TWI422056B - 製造具有模製封裝物之發光裝置的方法 - Google Patents
製造具有模製封裝物之發光裝置的方法 Download PDFInfo
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- TWI422056B TWI422056B TW095139017A TW95139017A TWI422056B TW I422056 B TWI422056 B TW I422056B TW 095139017 A TW095139017 A TW 095139017A TW 95139017 A TW95139017 A TW 95139017A TW I422056 B TWI422056 B TW I422056B
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Description
本發明係關於一種製造一具有一LED晶粒及一封裝物之發光裝置的方法,其中該封裝物經模製且包含含矽樹脂。
慣常使用轉移模製(transfer molding)方法實現對半導體裝置之封裝,在該轉移模製方法中,以電介質預熱熱固性模製化合物(通常為固體環氧樹脂預成型體(epoxy preform))且隨後將其置放於模製工具之罐中。使用轉移筒(transfer cylinder)或栓塞將模製化合物推入塑模之流動系統及閘門內。隨後,使模製化合物流過晶片、接線及引線框,封裝半導體裝置。大多數轉移模製方法中均存在因填充塑模所需之高操作溫度(室溫下模製化合物為固體)及高壓力而引起的重大問題(即使在熔融狀態下,模製化合物仍具有高黏度且黏度隨反應而進一步增加)。該等問題會導致塑模填充不完全、熱應力(由於反應溫度遠高於最終使用溫度)及引線彎曲(wire sweep)。
本文揭示一種在低溫下使用低度至中度黏度樹脂製造具有模製含矽封裝物之經封裝LED的方法。該方法避免與如上文所述之引線彎曲相關的問題。
本文所揭示之方法係用於製造發光裝置,該方法包含以下步驟:提供LED;使該LED與包含含矽樹脂(包含與矽結合之氫及脂族不飽和基)、可由光化輻射活化之第一含金屬催化劑及可由熱(而非光化輻射)活化之第二含金屬催化劑的可光聚合組合物接觸;及使該可光聚合組合物與塑模接觸。與塑模接觸之後,可對可光聚合組合物施加光化輻射,其中光化輻射為700 nm或更小之波長並引發含矽樹脂內之氫化矽烷化反應,氫化矽烷化反應包含與矽結合之氫與脂族不飽和基之間的反應。光化輻射可用於形成部分聚合之組合物,因此,該方法可另外包含加熱以進一步引發含矽樹脂內之氫化矽烷化反應。或者,在使可光聚合組合物與塑模接觸之後,可藉由將其加熱至低於約150℃之溫度而引發氫化矽烷化。
該方法亦可包含在與塑模接觸之前對光聚合組合物施加光化輻射,以便形成部分聚合之組合物。隨後,在與塑模接觸之後,可對部分聚合之組合物施加光化輻射,從而進一步引發含矽樹脂內之氫化矽烷化,並形成第二經部分聚合之組合物。或者,可藉由將部分聚合之組合物加熱至低於約150℃之溫度而引發氫化矽烷化。
該方法亦可包含在與塑模接觸之前將部分聚合之組合物加熱至低於約150℃之溫度,以便形成部分聚合之組合物。隨後,在與塑模接觸之後,可對部分聚合之組合物施加光化輻射,從而進一步引發含矽樹脂內之氫化矽烷化,並形成第二經部分聚合之組合物。或者,可藉由將部分聚合之組合物加熱至低於約150℃之溫度以進一步引發氫化矽烷化。
可使塑模成形以賦予任何可用之結構,例如,正透鏡或負透鏡,或一些宏觀結構及/或微觀結構之組合。
本發明之該等及其他態樣將自下文之詳細描述及圖式顯而易見。上文之概述決不應解釋為對所主張之標的物的限制,因專利申請期間可對其進行修改,故該標的物僅由附屬申請專利範圍定義。
本申請案係關於Thompson等人題為"製造具有模製封裝物之發光裝置的方法(Method of Making Light Emitting Device Having a Molded Encapsulant)"之美國專利申請第11/551,323號,且與本申請案同一日期申請(檔案號61404US003)。本申請案亦係關於:Boardman等人於2005年10月21日申請之題為"製造具有含矽封裝物之發光裝置的方法(Method of Making Light Emitting Device with Silicon-Containing Encapsulant)"之共同讓渡、同在申請的美國專利申請案第11/255711號,其主張Boardman等人於2005年10月17日申請之題為"製造具有含矽封裝物之發光裝置的方法(Method of Making Light Emitting Device with Silicon-Containing Encapsulant)"的美國臨時申請案第60/727472號的優先權;Boardman等人於2005年10月21日申請之題為"製造具有含矽封裝物之發光裝置的方法(Method of Making Light Emitting Device with Silicon-Containing Encapsulant)"之共同讓渡、同在申請的美國專利申請案第11/255712號,其主張Boardman等人於2005年10月17日申請之題為"製造具有含矽封裝物之發光裝置的方法(Method of Making Light Emitting Device with Silicon-Containing Encapsulant)"的美國臨時申請案第60/727532號的優先權;及Boardman等人題為"製造具有含矽封裝物之發光裝置的方法(Method of Making Light Emitting Device with Silicon-Containing Encapsulant)"且於2005年10月17日申請之共同讓渡、同在申請的美國專利申請案第11/252336號,其為於2004年11月18日申請、現已批准之美國專利申請案第10/993,460號之部分接續案;該等專利之揭示內容係以全文引用之方式併入本文中。
本文所述之方法使用包含模製材料且可經成形從而對封裝物之外表面賦予所需之良好形狀的塑模。如本文所使用之"封裝物"係指至少部分聚合之含矽樹脂。能夠形成為塑模之任何材料均可使用,且一般而言,通常需要模製材料具有高於如下文所述之製造發光裝置的方法中所使用之特定溫度的玻璃轉移溫度。模製材料之實例包括聚合材料,諸如含氟彈性體(fluoroelastomer)、聚烯烴、聚苯乙烯、聚酯、聚胺基甲酸酯、聚醚、聚碳酸酯、聚甲基丙烯酸甲酯;及無機材料,包含陶瓷、石英、藍寶石、金屬及某些玻璃。甚至有機-無機混合材料亦可用作塑模;例示性混合材料包括Choi等人於Langmuir,第21卷,第9390頁(2005)中所述之氟化材料。塑模可為透明,諸如透明陶瓷;透明塑模可用於穿過塑模施加光化輻射的情況中。塑模亦可不透明,諸如不透明陶瓷、不透明塑膠或金屬。可藉由習知之加工、金剛石車削法(diamond turning)、接觸式蝕刻法(contact lithography)、投射蝕刻法(projection lithography)、干涉蝕刻法(interference lithography)、蝕刻法或任何其他合適技術製造塑模。塑模可為原始主模或其子模。模製可稱為反應性壓印。
塑模接觸可光聚合組合物或已部分聚合之組合物之表面可經脫模材料塗覆,以便促進將塑模自已模製之表面移除。舉例而言,當使用鋼製或鎳製塑模時,每5至10個週期以2至5重量%家用清潔劑於水中之溶液噴灑模製表面可為有益。亦可使用碳氟化合物脫模劑。可使用單個塑模同時製造一個發光裝置或複數個發光裝置。
可使塑模成形,從而在可光聚合組合物或已部分聚合之組合物之表面上賦予任何可用結構。舉例而言,可使塑模成形,從而於LED上形成折射透鏡。透鏡化係指用以形成正透鏡或負透鏡之封裝物表面之實質部分具有均一(或接近均一)曲率,該表面之直徑大致為包裝或反射杯之尺寸。一般而言,透鏡狀表面可以"曲率半徑"表徵。曲率半徑可為正值,表示凸面;或為負值,表示凹面;或為無窮大,表示平坦表面。透鏡化可藉由減少封裝物-空氣界面處之入射光的總內反射而改良光提取(light extraction)。其亦可改變自發光裝置發射之光線的角分佈。
參看圖1,已展示包含未經模製之封裝物6的發光裝置10。LED 2係安裝於置於反射杯4中之基板7上之經金屬處理之接觸件3a上。LED 2在其最底面具有一電接觸件且在其最上面具有另一電接觸件,後者藉由接線5連接於單獨電接觸件3b。可將電源耦接於電接觸件以使LED通電。封裝物6之表面8未經模製。圖2展示例示性發光裝置20之示意性截面圖,其中封裝物24之表面22經模製成大致反射杯26之尺寸之半球形透鏡的形狀。圖3展示另一例示性發光裝置30之示意性截面圖,但該裝置並不具有反射杯。在此情形中,封裝物34之表面32亦經模製成半球形透鏡之形狀。
亦可成形具有宏觀結構之表面,該宏觀結構具有小於包裝尺寸但遠大於可見光波長的特徵尺寸。亦即,每一宏觀結構可具有10 μm至1 mm之尺寸。每一宏觀結構之間之間隔或週期亦可為10 μm至1 mm(或為LED包裝尺寸之約1/3)。宏觀結構之實例包括當於橫截面觀察時看來似乎成形為類似正弦波、三角波、方波、經校正之正弦波、鋸齒波、擺線(更通常為長幅圓滾線)或波動的表面。宏觀結構之週期性可為一維或二維。具有一維週期性之表面具有僅沿該表面之一個主要方向的重複結構。在一特定實例中,塑模可包含購自3M Company之任何VikuitiT M
增亮膜。
可將塑模成形以賦予能夠製造可產生側向發光模式之模製封裝物的透鏡結構。舉例而言,模製封裝物具有中心軸,且反射進入該模製封裝之光線並折射,且最終以與中心軸大體上垂直之方向出射;該等類型之側向發光透鏡形狀及裝置的實例描述於U.S.6,679,621 B2及U.S.6,598,998 B2中。舉例而言,模製封裝物具有一般平坦表面,其中一光滑曲面界定延伸至封裝物中之渦旋形狀,且其具有形成於齒尖中之等角螺旋形狀;此類輪廓之實例描述於U.S.6,473,554 B1,尤其係圖15、16及16A中。
具有二維週期性之表面具有沿宏觀結構平面內之任何兩個正交方向的重複結構。具有二維週期性之宏觀結構的實例包括隨機表面、二維正弦曲線、錐形陣列、諸如立體角稜鏡(cube-corner)之稜鏡陣列及微透鏡陣列。圖4展示另一例示性發光裝置40之加高圖,其中封裝物之表面42經成形為費涅爾透鏡(Fresnal lens),該透鏡通常具有圓形對稱且可設計成在佔據遠小於固體透鏡之體積的同時複製任何正或負透鏡之光學特性。圖4亦展示安置於反射杯44中之基板47上的經金屬處理之接觸件43a及43b(LED及接線不可見)。
一般而言,宏觀結構之表面無需具有均一尺寸。舉例而言,其可朝向包裝之邊緣變大或變小,或其可改變形狀。該表面可由本文所述之形狀的任何線性組合組成。
該表面亦可經成形而具有微觀結構,該微觀結構具有與可見光波長之數值範圍類似之數值範圍的特徵尺寸。亦即,每一微觀結構可具有100 nm至小於10 μm之尺寸。當光線與微觀結構化表面相互作用時,其傾向於繞射。因此,微觀結構化表面之設計需要特別注意光線的波樣(wave-like)性質。微觀結構之實例為一維及二維繞射光柵;一維、二維或三維光子晶體;二元光學元件;及"motheye"抗反射塗料。圖5展示例示性發光裝置50之示意性截面圖,其中封裝物54之表面52經模製而具有具一維週期性之線性稜鏡。亦展示具有良好形狀之表面58的塑模56。圖7展示另一例示性發光裝置70之加高圖,其中封裝物之表面72包含二維稜鏡之陣列。在圖6中,展示另一例示性發光裝置60的示意性截面圖,其中封裝物64之表面62經模製而具有微透鏡。
微觀結構之表面無需具有均一尺寸。舉例而言,該等元件可朝向包裝之邊緣而變大或變小,或其可改變形狀。表面可由本文所述之形狀的任何線性組合組成。圖8展示另一例示性發光裝置80之加高圖,其中封裝物之表面82包含隨機安置之凸起及凹陷。
封裝物之表面可包含來自所有三個尺寸範圍的結構。使所有包裝表面透鏡化而具有一定曲率半徑,該曲率半徑可為正值、負值或無窮大。可將宏觀結構或微觀結構添加至透鏡化表面以進一步增強光輸出或使指定應用中之角分佈最佳化。表面可甚至在透鏡化表面之宏觀結構上併入微觀結構。
本文所述之方法亦包括提供包含含矽樹脂之可光聚合組合物,該含矽樹脂包含與矽結合之氫及脂族不飽和基。含矽樹脂可包括單體、寡聚體、聚合物或其混合物。其包括與矽結合之氫及脂族不飽和基,其允許氫化矽烷化(亦即,跨碳碳雙鍵或三鍵添加與矽結合之氫)。與矽結合之氫及脂族不飽和基可或可不存在於同一分子中。此外,脂族不飽和基可或可不直接與矽結合。
較佳之含矽樹脂為提供封裝物之者,其可為液體、凝膠、彈性體或非彈性固體之形式,且其為熱穩定及光化學穩定。對於UV光而言,具有至少1.34之折射率的含矽樹脂較佳。對於一些實施例而言,具有至少1.50之折射率的含矽樹脂較佳。
選擇較佳含矽樹脂從而使其提供光穩定且熱穩定之封裝物。在本文中,光穩定係指延長曝露於光化輻射後未化學降解之材料,尤其不涉及有色或吸光降解產物的形成。在本文中,熱穩定係指延長暴露於熱後未化學降解之材料,尤其不涉及有色或吸光降解產物的形成。此外,較佳之含矽樹脂為具有相對快速硬化機制(例如數秒至小於30分鐘)以便加速製造時間並降低整個LED成本的含矽樹脂。
合適含矽樹脂之實例揭示於(例如)美國專利第6,376,569號(Oxman等人)、第4,916,169號(Boardman等人)、第6,046,250號(Boardman等人)、第5,145,886號(Oxman等人)、第6,150,546號(Butts)及美國專利申請案第2004/0116640號(Miyoshi)中。較佳之含矽樹脂包含有機矽氧烷(亦即,聚矽氧),其包括有機聚矽氧烷。該等樹脂通常包括至少兩種組份,一種具有與矽結合之氫且另一種具有脂族不飽和基。然而,與矽結合之氫與烯烴不飽和物均可存在於同一分子中。
在一實施例中,含矽樹脂可包括具有至少兩個結合於分子中之矽原子的脂族不飽和基(例如烯基或炔基)位點的聚矽氧組份,及具有至少兩個結合於分子中之矽原子之氫原子的有機氫矽烷及/或有機氫聚矽氧烷組份。含矽樹脂較佳包括兩種組份,其中含有聚矽氧之脂族不飽和基作為基質聚合物(亦即,組合物中的主要有機矽氧烷組份)。較佳之含矽樹脂為有機聚矽氧烷。該等樹脂通常包含至少兩種組份,該等組份之至少一種含有脂族不飽和基且該等組份之至少一種含有與矽結合之氫。此等有機聚矽氧烷已為此項技術中已知,且揭示於諸如US 3,159,662(Ashby)、US 3,220,972(Lamoreauz)、US 3,410,886(Joy)、US 4,609,574(Keryk)、US 5,145,886(Oxman等人)及US 4,916,169(Boardman等人)之專利中。若單一樹脂組份均含有脂族不飽和基及與矽結合之氫,則可能硬化一種組份有機聚矽氧烷樹脂。
含有脂族不飽和基之有機聚矽氧烷較佳為包含式R1 a
R2 b
SiO( 4 - a - b ) / 2
之單元的直鏈、環狀或支鏈有機聚矽氧烷,其中:R1
為單價直鏈、支鏈或環狀未經取代或經取代烴基,其無脂族不飽和基且具有1至18個碳原子;R2
為具有脂族不飽和基及2至10個碳原子之單價烴基;a為0、1、2或3;b為0、1、2或3;且a+b之總和為0、1、2或3;其限制條件為平均每個分子中存在至少一個R2
。
含有脂族不飽和基之有機聚矽氧烷在25℃下較佳具有至少5 mPa.s的平均黏度。
合適R1
基團之實例為烷基,諸如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、第三戊基、環戊基、正己基、環己基、正辛基、2,2,4-三甲基戊基、正癸基、正十二烷基及正十八烷基;芳族基團,諸如苯基或萘基;烷芳基,諸如4-甲苯基;芳烷基,諸如苯甲基、1-苯基乙基及2-苯基乙基;及經取代烷基,諸如3,3,3-三氟-正丙基、1,1,2,2-四氫全氟-正己基及3-氯-正丙基。
合適R2
基團的實例為烯基,諸如乙烯基、5-己烯基、1-丙烯基、烯丙基、3-丁烯基、4-戊烯基、7-辛烯基及9-癸烯基;及炔基,諸如乙炔基、炔丙基及1-丙炔基。在本發明中,具有脂族碳碳多鍵之基團包括具有環脂族碳碳多鍵之基團。
含有與矽結合之氫之有機聚矽氧烷較佳為包含式R1 a
Hc
SiO( 4 - a - c ) / 2
之單元的直鏈、環狀或支鏈有機聚矽氧烷,其中:R1
如上文所定義;a為0、1、2或3;c為0、1或2;且a+c之總和為0、1、2或3;其限制條件為平均每個分子中存在至少一個與矽結合之氫原子。
含有與矽結合之氫之有機聚矽氧烷在25℃下較佳具有至少5 mPa.s的平均黏度。
含有脂族不飽和基及與矽結合之氫的有機聚矽氧烷較佳包含式R1 a
R2 b
SiO( 4 - a - b ) / 2
與R1 a
Hc
SiO( 4 - a - c ) / 2
之單元。在該等式中,R1
、R2
、a、b及c如上文所定義,其限制條件為平均每一分子中存在至少一個含有脂族不飽和基及1個與矽結合之氫的基團。
在含矽樹脂(尤其係有機聚矽氧烷樹脂)中,與矽結合之氫原子比脂族不飽和基的莫耳比可在0.5至10.0 mol/mol、較佳在0.8至4.0 mol/mol且更佳在1.0至3.0 mol/mol之範圍內。
就某些實施例而言,由於併入苯基或其他芳基、芳烷基或烷芳基使材料具有比所有R1
基團均為(例如)甲基之材料折射率高的折射率,因此大部分R1
基團為苯基或其他芳基、芳烷基或烷芳基之上述有機聚矽氧烷樹脂係較佳的。
所揭示之組合物亦包括第一及第二含金屬催化劑。該等催化劑已為此項技術中所知,且通常包括諸如鉑、銠、銥、鈷、鎳及鈀之貴金屬的錯合物。第一及/或第二含金屬催化劑可包含鉑。可使用兩種或兩種以上之第一及/或第二含金屬催化劑。
多種第一含金屬催化劑揭示於(例如)美國專利第6,376,569號(Oxman等人)、第4,916,169號(Boardman等人)、第6,046,250號(Boardman等人)、第5,145,886號(Oxman等人)、第6,150,546號(Butts)、第4,530,879號(Drahnak)、第4,510,094號(Drahnak)、第5,496,961號(Dauth)、第5,523,436號(Dauth)、第4,670,531號(Eckberg)以及國際公開案第WO 95/025735號(Mignani)中。
第一含金屬之催化劑可選自由β-二酮酸Pt(II)(Pt(II)β-diketonate)錯合物(諸如揭示於美國專利第5,145,886號(Oxman等人)中之者)、(η5
-環戊二烯基)三(σ-脂族基)鉑錯合物(諸如揭示於美國專利第4,916,169號(Boardman等人)及美國專利第4,510,094號(Drahnak)中之者)及經C7 - 2 0
-芳族基取代之(η5
-環戊二烯基)三(σ-脂族基)鉑錯合物(諸如揭示於美國專利第6,150,546號(Butts)中之者)組成之群。
多種第二含金屬催化劑揭示於(例如)美國專利第2,823,218號(Speier等人)、第3,419,593號(Willing)、第3,715,334號及第3,814,730號(Karstedt)、第4,421,903號(Ashby)、第3,220,972號(Lamoreaux)、第4,613,215號(Chandra等人)及第4,705,765號(Lewis)。在一些實施例中,第二含金屬催化劑包含乙烯基矽氧烷鉑(platinum vinylsiloxane)錯合物。
可光聚合組合物中所使用之第一及第二含金屬催化劑的量可視多種因素而定,諸如是否使用光化輻射及/或熱、輻射源、時間量、溫度等,以及視含矽樹脂之特定化學性質、其反應性、發光裝置中之存在量等而定。第一及第二含金屬催化劑之量可獨立地以每一百萬份可光聚合組合物之至少1份且更佳為至少5份的量使用。可光聚合組合物中較佳包括每一百萬份可光聚合組合物之不高於1000份金屬且更佳不高於200份金屬之量的該等催化劑。
除含矽樹脂及催化劑外,可光聚合組合物亦可包括非吸收性金屬氧化物微粒、半導體微粒、磷光體、增感劑(sensitizer)、光引發劑、抗氧化劑、催化劑抑制劑及顏料。若使用,則使用產生所需作用之量之該等添加劑。
可光聚合組合物內包括的微粒可經表面處理以改良微粒於樹脂內之分散性。該等用於表面處理之化學物質的實例包括矽烷、矽氧烷、羧酸、膦酸、鋯酸鹽、鈦酸鹽及其類似物。已知用於塗覆該等表面處理化學物質的技術。
可光聚合組合物中可視情況包括非吸收性金屬氧化物及半導體微粒以增加封裝物之折射率。合適非吸收性微粒為在LED發光頻寬上大體上透明的微粒。非吸收性金屬氧化物及半導體微粒之實例包括(但不限於)Al2
O3
、ZrO2
、TiO2
、V2
O5
、ZnO、SnO2
、ZnS、SiO2
及其混合物;以及其他足夠透明之非氧化物陶瓷材料,諸如包括(諸如)ZnS、CdS及GaN之材料之半導體材料。在一些應用中,具有相對較低折射率之二氧化矽(SiO2
)亦可用作微粒材料,但更重要的是,其亦可用作由較高折射率材料製成之微粒的薄表面處理,以允許用有機矽烷更容易地進行表面處理。就此方面而言,微粒可包括具有一種材料核心的物質,在該核心上沈積另一類材料。若使用,則可光聚合組合物中較佳包括以該可光聚合組合物之總重量計不大於85 wt%之量的此等非吸收性金屬氧化物及半導體微粒。可光聚合組合物中較佳包括以該可光聚合組合物之總重量計至少10 wt%之量且更佳為至少45 wt%之量的非吸收性金屬氧化物及半導體微粒。通常,微粒之尺寸可在1奈米至1微米、較佳10奈米至300奈米、更佳10奈米至100奈米之範圍內。此粒度為平均粒度,其中粒度為微粒之最長尺寸,亦即球狀微粒之直徑。熟習此項技術者應瞭解,若球狀微粒具有單峰分佈,則金屬氧化物及/或半導體微粒之體積百分比不能超過74體積%。
可光聚合組合物中可視情況包括磷光體以調節由LED發光之顏色。如本文所述,磷光體由螢光材料組成。螢光材料可為無機微粒、有機微粒或有機分子,或其組合。合適無機微粒包括摻雜榴石(諸如YAG:Ce及(Y,Gd)AG:Ce)、鋁酸鹽(諸如Sr2
Al1 4
O2 5
:Eu及BAM:Eu)、矽酸鹽(諸如SrBaSiO:Eu)、硫化物(諸如ZnS:Ag、CaS:Eu及SrGa2
S4
:Eu)、氧基-硫化物(oxy-sulfide)、氧基-氮化物(oxy-nitride)、磷酸鹽、硼酸鹽及鎢酸鹽(諸如CaWO4
)。該等物質可為習知之磷光體粉末或奈米微粒磷光體粉末之形式。另一類合適之無機微粒為由包括Si、Ge、CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、PbS、PbSe、PbTe、InN、InP、InAs、AlN、AlP、AlAs、GaN、GaP、GaAs及其組合之半導體奈米微粒製成的所謂量子點磷光體。通常,每一量子點之表面應至少經有機分子部分塗覆以防止聚結並增加與黏合劑之相容性。在一些情況中,半導體量子點可由若干層不同物質以核-殼構造製造。合適有機分子包括螢光染料,諸如列於美國專利第6,600,175號(Baretz等人)中之螢光染料。較佳螢光材料為展示良好耐久性及穩定光學特性的螢光材料。磷光體層可由單層或多層不同類型磷光體之摻合物組成,各層含有一或多種類型磷光體。磷光體層中之無機磷光體微粒的尺寸(例如直徑)可變化,且可使該等微粒分離從而使併入該等微粒之矽氧烷層之截面的平均粒度不均一。若使用,則可光聚合組合物中較佳包括以該可光聚合組合物之總重量計不大於85 wt%之量且至少1 wt%之量的磷光體微粒。應根據含有磷光體之矽氧烷層的厚度及所需發射光的顏色調整所使用之磷光體的量。
可光聚合組合物中可視情況包括增感劑以在給定引發輻射波長下增加硬化過程(或氫化矽烷化反應)之總速率與/或將引發輻射之最佳有效波長改變為較大值。可用之增感劑包括(例如)含有酮發色團之多環芳族化合物及芳族化合物(諸如揭示於美國專利第4,916,169號(Boardman等人)及美國專利第6,376,569號(Oxman等人)之增感劑)。可用之增感劑之實例包括(但不限於)2-氯噻噸酮(2-chlorothioxanthone)、9,10-二甲基蒽(9,10-dimethylanthracene)、9,10-二氯蒽(9,10-dichloroanthracene)及2-乙基-9,10-二甲基蒽(2-ethyl-9,10-dimethylanthracene)。若使用,則可光聚合組合物中較佳包括每一百萬份該組合物之不大於50,000重量份且更佳不大於5000重量份之量的該等增感劑。若使用,則可光聚合組合物中較佳包括每一百萬份該組合物之至少50重量份且更佳至少100重量份之量的該等增感劑。
可光聚合組合物中可視情況包括光引發劑以增加硬化過程(或氫化矽烷化反應)之總速率。可用之光引發劑包括(例如)α-二酮或α-酮醛及醇酮之單縮酮及其相應醚(諸如揭示於美國專利第6,376,569號(Oxman等人)之光引發劑)。若使用,則可光聚合組合物中較佳包括每一百萬份該組合物之不大於50,000重量份且更佳不大於5000重量份之量的該等光引發劑。若使用,則可光聚合組合物中較佳包括每一百萬份該組合物之至少50重量份且更佳至少100重量份之量的該等光引發劑。
可光聚合組合物可視情況包括催化劑抑制劑以進一步延長該組合物之可用存放期。催化劑抑制劑已為此項技術中所知,且包括諸如炔醇(例如,參看美國專利第3,989,666號(Niemi)及第3,445,420號(Kookootsedes等人))、不飽和羧酸酯(例如,參看美國專利第4,504,645號(Melancon)、第4,256,870號(Eckberg)、第4,347,346號(Eckberg)及第4,774,111號(Lo))及某些烯烴矽氧烷(例如,參看美國專利第3,933,880號(Bergstrom)、第3,989,666號(Niemi)及第3,989,667號(Lee等人))之物質。若使用,則可光聚合組合物中較佳包括以莫耳數計高達含金屬催化劑之約十倍量的此等催化劑抑制劑。
本文所述之方法包含提供LED。LED為發射可見光區、紫外區及/或紅外區之光線的二極體。LED可包含諸如單色LED之單一LED,或其可包含一個以上的LED。在某些情況下,例如當藉由活化LED自身來施加光化輻射時,可用LED發射350至500 nm之光線。LED包括以"LED"(無論為習知或超光(super-radiant)種類)銷售之固有包裝環氧樹脂之半導體裝置。垂直腔面發射雷射二極體為LED之另一種形式。"LED晶粒"係最基本形式(亦即由半導體晶圓加工製程所製得之個別組件或晶片形式)之LED。該組件或晶片之個別層及其他功能元件通常形成於晶圓範圍內,所得晶圓最終經切割成個別工件以得到多重LED晶粒。LED可包括適於施加電能以使裝置通電之電接觸件。
根據本文所述之方法可製得任何合適之發光裝置。在一實例中,發光裝置為具有不同顏色LED(例如,紅色、綠色及藍色;或藍色及黃色)之直接發光組態的白色光源。在另一實例中,發光裝置可包含單一LED及極為接近LED附著或嵌入之磷光體。LED在窄波長範圍內產生光線,從而使光線觸動並激發磷光體材料以產生可見光。磷光體材料可包含一種磷光體材料,或不同磷光體材料之混合物或組合,且由磷光體材料所發射之光線可包括複數條分佈於可見光波長範圍內的狹窄發射線,從而使所發射之光線人肉眼看來大體呈白色。可將磷光體材料作為可光聚合組合物之部分塗覆於LED上。或者,可以在單獨步驟中將磷光體材料塗覆於LED上,例如,可在使LED與可光聚合組合物接觸之前,將磷光體塗覆於LED上。磷光體-LED或PLED之實例為照明磷光體之藍光LED,其將藍光波長轉換為紅光與綠光波長。一部分藍色激發光並未由磷光體吸收,且剩餘藍色激發光與由磷光體所發射之紅光及綠光組合。
PLED之另一實例為照明磷光體之UV-LED,其吸收並將UV光轉換為紅光、綠光及藍光。較佳將R1
基團較小(如下文所述)且具有最小UV吸收(例如甲基)之有機聚矽氧烷用於UV-LED。熟習此項技術者應瞭解磷光體對光化輻射之競爭性吸收將減少光引發劑或含金屬之催化劑之吸收,減緩或甚至防止未小心建構系統時出現之硬化。
LED可以多種組態包裝。舉例而言,可將LED表面安裝或側面安裝於陶瓷或聚合物包裝中,其可或可不包括反射杯。亦可將LED安裝於電路板上或塑料電子基板上。
本文所揭示之方法亦利用藉由併入脂族不飽和基及與矽結合之氫中之基團之間的金屬催化氫化矽烷化反應而硬化的有機矽氧烷組合物,該等基團係結合於有機矽氧烷組份。第一與第二含金屬之催化劑的組合提供:(1)在不使LED、其所附著之基板或存在於包裝或系統中之任何其他材料經受光化輻射及/或高溫之潛在有害水平的情況下,硬化可光聚合組合物之能力;(2)調配顯示出長工作時間(亦已知為鍍液壽命(bath life)或存放期)之單成分(one-part)可光聚合組合物的能力;(3)應使用者判斷力之要求形成封裝物的能力。
如本文所揭示之方法所述,可對可光聚合組合物、部分聚合之組合物、第二經部分聚合之組合物、大體上聚合之組合物等中之任一者施加光化輻射。一般而言,使用光化輻射活化第一含金屬催化劑,從而引發含矽樹脂內之氫化矽烷化(或如下文所述進一步引發)。可施加光化輻射直至獲得所需特性。舉例而言,可施加光化輻射直至形成在品質上無黏性之彈性組合物,或直至形成在品質上呈黏性之凝膠。可需要後者以便控制可能存在之諸如微粒、磷光體之任何其他組份沉降。
光化輻射通常具有小於或等於700 nm(包括可見光及UV光)之波長,但其較佳為600 nm或更小,200至600 nm或250至500 nm。光化輻射較佳具有至少200 nm且更佳至少250 nm之波長。光化輻射光源之實例包括鹵鎢燈、氙弧燈、水銀弧光燈、白熾燈、殺菌燈及螢光燈。在某些實施例中,光化輻射光源為LED。
如本文所揭示之方法所述,可對可光聚合組合物、部分聚合之組合物、大體上聚合之組合物等中之任一者施加熱。例如,當需要加速光化矽烷化反應或減少使組合物曝露於光化輻射之時間量時,可於施加光化輻射之同時施加熱。如上文所述,可施加熱直至獲得所需特性,亦即,直至形成在品質上無黏性之彈性組合物,或直至形成在品質上呈黏性之凝膠。在施加光化輻射期間所施加的熱可低於120℃之溫度、更佳低於60℃之溫度且更佳為25℃或更低溫度。
可在應用塑模之前對指定組合物施加熱,以便降低組合物之黏度且促進組合物與塑模之間之接觸。如下文所述,通常亦可以一單獨步驟施加熱以活化第二含金屬催化劑。用於活化第二含金屬催化劑所施加之熱可低於150℃或更佳低於100℃且更佳低於60℃。可使用任何加熱方式,諸如紅外燈、強迫通風強制空氣烘箱(forced air oven)或加熱板。
出於製造含矽封裝物之目的,使用兩種不同催化劑之方法(一種經光化輻射活化而另一種經熱活化)描述於美國專利申請案第11/255711號及第11/255712號中。基本上,可在形成封裝物之步驟的給定次序中的任何時間處應用塑模,只要能夠模製組合物且組合物可充分接觸或潤濕塑模即可。
與塑模接觸之後,可對可光聚合組合物施加光化輻射以形成部分聚合之組合物或大體上聚合之組合物。隨後,可藉由對組合物施加熱以進一步引發氫化矽烷化,以便增加氫化矽烷化進行之程度。舉例而言,可施加光化輻射以形成部分聚合之組合物,且隨後,可施加熱以形成封裝物。另一選擇為在使可光聚合組合物與塑模接觸之後將其加熱,從而形成封裝物。在此情況下,第一含金屬催化劑應未經活化。
在使可光聚合組合物與塑模接觸之前,對可光聚合組合物施加光化輻射。此方法包含:提供發光二極體;使該發光二極體與可光聚合組合物接觸,該可光聚合組合物包含:包含與矽結合之氫及脂族不飽和基之含矽樹脂、可由光化輻射活化之第一含金屬催化劑及可由熱(而非光化輻射)活化之第二含金屬催化劑;及對該可光聚合組合物施加光化輻射,其中光化輻射為700 nm或更小之波長且引發含矽樹脂內之氫化矽烷化,藉此形成部分聚合之組合物,氫化矽烷化包含與矽結合之氫與脂族不飽和基之間的反應;及使部分聚合之組合物與塑模接觸。隨後,在使部分聚合之組合物與塑模接觸之後,可對該部分聚合之組合物施加光化輻射及/或熱以進一步引發含矽樹脂內之氫化矽烷化。
在使可光聚合組合物與塑模接觸之前,可對可光聚合組合物施加熱。此方法包含:提供發光二極體;使該發光二極體與可光聚合組合物接觸,該可光聚合組合物包含:包含與矽結合之氫及脂族不飽和基之含矽樹脂、可由光化輻射活化之第一含金屬催化劑及可由熱(而非光化輻射)活化之第二含金屬催化劑;及將該可光聚合組合物加熱至低於約150℃之溫度以引發含矽樹脂內之氫化矽烷化,藉此形成部分聚合之組合物,氫化矽烷化包含與矽結合之氫與脂族不飽和基之間的反應;及使部分聚合之組合物與塑模接觸。隨後,在使部分聚合之組合物與塑模接觸之後,可對部分聚合之組合物施加光化輻射及/或熱以進一步引發含矽樹脂內之氫化矽烷化。
使用以水為主之鹵化物流(Superior No.30,Superior Flux & Mfg.Co.)將Cree XB晶粒(Cree Inc.,Part No.C460XB290-0103-A)結合於Kyocera包裝中(Kyocera America,Inc.,Part No.KD-LA2707-A)。藉由使用1密耳(mil)金線線接(Kulicke and Soffa Industries,Inc.4524 Digital Series Manual Wire Bonder)Cree XB晶粒來完成LED裝置。LED之峰值發光波長為455-457 nm。
向10.00 g H2
C=CH-Si(CH3
)2
O-[Si(CH3
)2
O]8 0
-[Si(C6
H5
)2
O]2 6
-Si(CH3
)2
-CH=CH2
(以PDV-2331購自Gelest)中添加10 mg Pt{[H2
C=CH-Si(CH3
)2
]O}2
於10 mL庚烷中之溶液的25 μL等分試樣。向1.00 g此組合物中添加另外之1.50 g PDV-2331、0.26 g H(CH3
)2
SiO-[Si(CH3
)HO]1 5
-[Si(CH3
)(C6
H5
)O]1 5
-Si(CH3
)2
H(以HPM-502購自Gelest)及33 mg CH3
CpPt(CH3
)3
(購自Strem Chemicals)於1 mL甲苯中之溶液的25 μL等分試樣。真空下使混合物脫氣,並將最終組合物標記為封裝物A。
使用注射器針尖將一小滴封裝物A置放於上文所述之藍光LED裝置中,從而覆蓋LED及接線,並將裝置填充至反射杯頂部之水平。由距離經封裝之LED 20 mm之在裝備有兩個16吋Philips F15T8/BL 15 W燈泡之UVP Blak-Ray Lamp Model XX-15下照射矽氧烷封裝物1分鐘,該等兩個燈泡在365 nm下發光。將一片購自3M之增亮膜(BEF II)壓製於部分硬化之封裝物中。隨後,再照射經部分硬化之封裝物5分鐘。將BEF膜自封裝物剝離。使用顯微鏡檢驗發光裝置展示封裝物之表面上存在一系列稜鏡。
用實例1所述之封裝物A填充藍光LED裝置。如實例1所述照射矽氧烷封裝物1分鐘。將一片BEF膜壓製於部分硬化之封裝物中。隨後,將含有經照射封裝物之LED裝置置放於設定為100℃之熱板下30秒。將BEF膜自封裝物剝離。使用顯微鏡檢驗發光裝置展示封裝物之表面上存在一系列稜鏡。
熟習此項技術者應瞭解在不悖離本發明之範疇及精神之情況下之多種修改及變更。
2...LED
3a...經金屬處理之接觸件
3b...電接觸件
4...反射杯
5...接線
6...封裝物
7...基板
20...發光裝置
47...基板
圖1展示具有未經模製之封裝物之例示性發光裝置的示意性截面圖。
圖2-8圖示其中封裝物經模製之例示性發光裝置。
慮及下文之詳細描述聯繫上述圖式可更為完全地理解本發明。該等圖式僅為說明性實例。
6...封裝物
20...發光裝置
Claims (28)
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;及使該可光聚合組合物與一塑模接觸。
- 如請求項1之方法,其進一步包含:在該可光聚合組合物與該塑模接觸之後,對該可光聚合組合物施加光化輻射,其中該光化輻射為700 nm或更小之波長且引發該含矽樹脂內之氫化矽烷化,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應。
- 如請求項1之方法,其進一步包含:在使該可光聚合組合物與該塑模接觸之後,將該可光聚合組合物加熱至低於約150℃之溫度,其中加熱引發該含矽樹脂內之氫化矽烷化,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應。
- 如請求項1之方法,其進一步包含:在使該可光聚合組合物與該塑模接觸之後,對該可光聚合組合物施加光化輻射,其中該光化輻射為700 nm或更小之波長且引發該含矽樹脂內之氫化矽烷化,藉此形成一經部分聚合之組合物,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;及將該經部分聚合之組合物加熱至低於約150℃之溫度以進一步引發氫化矽烷化。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;及對該可光聚合組合物施加光化輻射,其中該光化輻射為700 nm或更小之波長且引發該含矽樹脂內之氫化矽烷化,藉此形成一經部分聚合之組合物,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;及使該經部分聚合之組合物與一塑模接觸。
- 如請求項5之方法,其進一步包含:在使該經部分聚合之組合物與該塑模接觸之後,對該經部分聚合之組合物施加光化輻射,其中該對該經部分聚合之組合物所施加之光化輻射為700 nm或更小之波長且進一步引發該含矽樹脂內之氫化矽烷化。
- 如請求項5之方法,其進一步包含:在使該經部分聚合之組合物與該塑模接觸之後,將該經部分聚合之組合物加熱至低於約150℃之溫度,其中加熱進一步引發該含矽樹脂內之氫化矽烷化。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;及將該可光聚合組合物加熱至低於約150℃之溫度以引發該含矽樹脂內之氫化矽烷化,藉此形成一經部分聚合之組合物,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;及使該經部分聚合之組合物與一塑模接觸。
- 如請求項8之方法,其進一步包含:對該經部分聚合之組合物施加光化輻射,其中該光化輻射為700 nm或更小之波長且進一步引發該含矽樹脂內之氫化矽烷化。
- 如請求項8之方法,其進一步包含:將該經部分聚合之組合物加熱至低於約150℃之溫度以進一步引發該含矽樹脂內之氫化矽烷化。
- 5及8中任一項之方法,其中該塑模對該光化輻射係透明的。
- 5、6及9中任一項之方法,其中施加光化輻射包含活化該發光二極體。
- 如請求項1之方法,該塑模包含一模製材料且經成形以對該可光聚合組合物之表面的實質部分賦予一正或負透鏡。
- 如請求項1之方法,該塑模包含一模製材料且經成形以賦予宏觀結構,每一宏觀結構均具有10 μm至1 mm之尺寸。
- 如請求項1之方法,該塑模包含一模製材料且經成形以賦予微觀結構,每一微觀結構均具有100 nm至小於10 μm之尺寸。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;藉由使該可光聚合組合物與一塑模接觸來使該可光聚合組合物之一表面成形;對該可光聚合組合物施加光化輻射以形成一至少經部分聚合之組合物,其中該光化輻射為700 nm或更小之波長且引發該含矽樹脂內之氫化矽烷化,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;自該至少經部分聚合之組合物分離該塑模。
- 一種如請求項16之方法製造的發光裝置。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;藉由使該可光聚合組合物與一塑模接觸來使該可光聚合組合物之一表面成形;將該可光聚合組合物加熱至低於約150℃之溫度以形成一至少經部分聚合之組合物,其中加熱引發該含矽樹脂內之氫化矽烷化,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;自該至少經部分聚合之組合物分離該塑模。
- 一種如請求項18之方法製造的發光裝置。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;對該可光聚合組合物施加光化輻射以形成一至少經部分聚合之組合物,其中該光化輻射為700 nm或更小之波長且引發該含矽樹脂內之氫化矽烷化,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;藉由使該至少經部分聚合之組合物與一塑模接觸來使該至少經部分聚合之組合物之一表面成形;藉由以下步驟進一步引發該經部分聚合之組合物之該含矽樹脂內的氫化矽烷化:施加為700 nm或更小波長之光化輻射,或加熱至低於約150℃之溫度;及自該經聚合之組合物分離該塑模。
- 一種如請求項20之方法製造的發光裝置。
- 一種製造一發光裝置之方法,該方法包含:提供一發光二極體;使該發光二極體與一可光聚合組合物接觸,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;將該可光聚合組合物加熱至低於約150℃之溫度以引發該含矽樹脂內之氫化矽烷化,藉此形成一經部分聚合之組合物,該氫化矽烷化包含該與矽結合之氫與該脂族不飽和基之間的反應;藉由使該至少經部分聚合之組合物與一塑模接觸來使該至少經部分聚合之組合物之一表面成形;藉由以下步驟進一步引發該經部分聚合之組合物之該含矽樹脂內的氫化矽烷化:施加為700 nm或更小波長之光化輻射,或加熱至低於約150℃之溫度;及自該經聚合之組合物分離該塑模。
- 一種如請求項22之方法製造的發光裝置。
- 一種發光裝置,其包含:一發光二極體;一可光聚合組合物,其包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,及第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;及一塑模。
- 如請求項24之發光裝置,其中該可光聚合組合物至少經部分聚合。
- 一種發光裝置,其包含:一發光二極體;一至少經部分聚合之組合物,其係與該發光二極體接觸且由一可光聚合組合物形成,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;且其中該至少經部分聚合之組合物之一表面的實質部分經成形為一正或負透鏡。
- 一種發光裝置,其包含:一發光二極體;一至少經部分聚合之組合物,其係與該發光二極體接觸且由一可光聚合組合物形成,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;且其中該至少經部分聚合之組合物之一表面經成形而具有宏觀結構,每一宏觀結構均具有10 μm至1 mm之尺寸。
- 一種發光裝置,其包含:一發光二極體;一至少經部分聚合之組合物,其係與該發光二極體接觸且由一可光聚合組合物形成,該可光聚合組合物包含:含矽樹脂,其包含與矽結合之氫及脂族不飽和基,第一含金屬之催化劑,其可藉由光化輻射活化,及第二含金屬之催化劑,其可藉由熱(而非光化輻射)活化;且其中該至少經部分聚合之組合物之一表面經成形而具有微觀結構,每一微觀結構均具有100 nm至小於10 μm之尺寸。
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- 2006-10-20 CN CN2006800398012A patent/CN101297411B/zh not_active Expired - Fee Related
- 2006-10-20 KR KR1020087009668A patent/KR101278415B1/ko not_active IP Right Cessation
- 2006-10-20 WO PCT/US2006/041213 patent/WO2007050484A1/en active Application Filing
- 2006-10-20 JP JP2008536856A patent/JP2009513021A/ja active Pending
- 2006-10-20 EP EP06817263.4A patent/EP1949459A4/en not_active Withdrawn
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- 2006-10-20 US US11/551,309 patent/US20070092636A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
CN101297411A (zh) | 2008-10-29 |
WO2007050484A8 (en) | 2007-10-11 |
TW200807750A (en) | 2008-02-01 |
US20070092636A1 (en) | 2007-04-26 |
EP1949459A1 (en) | 2008-07-30 |
CN101297411B (zh) | 2010-05-19 |
WO2007050483A3 (en) | 2007-06-14 |
EP1949459A4 (en) | 2014-04-30 |
JP2009513021A (ja) | 2009-03-26 |
WO2007050484A1 (en) | 2007-05-03 |
KR101278415B1 (ko) | 2013-06-24 |
KR20080059584A (ko) | 2008-06-30 |
TWI415289B (zh) | 2013-11-11 |
TW200731573A (en) | 2007-08-16 |
WO2007050483A2 (en) | 2007-05-03 |
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