TWI774664B - 用於製造經囊封量子點之方法 - Google Patents
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Abstract
一種用於囊封量子點之方法。所述方法包括以下步驟：(a)使量子點與分子量為1,000至200,000且溶解度參數為14至18.75(J/cm3)1/2之聚合物及溶劑混合，以形成混合物；及(b)噴霧乾燥所述混合物以製造經囊封量子點粉末。
Description
本發明係關於一種用於製造經囊封量子點之方法。
半導體量子點(QD)提供與塊體材料之光學吸收及發射(光致發光PL或電致發光EL)特性顯著不同之彼等特性。隨著粒度減小，有效能帶隙(Eg)或可利用之能階會有所增加且產生藍移PL光譜。由相同材料內粒度依賴性量子限制作用所導致之此光譜可調諧性為優於習知塊體半導體之關鍵優點。由於QD之獨特光學特性，其在諸多顯示器及照明應用中已受到極大關注。大多數QD具有無機殼體，其具有較大帶隙材料以將電子與空穴對限制於核心區內且防止任何表面電荷狀態。外部殼體隨後經有機配位體封蓋以減少可導致量子產率(QY)降低的殼體之捕獲狀態。有機配位體有助於QD分散於有機溶劑/水性溶劑中。包圍QD之典型有機配位體具有相對長的烷基鏈，其提供在非極性溶劑或單體中之高溶解度。令人遺憾的是，QD在光吸收/轉化過程中極易受光氧化影響。此外，當配位體不與溶劑或單體相容時，水分可具有類似影響。QD通常囊封於聚合物基質中以保護QD不受水及氧氣
之不利影響。舉例而言，US8859442揭示聚合物基質中之經囊封量子點。然而，此參考文獻並未揭示本文中所描述之方法。
本發明提供一種用於囊封量子點之方法。所述方法包括以下步驟：(a)使量子點與分子量為1,000至200,000且溶解度參數為14至18.75(J/cm3)1/2之聚合物及溶劑混合，以形成混合物；(b)噴霧乾燥所述混合物以製造粒度為1-10微米之經囊封量子點粉末。
除非另外規定，否則百分比為重量百分比(wt%)且溫度以℃為單位。除非另外規定，否則操作在室溫(20-25℃)下進行。在大氣壓(大約101kPa)下量測沸點。術語「(甲基)丙烯酸酯」意謂丙烯酸酯或甲基丙烯酸酯。量子點在此項技術中已熟知，參見例如US2012/0113672。分子量以道爾頓為單位進行量測且為單體化合物之原子量與混合物例如寡聚或聚合化合物之重量平均分子量(Mw)的總和。
較佳地，聚合物之酸值為0至500mg KOH/g；較佳不大於350，較佳不大於200。較佳地，聚合物之分子量為至少2,000，較佳為至少3,000；較佳不大於200,000，較佳不大於175,000，較佳不大於150,000。較佳地，聚合物之溶解度參數為至少15(J/cm3)1/2；較佳為至少15.5；較佳不大於18.5，較佳不大於18.25。聚合物之玻璃轉移溫度(Tg)或熔融溫度
較佳為至少50℃，較佳為至少60℃；較佳不大於200℃，較佳不大於150℃。
較佳地，聚合物包含包括至少一個可易於聚合之乙烯基之化合物；化合物之分子量較佳為至少28，較佳為至少72，較佳為至少86；較佳不大於500，較佳不大於400。較佳地，包括至少一個可易於聚合之乙烯基之化合物具有一個或兩個可易於聚合之乙烯基，較佳一個；即使當此化合物僅含有一個可易於聚合之乙烯基時，可能存在具有更高官能性之額外單體。當包括至少一個可易於聚合之乙烯基之化合物為寡聚物時，乙烯基之數目為分佈之平均數目。較佳地，可易於聚合之乙烯基為(甲基)丙烯酸酯基(CH2=C(R)C(O)O-，其中R為H或CH3；亦稱為(甲基)丙烯醯氧基)。較佳地，包括至少一個可易於聚合之乙烯基之化合物不具有除碳、氫、氧及氮原子、較佳碳、氫及氧以外的原子(此不把痕量級排除在雜質之外)。
較佳地，溶劑之溶解度參數為14.5至18.5(J/cm3)1/2；較佳為至少14.75，較佳為至少15.0；較佳不大於18.25，較佳不大於18.0。較佳地，溶劑為C6-C12烴或乙醚溶劑，較佳為C6-C10烴或乙醚溶劑，較佳為C6-C10烴溶劑。較佳地，溶劑為芳族的，亦即其含有至少一個芳環。若使用多於一種溶劑，則溶劑混合物之溶解度參數為個別溶劑之溶解度參數的加權平均值。
較佳之聚合物為不含有任何酸官能性之高Tg非晶形聚合物。尤其較佳之聚合物包含烯烴類(共)聚合物、烷基苯乙烯類(共)聚合物及(甲基)丙烯酸酯類(共)聚合物。尤其較
佳的包括至少一個可易於聚合之乙烯基之化合物包含(甲基)丙烯酸異冰片酯、(甲基)丙烯酸C2-C18烷基酯(例如(甲基)丙烯酸異丁酯、丙烯酸3,5,5-三甲基己酯、丙烯酸十二烷基酯、丙烯酸癸酯、丙烯酸十三烷基酯及丙烯酸異癸酯)、丙烯酸L-薄荷酯、丙烯酸三環[5.2.1.02,6]癸基甲酯、C1-C6烷基苯乙烯、甲基丙烯酸3,3,5-三甲基環己酯。
較佳地，經噴霧乾燥之物質，亦即量子點與溶劑及聚合物之混合物，包括0.001至2.4wt%量子點；較佳為至少0.0025wt%，較佳為至少0.005wt%；較佳不大於1.6wt%，較佳不大於0.8wt%。較佳地，經噴霧乾燥之物質包括1至30wt%第一聚合物；較佳為至少3wt%，較佳為至少5wt%；較佳不大於25wt%、較佳不大於20wt%。較佳地，經噴霧乾燥之物質包括50至99wt%溶劑；較佳為至少60wt%，較佳為至少70wt%；較佳不大於97wt%，較佳不大於95wt%。
較佳地，噴霧乾燥在惰性氛圍下在<100℃、較佳<80℃、較佳<60℃之出口溫度下進行。較佳地，噴霧乾燥器配備有兩個流體霧化器。較佳地，乾粉之平均粒度為0.1-10微米，較佳為至少0.5微米，較佳為至少1微米；較佳不大於8微米，較佳不大於6微米。
經囊封QD之噴霧乾燥粉末分散於具有散射劑及光引發劑之液體單體中且固化於固體膜中。樹脂在物理性質上穩定且可更容易地測試。
實例
用於實例之縮寫：PiBOMA為來自Scientific Polymer Products之甲基丙烯
聚異冰片酯(Mw=100kg/mol，Tg=110℃)
PTBS：來自Scientific Polymer Products之聚(對第三丁基苯乙烯)(Tg=132℃)
COC 5013為來自TOPAS之乙烯-降冰片烯共聚物(Mw=80.5kg/mol，Tg=140℃)
SMA EF-60為來自Cray Valley之苯乙烯-順丁烯二酸酐共聚物(Mw=11.5kg/mol，酸值=156KOH/g)
HEA為來自西格瑪奧德里奇公司(Sigma-Aldrich,Inc.)之丙烯酸2-羥基乙酯
SR494為來自沙多瑪公司(Sartomer,Inc.)之C{CH2OCH2CH2OC(O)CH=CH2}4
I-819為來自汽巴-嘉基公司(Ciba-Geigy Corp.)之IRGACURE光敏性聚合引發劑
FINEX 30S LP2為來自堺化學工業公司(Sakai Chemical Industry Co.)之超細氧化鋅。
除非指定，否則下文描述典型之噴霧乾燥條件。將噴水雙流體噴嘴霧化器配備在MOBILE MINOR噴霧乾燥器(基伊埃工程技術有限公司(GEA Process Engineering Inc.))上。使用蠕動泵(MASTERFLEX L/S)將聚合物/QD溶液饋入噴霧乾燥器中。入口溫度為80℃且出口溫度為55℃。液體饋料速率=10mL/min(設定)且噴嘴霧化器之N2流動速率=1巴60%流量。噴霧乾燥製程製造經良好控制之粒度為~5微米之自由流動的QD聚合物粉末，其中QD均一地分散於聚合物基質中而不聚集。
PLQY量測
使用絕對PL量子產率光譜儀(日本濱松(Hamamatsu,Japan)的QUANTAURUS(C11347-01))量測PLQY。積分球允許350nm~1600nm的~99%反射。入射光子及發射光子必須經歷多次反射以便達至偵測器(此有助於消除量子產率量測中之光學各向異性)。激發波長設定在450nm下且PL之波長在460nm與950nm之間。將溶液樣品置放於積分球之中央(透射)；將膜樣品置放於底部。絕對PLQY之直接量測為所發射光子號與所吸收光子號之比。
製備QD樹脂膜
在無氧環境中(例如在手套工作箱中)製備膜調配物
1.在真空下使單體脫氣1小時
2.藉由使用速度混合器(FlackTek Inc，南卡羅來納州蘭德拉姆市(Landrum,SC))製備50wt% FINEX 30S LP2於上文單體中之溶液。
3.藉由在室溫下攪拌混合物來製備1.75wt% I-819於上文單體中之溶液
4.將I-819/單體引入QD樣品中
6.藉由使用速度混合器將FINEX 30S LP2/單體溶液混合於上文溶液中
7.藉由在由兩種異組分阻擋膜包夾的UV(UVA，~400mJ/cm2)下固化單體來製備~100um之QD膜，以用於QY測試
實例1：
聚合物與綠色QD於甲苯中之溶液PLQY
實例2：HEA/CN104單體中之CF-QD®
甲苯中之紅色QD：Manc11_ZA1(151.2 OD/mL(450nm激發))
PTBS：Mw=50-100kg/mol，Tg=144℃
QD粉末規格
PTBS粉末1：0.5wt%紅色QD(8.75 OD/g)
PtBSt粉末2：2.5wt%紅色QD(43.75 OD/g)
IBOA中之對照樣品QD
2.098g IBOA+0.5mL甲苯中之QD(0.5×151.2/2.098=35 OD/g)
實例3-HEA/SR-494單體中PIBOMA中之CF-QD®
PiBOMA/QD經囊封粉末：2wt%綠色QD
囊封QD樹脂膜：
SR494之結構
囊封QD展示極性基質中更好的QY保持力及更低的發射峰紅移
60℃/95% RH下老化QD樹脂膜
含由經囊封QD之膜在老化條件下展示更好的QY保持力。
Claims (3)
- 一種用於囊封量子點之方法；所述方法包括以下步驟：(a)使量子點與分子量為1,000至200,000且溶解度參數為14至18.75(J/cm3)1/2之聚合物及溶劑混合，以形成混合物，其中，所述聚合物包括選自(甲基)丙烯酸異冰片酯、丙烯酸L-薄荷酯、丙烯酸三環[5.2.1.02,6]癸基甲酯、C1-C6烷基苯乙烯、甲基丙烯酸3,3,5-三甲基環己酯之至少一聚合單元，其中，所述量子點、所述溶劑及所述聚合物之所述混合物包括0.001至0.8wt%量子點及5至30wt%聚合物；及(b)噴霧乾燥所述混合物以製造經囊封量子點粉末。
- 一種用於囊封量子點之方法，所述方法包括以下步驟：(a)使量子點與分子量為1,000至200,000且溶解度參數為14至18.75(J/cm3)1/2之聚合物及溶劑混合，以形成混合物，其中，所述聚合物係選自聚甲基丙烯酸異冰片酯、聚(對第三丁基苯乙烯)、乙烯-降冰片烯共聚物及苯乙烯-順丁烯二酸酐共聚物，其中，所述量子點、所述溶劑及所述聚合物之所述混合物包括0.001至0.8wt%量子點及5至30wt%聚合物；及(b)噴霧乾燥所述混合物以製造經囊封量子點粉末。
- 如申請專利範圍第1或2項所述的方法，其中所述噴霧乾 燥在配備有兩個流體噴嘴霧化器之噴霧乾燥器中進行。
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