TWI425695B - 高分子薄膜及其製造方法暨包含該高分子薄膜的光電元件及其製造方法 - Google Patents
高分子薄膜及其製造方法暨包含該高分子薄膜的光電元件及其製造方法 Download PDFInfo
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Description
本發明係關於一種高分子薄膜、光電元件以及製造該高分子薄膜與該光電元件之方法。
高分子係指由小分子重覆鍵結所構成的大分子,其常見的結構有線形(linear)、網狀(network)、分枝(branched)等形態。隨著對高分子特性的瞭解以及掌握,利用高分子材料所製成的各類用品已經大量充斥於現代人的生活中,例如:包裝食物的保鮮膜、紡織用的纖維、生醫領域中的人工關節等。
傳統的高分子材料大多為絕緣體,在過去的研究中,透過金屬粉末或其它導電材料的加入而使高分子材料具有導電性。近年來,研究人員發現了多種本身具有導電性值的共軛高分子,在經過如氧化還原或其它程序處理後,這些共軛高分子可達到如半導體,甚至是導體般的導電度。
此外,藉由功能性官能基的導入,也可改變這些共軛高分子的導電性、液晶性、光選擇性、光活性等性質,使其變為半導體高分子。由於共軛高分子所製成的光電元件具有成本低、製程簡單、可大面積製作以及具有可撓性(flexibility)等優點。該領域的研究者正積極研究這類共軛高分子材料於光電領域的應用。
舉例來說,高分子發光二極體(polymer light emitting
diode,PLED)便是共軛高分子目前被積極研究的應用。簡而言之,PLED係利用共軛高分子當發光材料,在正、負電極之間塗佈共軛高分子材料形成發光薄膜。當施予正向偏壓(forward bias)時,電洞(holes)由正極注入高分子薄膜內,進入價帶(valence band)形成正偏極子(polaron),而電子(electron)則由負極注入,進入傳導帶(conducting band)形成負偏極子,兩種偏極子在高分子共軛鍵上往相對方向移動,進而結合而放射出螢光(可見光)。
高分子發光二極體在適當的設計與製程下,可成為高分子半導體雷射,其工作原理大體與高分子發光二極體類似,但特別導入共振腔結構以及利用電子能階相反佔位(population inversion),使得光在半導體高分子層內傳遞時,誘發能隙波長光子,發出高強度的同相(coherent)發光源。
再舉例而言,類似前述架構的元件也可被應用來產生電能,例如,製成太陽能發電元件。其利用光子的能量使電子-電洞對分離,分離後的電洞彺陽極移動,電子則彺陰極移動,形成提供外部電路所需的電荷,因而將光能轉換成電能。
無論是前述的發光或發電元件,都需要更大的效率以增進其應用性。
因此,本發明之第一範疇在於提供一種高分子薄膜。特別地,該高分子薄膜具有較高的發光/發電效率,可被廣
泛應用於製成各種光電元件。
根據一具體實施例,該高分子薄膜係經由一變形製程形成於一基材上。特別地,該高分子薄膜包含複數個共軛高分子,其中至少一共軛高分子具有拉伸的分子結構。
本發明之第二範疇在於提供一種製造前述高分子薄膜的方法。
根據一具體實施例,該方法包含下列步驟:首先,於一基材上塗佈一共軛高分子材料以形成一高分子材料層;接著,使該高分子材料層處於不穩定狀態而形成該高分子薄膜;其中該高分子薄膜中的至少一共軛高分子具有拉伸的分子結構。
於一具體實施例中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:將該高分子材料層置於一溶劑的蒸氣中。
於另一具體實施例中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:加熱該高分子材料層至該共軛高分子材料之玻璃轉移溫度以上。
本發明之第三範疇在於提供一種光電元件,其包含如前述之高分子薄膜,因此具有較高的發光/發電效率。
根據一具體實施例,該光電元件包含一基材、該高分子薄膜以及一保護層。此基材與保護層可兼為電極或電子電洞之傳輸層。該高分子薄膜形成於該基材上,而該保護層則形成於該高分子薄膜上,以保護該高分子薄膜不被氧化或者磨損。
本發明之第四範疇在於提供製造前述光電元件的方法。
根據一具體實施例,該方法包含下列步驟:首先,製備一基材。隨後,於該基材上塗佈一共軛高分子材料以形成一高分子材料層。接著,使該高分子材料層處於不穩定狀態而形成該高分子薄膜;其中該高分子薄膜中的至少一共軛高分子具有拉伸的分子結構。
關於本發明之優點與精神可以藉由以下的發明詳述及所附圖式得到進一步的瞭解。
本發明提供一種高分子薄膜、光電元件以及製造該高分子薄膜與該光電元件之方法。以下將詳述本發明之具體實施例以及實際應用案例,藉以充分說明本發明之特徵、精神及優點。
請一併參見第1圖以及第2A圖至第2C圖,第1圖繪示根據本發明之一具體實施例的高分子薄膜製造方法流程圖;第2A圖繪示第1圖中之步驟S50所形成的基材10;第2B圖繪示第1圖中之步驟S52所形成的高分子材料層12;而第2C圖則繪示第1圖中之步驟S54所形成之高分子薄膜14。如圖所示,根據本具體實施例的製造方法包含下列步驟:
步驟S50,製備一基材10,例如,但不受限於,玻璃基材、氧化銦錫(Indium Tin Oxides,ITO)基材等等。
步驟S52,藉由塗佈共軛高分子材料,以形成一高分子
材料層12於該基材10上。於實際應用中,該共軛高分子材料係以旋塗(spin coating)或其它合適方式塗佈於該基材10上。於實際應用中,該高分子材料層12的厚度小於300nm,例如,200nm、50nm、50nm,並且較佳地小於30nm。於實務中,該共軛高分子材料可為單一種高分子,或者為數種高分子之混合或共聚物。共軛高分子包含,但不局限於,聚[1-甲氧基-4-(2’-乙基-己氧基)-2,5-苯乙烯](poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylene vinylene],MEH-PPV)、聚噻吩(polythiophene)或聚苯醚(polyphenylene)等。此外,於實務中,該共軛高分子材料還可摻混包含其它非共軛高分子材料,如聚苯乙烯(polystyrene)如聚苯乙烯(Polystyrene,PS),並可包含其它適當的添加物。
步驟S54,加熱該高分子材料層12至原高分子材料層之玻璃轉移溫度(Tg)以上,致使該高分子材料層12形變而形成該高分子薄膜14。
如第2C圖所示,該高分子薄膜14具有複數個凸起區域140以及可能為複數個連續性的複數個凹陷區域142。特別地,於該複數個凹陷區域142中的至少一共軛高分子具有單拉伸的分子結構。並且,於實際應用中,該凹陷區域142之表面1420與該基材10之表面102的距離小於100nm,例如,介於0.5nm至50nm之間,且較佳地小於20nm。在實際應用中,藉著基材表面之表面能處理,可控制此凹陷區域的厚度。
於實際應用中,步驟S54即是習知的除潤(Dewetting)步驟,該步驟可將共軛高分子在基材表面拖行,使共軛高分子在基材表面形成具有拉直的分子結構的薄膜,且使原本平整的高分子材料層分裂成液滴狀(droplet)的圖樣(如前述之凸起區域)。而由於共軛高分子被拉直,使共軛高分子較不易產生曲折,使得電荷(包含電子、電洞)可在高分子鏈上較自由地活動,而不會拘束固著在高分子鏈上,因此較容易發光/發電。經由初步實驗證實,除潤後的高分子薄膜之發光效率較未除潤前的發光效率更增加二個數量級以上。
請參見第3圖,第3圖繪示根據本發明之另一具體實施例的高分子薄膜製造方法流程圖。如第3圖所示,第1圖中之步驟S54可由步驟S56取代:於室溫下,將高分子材料層置於某溶劑(例如,甲苯、對甲苯、四氫呋喃(THF)、甲醇或其它適當的溶劑)的蒸氣中,使該高分子材料層12處於不穩定狀態,並形變而形成該高分子薄膜14。
此外,於實務中,前述步驟S52以及S54/S56可被重複進行,以形成多層高分子薄膜,以提升發光/發電效率。此外,於實際應用中,本發明之方法還可包含下列步驟:視需求移除該凸起區域高於該凹陷區域之部分,致使該高分子薄膜具有大體上呈平坦之表面。藉此,可避免凹陷區域所發出的光線受到凸起區域的影響。反之,當步驟S52以及S54被重複進行而形成多層高分子薄膜時,可不移除該凸起區域,以藉由該凸起區域協助各層薄膜之間的固定。
請參見第4圖,第4圖繪示根據本發明之一具體實施例的高分子薄膜於除潤過程中,對應不同除潤時間的發光效率曲線圖。於本具體實施例中,發光高分子材料MEH-PPV被以旋塗法製成約20nm厚的薄膜於氧化矽上,並且在100℃下放置不同的時間進行除潤。此外,第4圖係以螢光光譜儀測量所得之結果。如圖所示,當除潤時間為300分鐘時,薄膜已除潤完成,且其發光效率較未除潤時增加約150倍。
本發明還提供了包含前述高分子薄膜的光電元件及其製造方法。該光電元件可應用於多種不同的領域中,例如,作為高分子發光二極體、高分子半導體雷射、太陽能電池元件等,但不以此為限。
請參見第5圖,第5圖係繪示根據本發明之一具體實施例的發光元件剖面示意圖。如圖所示,根據本發明之發光元件2包含基材20、陽極22、電洞傳輸層24、發光層26以及陰極28。
於實際應用中,基材20可由透明玻璃或其他適當的材料製成。陽極22可由導電材料,如氧化銦錫(Indium oxide,ITO)所製成。電洞傳輸層24可以導電性高分子材料(3,4-polyethylenedioxythiophene/polystyrenesulfonate blend,PEDOT/PSS)製成。發光層26則係以本發明之高分子薄膜所製成。此外,陰極28可由鋁或其他金屬所製成。
於實際應用中,根據本發明之光電元件除了包含前述
之基材以及高分子薄膜外,還可包含形成於該高分子薄膜上之保護層,以保護該高分子薄膜不被氧化或受到磨損。
此外,根據本發明之光電元件可包含正負電極,分別設置於基材以及保護層上。當然,於實務中,本發明之光電元件還可視情況包含其它功能層,並且各功能層以及電極之位置可視情況進行調整,並不受限於任何特定的形式。
綜上所述,本發明之高分子薄膜以及光電元件藉由拉直共軛高分子所形成的凹陷區域來增加發光/發電的效率。並且,這個過程並不需要增加太多的時間以及費用便可達成,具有很高的產業利用價值。
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明之範圍,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
10‧‧‧基材
102‧‧‧基材表面
12‧‧‧高分子材料層
14‧‧‧高分子薄膜
140‧‧‧凸起區域
142‧‧‧凹陷區域
1420‧‧‧凹陷區域表面
2‧‧‧發光元件
20‧‧‧基材
22‧‧‧陽極
24‧‧‧電洞傳輸層
26‧‧‧發光層
28‧‧‧陰極
S50~S56‧‧‧流程步驟
第1圖繪示根據本發明之一具體實施例的高分子薄膜製造方法流程圖。
第2A圖繪示本發明之一具體實施例的基材。
第2B圖繪示本發明之一具體實施例的高分子材料層。
第2C圖繪示本發明之一具體實施例的高分子薄膜。
第3圖繪示根據本發明之一具體實施例的高分子薄膜製造方法流程圖。
第4圖繪示根據本發明之一具體實施例的高分子薄膜於除潤過程中,對應不同除潤時間的發光效率曲線圖。
第5圖係繪示根據本發明之一具體實施例的發光元件剖面示意圖
S50~S54‧‧‧流程步驟
Claims (31)
- 一種具有發光及發電效率的高分子薄膜,經由包含一除潤步驟的一變形製程直接形成於一基材上,並且該高分子薄膜包含一共軛高分子,其中該共軛高分子具有被拉伸的分子結構。
- 如申請專利範圍第1項所述之高分子薄膜,進一步包含複數個凸起區域以及至少一凹陷區域,並且具有被拉伸的分子結構之該至少一共軛高分子位於該凹陷區域。
- 如申請專利範圍第2項所述之高分子薄膜,其中該凹陷區域之表面與該基材之表面的距離小於100nm。
- 如申請專利範圍第3項所述之高分子薄膜,其中該凹陷區域之表面與該基材之表面的最佳距離約介於0.5nm至50nm之間。
- 如申請專利範圍第1項所述之高分子薄膜,其中該共軛高分子係聚[1-甲氧基-4-(2’-乙基-己氧基)-2,5-苯乙烯](poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylene vinylene],MEH-PPV)、聚噻吩(polythiophene)或聚苯醚(polyphenylene)。
- 如申請專利範圍第1項所述之高分子薄膜,其中該變形製程係將該等共軛高分子置於一溶劑中,致使該等共軛高分子處於不穩定狀態。
- 如申請專利範圍第6項所述之高分子薄膜,其中該變形製程係將該等共軛高分子置於該溶劑的蒸氣中。
- 如申請專利範圍第1項所述之高分子薄膜,其中該變形製程係將該等共軛高分子置於其玻璃轉移溫度以上,致使該等共軛高分子處於不穩定狀態。
- 一種製造如申請專利範圍第1項所述之具有發光及發電效率的高分子薄膜之方法,包含下列步驟:直接於一基材上塗佈一共軛高分子材料以形成一高分子材料層,該高分子材料層厚度小於300nm;以及使該高分子材料層處於不穩定狀態而形成該高分子薄膜;其中該高分子薄膜中的至少一共軛高分子具有被拉伸的分子結構。
- 如申請專利範圍第9項所述之方法,其中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:將該高分子材料層置於一溶劑中。
- 如申請專利範圍第10項所述之方法,其中該高分子材料層係置於該溶劑的蒸氣中。
- 如申請專利範圍第11項所述之方法,其中,將該高分子材料層置於該溶劑的蒸氣中之步驟係於室溫下進行。
- 如申請專利範圍第9項所述之方法,其中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:加熱該高分子材料層至其玻璃轉移溫度以上。
- 如申請專利範圍第9項所述之方法,其中該高分子薄膜進一步包含複數個凸起區域以及至少一凹陷區域,並且具有被拉伸之分子結構之該至少一共軛高分子位於該凹陷區域。
- 如申請專利範圍第14項所述之方法,進一步包含下列步驟:移除該凸起區域高於該凹陷區域之部分,致使該高 分子薄膜具有大體上呈平坦之表面。
- 如申請專利範圍第9項所述之方法,其中該共軛高分子係聚[1-甲氧基-4-(2’-乙基-己氧基)-2,5-苯乙烯](poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylene vinylene],MEH-PPV)、聚噻吩(polythiophene)或聚苯醚(polyphenylene)。
- 一種光電元件,包含如申請專利範圍第1項所述之具有發光及發電效率的高分子薄膜。
- 如申請專利範圍第17項所述之光電元件,進一步包含:一保護層,形成於該高分子薄膜上,以保護該高分子薄膜。
- 如申請專利範圍第17項所述之光電元件,進一步包含複數個凸起區域以及至少一凹陷區域,並且具有被拉伸之分子結構之該至少一共軛高分子位於該凹陷區域。
- 如申請專利範圍第19項所述之光電元件,其中該凹陷區域之表面與該基材之表面的距離小於100nm。
- 如申請專利範圍第20項所述之光電元件,其中該凹陷區域之表面與該基材之表面的最佳距離約介於0.5nm至50nm之間。
- 如申請專利範圍第17項所述之光電元件,其中該共軛高分子係聚[1-甲氧基-4-(2’-乙基-己氧基)-2,5-苯乙烯](poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylene vinylene],MEH-PPV)、聚噻吩(polythiophene)或聚苯醚(polyphenylene)。
- 一種製造如申請專利範圍第17項所述之光電元件之具有發光及發電效率的方法,包含下列步驟: 製備一基材;直接於該基材上塗佈一共軛高分子材料以形成一高分子材料層,該高分子材料層厚度小於300nm;以及使該高分子材料層處於不穩定狀態而形成該高分子薄膜;其中該高分子薄膜中的至少一共軛高分子具有被拉伸的分子結構。
- 如申請專利範圍第23項所述之方法,其中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:將該高分子材料層置於一溶劑中。
- 如申請專利範圍第24項所述之方法,其中該高分子材料層係置於該溶劑之蒸氣中。
- 如申請專利範圍第25項所述之方法,其中,將該高分子材料層置於該溶劑的蒸氣中之步驟係於室溫下進行。
- 如申請專利範圍第23項所述之方法,其中,使該高分子材料層處於不穩定狀態而形成該高分子薄膜之步驟進一步包含:加熱該高分子材料層至其玻璃轉移溫度以上。
- 如申請專利範圍第23項所述之方法,其中該高分子薄膜進一步包含複數個凸起區域以及至少一凹陷區域,並且具有被拉伸的分子結構之該至少一共軛高分子位於該凹陷區域。
- 如申請專利範圍第28項所述之方法,進一步包含下列步驟:移除該凸起區域高於該凹陷區域之部分,致使該高 分子薄膜具有大體上呈平坦之表面。
- 如申請專利範圍第23項所述之方法,進一步包含下列步驟:形成一保護層於該高分子薄膜上,以保護該高分子薄膜。
- 如申請專利範圍第23項所述之方法,其中該共軛高分子係聚[1-甲氧基-4-(2’-乙基-己氧基)-2,5-苯乙烯](poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylene vinylene],MEH-PPV)、聚吩(polythiophene)或聚苯醚(polyphenylene)。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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TW97150547A TWI425695B (zh) | 2008-12-24 | 2008-12-24 | 高分子薄膜及其製造方法暨包含該高分子薄膜的光電元件及其製造方法 |
US12/571,110 US8790746B2 (en) | 2008-12-24 | 2009-09-30 | Method for manufacturing a polymer molecular film for photo-electronic device |
US14/303,404 US9349959B2 (en) | 2008-12-24 | 2014-06-12 | Method of manufacturing a polymer molecular film |
US15/136,547 US20160240787A1 (en) | 2008-12-24 | 2016-04-22 | Photoelectronic element |
US15/136,578 US20160240788A1 (en) | 2008-12-24 | 2016-04-22 | Polymer molecular film |
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TWI560919B (en) * | 2011-08-25 | 2016-12-01 | Univ Nat Tsing Hua | Method for enhancing optoelectronic properties of conjugated polymers |
JP6164810B2 (ja) * | 2012-09-03 | 2017-07-19 | 日東電工株式会社 | 樹脂フィルム |
TWI567487B (zh) | 2015-04-15 | 2017-01-21 | 國立清華大學 | 薄膜圖案形成方法 |
US10615345B2 (en) * | 2016-06-03 | 2020-04-07 | The Trustees Of Princeton University | Method and device for using an organic underlayer to enable crystallization of disordered organic thin films |
CN108258057A (zh) * | 2018-01-19 | 2018-07-06 | 云谷(固安)科技有限公司 | 柔性基底结构及其制备方法与柔性器件 |
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JPH02298552A (ja) * | 1989-03-02 | 1990-12-10 | Katsumi Yoshino | 共役系重合体機能ゲル及びその変形方法 |
US5204038A (en) * | 1990-12-27 | 1993-04-20 | The Regents Of The University Of California | Process for forming polymers |
TW592743B (en) * | 2002-12-30 | 2004-06-21 | Ind Tech Res Inst | A process for manufacturing an implanting cuff electrode |
WO2008084350A2 (en) * | 2007-01-08 | 2008-07-17 | Consejo Nacional De Investigaciones Científicas Y Técnicas (Conicet) | Implantable ocular microapparatus to ameliorate glaucoma or an ocular overpressure causing disease |
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JPH02103123A (ja) * | 1988-10-12 | 1990-04-16 | Kao Corp | 高強度全共役系ポリマーフィルムの製造方法 |
US5217650A (en) * | 1989-02-03 | 1993-06-08 | Trustees Of The University Of Pennsylvania | Oriented films of conductive polymers |
SE503039C2 (sv) * | 1994-07-19 | 1996-03-11 | Forskarpatent I Linkoeping Ab | Elektroluminescerande anordning samt sätt att framställa denna |
EP0996176B8 (en) * | 1998-10-13 | 2005-10-19 | Sony Deutschland GmbH | Method of fabricating an active matrix light-emitting display device |
US6339012B1 (en) * | 1999-11-29 | 2002-01-15 | Thomas Jackson | Method of fabricating a semiconducting thin film of polymer with improved chain ordering by drying in solvent rich atmosphere |
US7829143B1 (en) * | 2003-11-21 | 2010-11-09 | Nanosolar, Inc. | Solvent vapor annealing of organic films |
JP4225510B2 (ja) * | 2005-07-06 | 2009-02-18 | 昭和電工株式会社 | 化合物半導体発光ダイオードおよびその製造方法 |
WO2007114179A1 (ja) * | 2006-03-28 | 2007-10-11 | Dai Nippon Printing Co., Ltd. | 光学積層体 |
US8350995B2 (en) * | 2006-06-19 | 2013-01-08 | Fujifilm Corporation | Optical film, production method of optical film, optically-compensatory film, polarizing plate and liquid crystal display device |
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2008
- 2008-12-24 TW TW97150547A patent/TWI425695B/zh not_active IP Right Cessation
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2009
- 2009-09-30 US US12/571,110 patent/US8790746B2/en not_active Expired - Fee Related
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2014
- 2014-06-12 US US14/303,404 patent/US9349959B2/en active Active
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2016
- 2016-04-22 US US15/136,547 patent/US20160240787A1/en not_active Abandoned
- 2016-04-22 US US15/136,578 patent/US20160240788A1/en not_active Abandoned
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JPH02298552A (ja) * | 1989-03-02 | 1990-12-10 | Katsumi Yoshino | 共役系重合体機能ゲル及びその変形方法 |
US5204038A (en) * | 1990-12-27 | 1993-04-20 | The Regents Of The University Of California | Process for forming polymers |
TW592743B (en) * | 2002-12-30 | 2004-06-21 | Ind Tech Res Inst | A process for manufacturing an implanting cuff electrode |
WO2008084350A2 (en) * | 2007-01-08 | 2008-07-17 | Consejo Nacional De Investigaciones Científicas Y Técnicas (Conicet) | Implantable ocular microapparatus to ameliorate glaucoma or an ocular overpressure causing disease |
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Efficient Luminescence Polarization of Conjugated Polymer films under low stretching level using transparent and flexible plastic substrate. * |
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US20100159205A1 (en) | 2010-06-24 |
US20140295137A1 (en) | 2014-10-02 |
US9349959B2 (en) | 2016-05-24 |
US20160240788A1 (en) | 2016-08-18 |
TW201025696A (en) | 2010-07-01 |
US8790746B2 (en) | 2014-07-29 |
US20160240787A1 (en) | 2016-08-18 |
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