')中提供的轉換磷光體。較佳地以粉末形式提供文中之轉換磷光體。文中之轉換磷光體粉末的平均顆粒大小較佳在1至10μm之範圍內。
所用鋁氧化物可為能夠在步驟c')中與含W或Mo之化合物的燒結 中形成具有負熱膨脹係數的材料的任何氧化性鋁化合物。所用鋁氧化物較佳係Al2O3，尤其較佳地呈γ-變體。
含W或Mo之組分用於表示藉由燒結可與鋁氧化物反應以產生具有負熱膨脹係數之材料的無機化合物。所用含W或Mo之組分較佳係WO3或MoO3。具有負熱膨脹係數的材料於文中應以與複合陶瓷有關而定義之另一材料完全相同的方式定義。
該替代性製造方法在步驟c')中產生轉換磷光體之顆粒係由具有負熱膨脹係數之材料包圍的複合陶瓷。
本發明進一步係關於以根據本發明之複合陶瓷或藉由根據本發明之方法製造之複合陶瓷於作為發射轉換材料的用途。
由於在複合陶瓷中存在轉換磷光體，複合陶瓷亦具有可將一種激發波長之光/輻射轉換成另一波長的光的性質。因此，該發射轉換材料較佳地用於光源中。該光源尤其較佳地為或包含LED(發光二極體)。而且，該光源較佳地發射白光。
因此，本發明進一步亦係關於一種包括根據本發明之複合陶瓷或藉由根據本發明之方法製造之複合陶瓷的光源。該光源可為任何類型，其中來自一次光源之光可經轉換磷光體轉換。然而，該光源較佳地為或包含LED。
在根據本發明之LED的情形下，亦慣用術語pc-LED表示「轉換磷光體LED」。
一次光源可為半導體晶片，基於ZnO、TCO(透明傳導性氧化物)，ZnSe或SiC之發光配置，基於有機發光層(OLED)之配置或電漿或放電源，較佳係半導體晶片。該類型之光源的可能形式為熟習此項技術者知曉。
若一次光源為半導體晶片，其較佳係特定而言具有式IniGajAlkN之發光氮化銦鋁鎵(InAlGaN)，其中0i，0j，0k及i+j+k=1。
光源中所用之複合陶瓷較佳係呈均質、薄且無孔板之形式直接應用至呈晶片之形式之一次光源的表面。這具有不會發生轉換磷光體之激發及發射之位置相依性的變化的優點，使得由其配置之光源可以發射均勻及顏色恆定的光錐及具有高的光輸出。呈陶瓷發射轉換模製物形式之複合陶瓷視需要可利用例如水-玻璃溶液固定至晶片基板。
在一個較佳實施例中，呈陶瓷發射轉換模製物之形式的複合陶瓷在與半導體晶片相對之側具有結構化(例如錐體)表面。因此，盡可能多的光可由陶瓷發射轉換模製物耦合出。陶瓷發射轉換模製物上之結構化表面較佳地藉由(例如在均壓壓製之情形下)具有結構化壓製模版及因此將結構壓印至表面中之壓製模子製造。若欲製造盡可能薄的陶瓷發射轉換模製物或小板，則需要結構化表面。熟習此項技術者知曉壓製條件(參見J.Kriegsmann,Technische keramische Werkstoffe[Industrial Ceramic Materials]，第4章，Deutscher Wirtschaftsdienst,1998)。
本發明進一步係關於一種特定而言用於顯示裝置之背光的發光單元，其包括至少一種根據本發明之光源。該類型之發光單元主要用於背光顯示裝置，特定而言液晶顯示裝置(LC顯示器)中。因此，本發明亦係關於一種該類型的顯示裝置。
在一個根據本發明之發光單元的同樣較佳的變體中，藉由光導配置較佳地發生介於發射轉換材料(複合陶瓷)與一次光源(特定而言半導體晶片)之間的光耦合。因此，一次光源可安裝在中央位置及視需要藉由光導裝置(諸如光纖)光耦合至發射轉換材料。以此方式，可實現適合照明願望的燈，該等燈僅由一或多種不同可經排列以形成光幕的轉換磷光體及耦合至一次光源的光波導組成。以此方式，可在有利於電氣設備之位置定位強一次光源及將包括耦合至光波導之發射轉換材料的燈安裝在任何要求的位置，無需其他電纜而僅藉由設置光波導 安裝。該概念亦稱為「遠端概念」或「遠端磷光體概念」。以用於光學激發所用之光源與根據本發明之陶瓷模製物保持距離之方式，將所述之陶瓷磷光體安裝於燈中。
以下實例及圖式欲說明本發明。然而，其不應以任何方式視為具有限制性。可用於製備中之所有化合物或組分為已知的及可購得，或可藉由已知方法合成。
實例： 實例1：製備由Y 3 (Al 1-a Si a/2 Mg a/2 ) 5 O 12 ：Ce及Al 2 W 3 O 12 組成之複合陶瓷
單獨製造用於複合陶瓷的粉末組分，即鋁酸釔及鎢酸鋁。所用起始材料為用於鋁酸釔之金屬硝酸鹽Y(NO3)3、Al(NO3)3、Ce(NO3)3及用於鎢酸鋁之含於氨水中之Al(NO3)3及WO3，其等在每一情形下係經混合以產生均質溶液。溶液中之金屬陽離子係藉由添加錯合劑(例如三羥甲基胺基甲烷(trisamine))而穩定及接著蒸發以產生固態殘留物。進一步加熱乾燥殘留物導致燃燒及形成海綿狀前驅物結構。在800至1000℃之溫度下煅燒該等前驅物及轉換成呈軟黏聚物之形式的化合物Y3-xCexAl5O12及Al2W3O12。藉由濕法化學方式，以Al2O3塗覆Al2W3O12粉末，其中該塗覆處理係藉由在混合反應器中，經添加作為催化劑之氨水，水解含於醇介質中之異丙醇鋁而實現。
在隨後步驟中，混合兩種粉末，其中該第二種組分之體積比例在10至60體積%之範圍內及經考慮成品陶瓷之膨脹測量值而測定。
以單軸及均壓之方式以兩個步驟將混合粉末壓製呈薄圓盤之形式，其中該壓製壓力在100至300MPa之範圍內。在空氣中以多步驟處理實現後續的燒結，其中該溫度在1000℃至1600℃之範圍內。經燒結之陶瓷係利用金剛石懸浮液研磨及藉由皮秒雷射(picolaser)切割成與激發源相匹配之尺寸。
實例2：製備由Y 3 (Al 1-a Si a/2 Mg a/2 ) 5 O 12 ：Ce及YAlW 3 O 12 (3：1)組成之複合陶瓷
藉由陶瓷法，單獨製造用於複合陶瓷的粉末組分，即經鎂及矽摻雜之鋁酸釔及鎢酸釔鋁。呈精細粉末形式之金屬氧化物係在800℃至1200℃之範圍內之溫度下混合、煅燒及合成。藉由濕法化學方式，以Al2O3塗覆YAlW3O12粉末，其中該塗覆處理係藉由在混合反應器中，經添加作為催化劑之氨水，水解含於醇介質中之異丙醇鋁而實現。精細地研磨Y3(Al1-aSia/2Mga/2)5O12：Ce粉末及與經Al2O3塗覆之YAlW3O12粉末混合。藉由兩步驟單軸及均壓壓製，將混合物成形呈薄圓盤之形式，其中該壓製壓力在100至300MPa之範圍內。在空氣中以多步驟處理實現後續的燒結，其中該溫度在1000℃至1600℃之範圍內。經燒結之陶瓷係利用金剛石懸浮液研磨及藉由皮秒雷射切割成與激發源相匹配之尺寸。
實例3：用於來自YAG：Ce及鎢酸鹽之複合陶瓷之製備的具體實驗程序((實例3a：Al 2 W 3 O 12 ；實例3b：AlYW 3 O 12 ))
步驟1：藉由自燃法製造YAG：Ce粉末，其中金屬之硝酸鹽水溶液係與三羥甲基胺基甲烷(TRIS：M=121.14g/mol)混合，乾燥及接著燃燒。在1000℃煅燒黑色前驅物及在該方法中轉換成精細顆粒無色粉末。
將8.4594g(0.02524mol)Y2O3溶於10ml HNO3及用H2O補足至約250ml。接著添加46.8913g(0.08421mol)Al(NO3)3* 9H2O及0.03256g(0.00005mol)Ce(NO3)3*9H2O及溶解。將TRIS添加至該均質溶液及用H2O補足至約500ml。在加溫後，蒸發H2O，及將殘留物燃燒。前驅物係在乾燥箱中乾燥12h，在研缽中研磨及接著在1000℃之爐子中煅燒1h。
步驟2：藉由陶瓷法製造Al2W3O12粉末，其中該等精細顆粒氧化 物Al2O3及WO3係以兩步驟(首先在1000℃的溫度下及接著在1100℃)混合及處理(在研缽中進行中間研磨)。
使用乙醇將1.019g(0.01mol)Al2O3(奈米)與6.955g(0.003mol)WO3研磨(瑪瑙研缽)。乾燥懸浮液及在研缽中均質化，接著在1000℃燒結12h，在研缽中研磨及在空氣中在1100℃煅燒12h。
步驟3：藉由陶瓷法，由氧化物Al2O3、WO3及Y2O3製造AlYW3O12粉末，其中在研缽中一起研磨所有氧化物粉末及以兩步驟(在1000℃(6h)及接著在1100℃(12h)的溫度下)在空氣中處理。
在乙醇中，將0.5098g(0.005mol)Al2O3(奈米大小)與6.955g(0.003mol)WO3及1.129g(0.005mol)Y2O3研磨。乾燥懸浮液及在研缽中均質化，接著在1000℃燒結12h，在研缽中研磨及在空氣中在1100℃煅燒12h。
步驟4：藉助於Al2W3O12粉末或AlYW3O12粉末之混合物製造包括YAG：Ce及一種上述金屬鎢酸鹽類的複合陶瓷。為此目的，將Y2.997Ce0.003Al5O12粉末(90-99重量%)及每一情形中之一種鎢酸鹽類(1-10重量%)在乙醇中研磨(在瑪瑙研缽中)、乾燥、利用幾滴壓製輔助聚乙烯醇潤濕(在瑪瑙研缽中)及接著單軸(約100MPa)及均壓(約300MPa)壓製以產生片(厚約2.5mm，直徑約12mm)、在空氣中乾燥及最後以兩步驟燒結(首先在1000℃的溫度下燒結12h及接著在1100℃燒結2h)。獲得陶瓷模製物。
對照實例A：製備不包括具有負熱膨脹係數之材料之複合陶瓷
為了對照，複合材料係由YAG：Ce及Al2O3製造，其中該YAG：Ce係藉由自燃法而製造。所用第二種組分為Al2O3奈米粉末(Degussa)。在混合粉末(有利地呈1：1之體積比)之後，陶瓷圓盤係以與以上實例中之彼等相似的方式製造。
對照實例B：
作為第二種對照材料，以不摻雜之YAG製造包括YAG：Ce之的陶瓷。藉由共同沈澱法製造YAG：Ce粉末，其中所用起始材料為金屬硝酸鹽類Y(NO3)3、Al(NO3)3、Ce(NO3)3及所用沉澱劑為NH4HCO3。藉由在800℃煅燒及在1000℃燒結，將產生之沉澱物轉換成YAG：Ce。在充分研磨之後，YAG：Ce變為精細顆粒及適合與以相似方式製造之YAG混合。藉由兩步驟單軸及均壓壓製，將混合物成形呈薄圓盤之形式，其中該壓製壓力在100至300MPa之範圍內。在空氣中以多步驟處理實現後續的燒結，其中該溫度在1000至1600℃之範圍內。經燒結之陶瓷係利用金剛石懸浮液研磨及藉由皮秒雷射切割成與激發源相匹配之尺寸。
實例4：利用實例3a及3b及對照實例A及B之複合陶瓷製造LED 實例4a：遠端磷光體配置
將具有5mm直徑及0.1mm厚度之由根據本發明之複合陶瓷組成的小板放置在填充液態矽氧烷OE 6550(Dow Corning)之SMD LED(晶片峰值波長450nm，工作電流強度350 mA，空腔開口直徑5.5mm)上，從而可以密封該圓形空腔。接著將該組件儲存在150℃之爐子中1h，期間矽氧烷硬化及牢固地結合至LED及陶瓷小板。
實例4b：晶片級轉換配置
藉助於1滴矽氧烷OE 6550(Dow Corning)，直接放置具有1x1mm之正方形尺寸及0.1mm厚度的陶瓷磷光體小板從而裝配於SMD覆晶LED之1x1mm LED晶片(晶片峰值波長450nm，工作電流強度350 mA)上。在150℃歷時1h之時期，矽氧烷已經硬化之後，LED之剩餘空腔係利用矽氧烷OE 6550(Dow Corning)澆注，及將整個組件儲存在150℃ 1h以硬化該矽氧烷。
實例5：發射強度
在圖1及2中，根據本發明之來自實例3a及3b之複合陶瓷相比來自 對照實例A及B之YAG：Ce陶瓷展現更低的強度，因YAG：Ce磷光體在複合陶瓷中係呈稀釋形式，這為可以預料的。利用Edinburgh Instruments FL900螢光光譜儀記錄光譜，其中所用激發源為Xe中壓燈(Osram)。
實例6：壽命
根據實例1、2及3之根據本發明之複合陶瓷的優點可經參考發光二極體中之長期使用而證實。根據本發明之材料相比來自先前技術中之陶瓷展現減少的斷裂。因此，效率未快速地下降，及可以良好的效率更長時間地使用陶瓷。
圖1：圖1顯示對照材料YAG：Ce及如實例3a所製造之由Y3Al5O12：Ce及Al2W3O12(3：1)組成的複合陶瓷的發射光譜。經利用Xe中壓燈(Osram)作為激發源之Edinburgh Instruments FL900螢光光譜儀記錄該光譜。
圖2：圖2顯示對照材料YAG：Ce及如實例3b所製造之由Y3Al5O12：Ce及YAlW3O12(3：1)組成的複合陶瓷的發射光譜。經利用Xe中壓燈(Osram)作為激發源之Edinburgh Instruments FL900螢光光譜儀記錄該光譜。

Claims (16)

  1. 一種複合陶瓷，其包括轉換磷光體及另一材料，其特徵在於該另一材料具有負熱膨脹係數，且係選自由Al2W3O12、YAlW3O12、Al2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、YAlMoW2O12及其混合物組成之清單。
  2. 如請求項1之複合陶瓷，其中該轉換磷光體為含Ce、Eu及/或Mn之材料。
  3. 如請求項2之複合陶瓷，其中該轉換磷光體基於在晶格位置置換含Ce、Eu及/或Mn之材料中之Ce、Eu及/或Mn的原子總數計，包括0.1至5原子%之Ce、Eu及/或Mn。
  4. 如請求項1至3中任一項之複合陶瓷，其中該轉換磷光體為含Ce之材料。
  5. 如請求項4之複合陶瓷，其中該轉換磷光體為含Ce之石榴石。
  6. 如請求項5之複合陶瓷，其中該含Ce之石榴石具有式E3G2(TO4)3：Ce，其中E係選自由Y、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu或其混合物組成之群，及G及T彼此獨立地分別選自由Al、Sc、Ga或其混合物組成之群，或G及T一起表示Mg/Si之組合或Mg/Ge之組合，其中Mg及Si或Mg及Ge各自係以相同莫耳比存在。
  7. 如請求項1至3中之任一項之複合陶瓷，其中該負熱膨脹係數在20℃至200℃之範圍內之溫度變化之情形下在1*10-6至12*10-6K-1之範圍內。
  8. 如請求項1至3中之任一項之複合陶瓷，其中該轉換磷光體與另一材料的莫耳比在1：0.5至10：1。
  9. 如請求項8之複合陶瓷，其中該轉換磷光體與另一材料的莫耳比在1：1至5：1之範圍內。
  10. 一種製造如請求項1至9中任一項之複合陶瓷的方法，其包括下列步驟：a)提供轉換磷光體；b)提供具有負熱膨脹係數的材料，其中該具有負熱膨脹係數的材料係選自由Al2W3O12、YAlW3O12、Al2Mo3O12、YAlMo3O12、ZrMo2O8、Al2WMo2O12、YAlWMo2O12、ZrWMoO8、Al2MoW2O12、YAlMoW2O12及其混合物組成之清單；c)將在步驟a)及b)中提供之兩種組分混合以產生混合物；及d)燒結該混合物。
  11. 如請求項10之方法，其中該燒結係在具有負熱膨脹係數之材料的熔化溫度之2/3至5/6的範圍內的溫度下進行。
  12. 一種製造如請求項1至9中任一項之複合陶瓷的方法，其包括下列步驟：a')以鋁氧化物塗覆轉換磷光體；b')將在步驟a')中獲得之經塗覆之轉換磷光體與含W或Mo之組分混合以產生混合物；及c')在1000至1600℃之範圍內之溫度下燒結步驟b')中獲得之混合物。
  13. 一種以如請求項1至9中之任一項或如請求項10至12中之任一項所製造之複合陶瓷於作為發射轉換材料的用途。
  14. 如請求項13之用途，其中該發射轉換材料用於光源中。
  15. 一種光源，其包括如請求項1至9中之任一項或如請求項10至12中之任一項所製造之複合陶瓷及一次光源。
  16. 一種發光單元，其包括至少一種如請求項15之光源。
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JP2015138168A (ja) * 2014-01-23 2015-07-30 セイコーエプソン株式会社 蛍光発光素子およびプロジェクター
DE102015102842A1 (de) * 2015-02-27 2016-09-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Leuchtstoffkompositkeramik sowie Verfahren zu deren Herstellung
CN105199728B (zh) * 2015-06-01 2017-03-22 井冈山大学 一种Eu3+和Mn2+共掺杂钨酸盐红色荧光材料
CN108610023B (zh) 2016-12-09 2021-07-23 深圳光峰科技股份有限公司 陶瓷复合材料的制备方法、陶瓷复合材料及波长转换器
US11014854B2 (en) 2017-08-07 2021-05-25 Consolidated Nuclear Security, LLC Ceramic radiation detector device and method
CN109896843A (zh) * 2017-12-07 2019-06-18 上海航空电器有限公司 用于激光照明的复相陶瓷阵列、制备方法及光源装置
CN109896853B (zh) * 2017-12-11 2022-07-15 上海航空电器有限公司 具有较低膨胀系数的陶瓷复合体、制备方法及光源装置
CN110386822B (zh) * 2018-04-19 2021-02-26 深圳光峰科技股份有限公司 一种复相荧光陶瓷及其制备方法
US20200161506A1 (en) * 2018-11-21 2020-05-21 Osram Opto Semiconductors Gmbh Method for Producing a Ceramic Converter Element, Ceramic Converter Element, and Optoelectronic Component
CN112410623B (zh) * 2019-08-21 2022-01-07 天津大学 一种高阻尼铝硅基复合材料及其制备方法
CN111087173B (zh) * 2019-12-30 2022-11-04 厦门天马微电子有限公司 一种负膨胀填料及其制备方法和应用
CN112159220B (zh) * 2020-09-24 2022-11-18 徐州凹凸光电科技有限公司 一种白光led/ld用高热稳定性高量子效率荧光陶瓷及其制备方法
CN116004231A (zh) * 2023-01-18 2023-04-25 海南大学 一种稀土掺杂的负热膨胀发光材料及其制备方法与应用
CN116355613A (zh) * 2023-03-31 2023-06-30 安徽工业大学 一种高灵敏度自激活荧光测温材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1266826A (zh) * 2000-03-10 2000-09-20 上海交通大学 低膨胀或负膨胀复相陶瓷及其制备方法
CN101142857A (zh) * 2005-03-14 2008-03-12 皇家飞利浦电子股份有限公司 多晶陶瓷结构中的磷光体和包括该磷光体的发光元件
TW200902685A (en) * 2007-03-06 2009-01-16 Merck Patent Gmbh Phosphors consisting of doped garnets for pcLEDs
TW200936729A (en) * 2007-11-08 2009-09-01 Merck Patent Gmbh Process for the preparation of coated phosphors
CN101632181A (zh) * 2007-03-12 2010-01-20 皇家飞利浦电子股份有限公司 包括低热膨胀系数的化合物的照明系统

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5919720A (en) 1997-04-15 1999-07-06 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University Materials with low or negative thermal expansion
WO2004063120A1 (ja) * 2003-01-14 2004-07-29 Matsushita Electric Industrial Co., Ltd. 低熱膨張材料
JP2005220299A (ja) * 2004-02-09 2005-08-18 Matsushita Electric Ind Co Ltd 蛍光体
EP1862035B1 (en) 2005-03-14 2013-05-15 Koninklijke Philips Electronics N.V. Phosphor in polycrystalline ceramic structure and a light-emitting element comprising same
KR100764148B1 (ko) * 2006-01-17 2007-10-05 루시미아 주식회사 시트상 형광체와 그 제조방법 및 이를 이용한 발광장치
DE102006054331A1 (de) * 2006-11-17 2008-05-21 Merck Patent Gmbh Leuchtstoffkörper basierend auf plättchenförmigen Substraten
DE102007001903A1 (de) * 2006-11-17 2008-05-21 Merck Patent Gmbh Leuchtstoffkörper enthaltend Rubin für weiße oder Color-on-demand LEDs
CN101697367B (zh) * 2009-09-30 2014-04-02 烁光特晶科技有限公司 一种利用透明陶瓷制备led的方法
KR101774434B1 (ko) * 2010-03-31 2017-09-04 오스람 실바니아 인코포레이티드 형광체 및 이를 함유한 ｌｅｄ
US20130049575A1 (en) 2010-07-14 2013-02-28 Shunsuke Fujita Phosphor composite member, led device and method for manufacturing phosphor composite member
WO2012008306A1 (ja) * 2010-07-14 2012-01-19 日本電気硝子株式会社 蛍光体複合部材、ｌｅｄデバイス及び蛍光体複合部材の製造方法
JP2012052061A (ja) * 2010-09-03 2012-03-15 Nippon Electric Glass Co Ltd 蛍光体複合部材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1266826A (zh) * 2000-03-10 2000-09-20 上海交通大学 低膨胀或负膨胀复相陶瓷及其制备方法
CN101142857A (zh) * 2005-03-14 2008-03-12 皇家飞利浦电子股份有限公司 多晶陶瓷结构中的磷光体和包括该磷光体的发光元件
TW200902685A (en) * 2007-03-06 2009-01-16 Merck Patent Gmbh Phosphors consisting of doped garnets for pcLEDs
CN101632181A (zh) * 2007-03-12 2010-01-20 皇家飞利浦电子股份有限公司 包括低热膨胀系数的化合物的照明系统
TW200936729A (en) * 2007-11-08 2009-09-01 Merck Patent Gmbh Process for the preparation of coated phosphors

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