TWI703084B - 無鎘量子點之奈米粒子 - Google Patents

無鎘量子點之奈米粒子 Download PDF

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TWI703084B
TWI703084B TW106108164A TW106108164A TWI703084B TW I703084 B TWI703084 B TW I703084B TW 106108164 A TW106108164 A TW 106108164A TW 106108164 A TW106108164 A TW 106108164A TW I703084 B TWI703084 B TW I703084B
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core
quantum dot
magnesium
semiconductor material
zinc
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安東尼 葛拉維保羅
哈利斯詹姆斯
丹尼爾斯史蒂芬
皮凱特耐吉
娜拉雅那斯娃咪亞瑞
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納諾柯技術有限公司
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Abstract

已發現向量子點核心中納入諸如鋅、鋁、鈣或鎂等離子之量子點半導體奈米粒子組合物對奧斯瓦爾德熟化(Ostwald ripening)更穩定。核心-殼量子點可具有包括銦、鎂及磷離子之半導體材料之核心。可除鎂外包括諸如鋅、鈣及/或鋁等離子，或包括該等離子代替鎂。該核心可進一步包括諸如硒及/或硫等其他離子。該核心可經一個(或多個)半導體材料殼包覆。實例性殼半導體材料包括含有鋅、硫、硒、鐵及/或氧離子之半導體。

Description

無鎘量子點之奈米粒子
本發明概言之係關於量子點奈米粒子。更特定而言，其係關於不含鎘或其他重金屬之量子點奈米粒子的合成。
包括在37 CFR 1.97及1.98下揭示之資訊之相關技術之說明
對尺寸為約2nm至100nm之化合物半導體粒子(常稱為量子點(QD)或奈米晶體)之製備及表徵存在極大興趣。此興趣主要係由於其大小可調諧之電子、光學及化學性質。舉例而言，許多QD顯示器在電磁光譜之可見區中相對強烈發射。此外，吸收及發射之光之波長隨QD之大小變化。由於QD之獨特光學性質，QD係生物標記、太陽能電池、催化、生物成像及光發射二極體(僅舉幾個例子)等多種多樣商業應用之有前景之材料。
迄今為止，研究且製備最多之半導體材料為II-VI族材料，即，ZnS、ZnSe、CdS、CdSe、CdTe；最引人注目的是CdSe，此乃因其在光譜之可見區內之可調諧度。半導體奈米粒子由於其不同於相同半導體材料之相應結晶體形式之性質之性質而具有學術及商業興趣。與個別奈米粒子之大小有關之兩個基本因素導致其具有獨特性質。第一因素係大的表面對體積比。隨著粒子變得較小，表面原子數對內部之彼等之比增加。此導致 表面性質在小粒子之整體性質中起重要作用。第二因素係對於半導體奈米粒子，材料之電子性質隨粒子之大小存在變化。具體而言，隨著粒子之大小減小，帶隙逐漸變寬。帶隙之此變化係由於量子侷限效應。此效應係由於「盒中之電子」之侷限，從而產生類似於原子及電子中觀察到之離散能級之彼等，而非如相應體半導體材料中之連續帶。因此，對於半導體奈米粒子，由光子之吸收產生之「電子及電洞」較在相應粗粒結晶材料中更緊密靠在一起，從而在電子與電洞之間產生不可忽略之庫倫(Coulombic)相互作用。此導致窄帶寬發射，其取決於粒徑及組成。因此，量子點較相應粗粒結晶材料具有更高動能且隨著粒子直徑減小，第一激子躍遷(帶隙)之能量增加。因此，具有較小直徑之量子點較具有較大直徑之量子點吸收並發射高能量之光。換言之，吸收並發射之光之顏色可隨粒子直徑變化「經調諧」。
由單一半導體材料(通常以及外部有機鈍化層)組成之單一核心奈米粒子往往因位於奈米粒子表面上之缺陷及懸鍵處發生之電子-電洞複合而具有相對較低量子效率，此導致非輻射電子-電洞複合。一種消除缺陷及懸鍵之方法係在核心粒子表面上生長包括具有較寬帶隙之第二半導體材料之殼以產生「核心-殼粒子」。殼半導體材料較佳與核心材料具有小的晶格失配，以使兩種材料之間之界面最小化。核心-殼粒子使侷限於核心中之電荷載流子與原本將用作非輻射複合中心之表面狀態分開。常見實例係在CdSe核心表面上生長之ZnS。過量應變可進一步產生缺陷及非輻射電子-電洞複合，從而產生低量子效率。
外部無機表面原子周圍之配位不完全，在表面上具有高度反應性「懸鍵」，此可導致粒子凝聚。此問題可藉由用保護性有機基團鈍化(封 端)「裸」表面原子部分克服。粒子之封端或鈍化不僅防止發生粒子凝聚，其亦保護粒子免受其周圍化學環境影響且為粒子提供電子穩定(鈍化)。封端劑通常採用共價鍵結至粒子之最外無機層之表面金屬原子的路易士鹼(Lewis base)化合物形式。
已報導製備半導體奈米粒子之若干合成方法。早期途徑應用習用膠態水性化學，而最近方法涉及使用有機金屬化合物使奈米微晶動力學受控沈澱。
由於QD之光學性質具有大小依賴性，故經常期望產生具有高單分散度之QD之群體，即群體中QD之大小具有高均勻度。同樣，具有高量子產率(QY，所發射光子對所吸收光子之比率)之QD之群體係合意的。已報導用以產生具有高單分散性且具有大於50%之量子產率之半導體QD的方法。大部分該等方法係基於由Murray、Norris及M.G.Bawendi,J.Am.Chem.Soc.1993,115,8706(其全文以引用方式併入)闡述之最初「成核及生長」方法，但使用除所用有機金屬者外之其他前體。Murray等人最初使用金屬-烷基(R2M)(M=Cd、Zn、Te；R=Me、Et)及三-正辛基膦硫化物/硒化物(TOPS/Se)溶解於三-正辛基膦(TOP)中之有機金屬溶液。端視所產生材料而定，在120℃至400℃之溫度範圍內將該等前體溶液注射至熱三-正辛基氧化膦(TOPO)中。此產生TOPO包覆/封蓋之II-VI族材料之半導體奈米粒子。粒子之大小係由溫度、所用前體之濃度及進行合成之時間長度來控制，且在較高溫度、較高前體濃度及延長之反應時間下獲得較大粒子。此有機金屬途徑具有優於其他合成方法之優勢，包括接近單分散性及高粒子結晶度。
習用QD中所用之鎘及其他限制性重金屬係高度毒性元素且呈現商業 應用中之重大疑慮。含鎘之QD之固有毒性妨礙其用於涉及動物或人類之應用中。舉例而言，最近研究表明由鎘硫屬化物半導體材料製得之QD除非經保護否則在生物環境中可具有細胞毒性。具體而言，經由多種途徑氧化或化學攻擊可引起在QD表面上形成鎘離子，其可釋放至周圍環境中。儘管表面塗層(例如ZnS)可顯著降低毒性，但不可完全將其消除，此乃因QD可保留於細胞中或累積於體內長時段，在此期間其塗層可經歷一定形式之降解，從而暴露富含鎘之核心。
毒性不僅影響生物應用之進展，且亦影響其他應用(包括光電子及通信)，此乃因基於重金屬之材料在許多商業產品包括家用電器(例如IT及電信設備)、發光設備、電及電子工具、玩具、休閒及運動設備)中相當普遍。用於在商業產品中限制或禁用某些重金屬之法律已在全世界之許多管轄區中實施。舉例而言，歐盟指令2002/95/EC(稱作「電子設備中有害物質之使用限制」(「Restrictions on the use of Hazardous Substances in electronic equipment」(或RoHS)禁止銷售含有超過特定量之鉛、鎘、汞、六價鉻以及多溴化聯苯(PBB)及多溴化二苯基醚(PBDE)阻燃劑之新穎電設備及電子設備。此法律要求製造商找出替代材料並研發新的工程方法來產生常見電子設備。另外，在2007年6月1日，歐洲共同體條例(European Community Regulation)關於化學物質及其安全使用開始生效(EC 1907/2006)。該條例係關於化學物質之登錄、評估、授權及限制且稱作「REACH」。REACH條例對工業強加更大責任以管控與化學物質相關之風險並提供關於該等物質之安全性資訊。預期類似條例將在世界範圍內(包括中國、韓國、日本及美國)頒佈。因此，研發II-VI族QD材料之替代物存在顯著經濟刺激。
III-V族及IV-VI族高度結晶半導體奈米粒子由於增加之共價性質而更難以製備且通常需要遠更長之退火時間。然而，以類似於用於II-VI族材料之方式製備之III-VI族及IV-VI族材料有新報導。該等III-VI族及IV-VI族材料之實例包括GaN、GaP、GaAs、InP、InAs及PbS及PbSe。
對於所有上述方法，快速粒子成核、之後緩慢粒子生長對於窄粒徑分別係必需的。所有該等合成方法皆係基於Murray等人之最初有機金屬「成核及生長」方法，其涉及向路易士鹼配位溶劑(封端劑)之熱溶液中快速注射前體，該路易士鹼配位溶劑亦可含有前體中之一者。添加較涼溶液隨後降低反應溫度並有助於粒子生長但抑制進一步成核。隨後維持該溫度一段時間，且所得粒子之大小取決於所用反應時間、溫度及封端劑對前體之比率。冷卻所得溶液，之後添加過量極性溶劑(甲醇或乙醇或有時丙酮)以產生可藉由過濾或離心分離之粒子沈澱。通常，較大粒子較較小粒子更容易沈澱。因此，沈澱提供分離量子點之方式，該方式隨量子點之大小變化。通常需要多個沈澱步驟以達成窄粒徑分佈。
基本地，該等先前技術製劑依賴於粒子成核、之後升至之原理。此外，為具有單分散之奈米粒子整體，較佳適當分開奈米粒子成核與奈米粒子生長，且後者係在較前者低的溫度下發生。此係藉由向熱配位溶劑(含有其他前體，否則不存在)中快速注射一種或兩種前體來達成，該配位溶劑起始粒子成核。隨後在注射後突然添加較冷溶液降低反應溫度(所添加之溶液體積通常為總溶液之約
Figure 106108164-A0305-02-0007-1
)並進一步抑制成核，從而維持窄奈米粒子大小分佈。此方法對於小規模合成而言可良好運作，其中可將一種溶液快速添加至另一者中，同時在整個反應中保持均勻之溫度。然而，在較大製備規模(其中需要較大體積之溶液以快速注射至另一者中)中，可在反應 中發生溫度差，其可導致大粒徑分佈。此外，實施多個大小選擇性純化步驟之需求對於製造大量QD並不實際。
美國專利第7,588,828號、第7,803,423號、第7,985,446號及第8,062,703號(本文中統稱為「種晶專利」)揭示製備單分散QD群體之合成方法，其不依賴於上述熱注射方法及大小選擇性純化步驟。該等專利中之每一者之揭示內容之全文皆以引用方式併入本文中。簡言之，該等專利中揭示之方法涉及使用分子簇「晶種」化合物，其作為模板用於QD半導體材料於溶液中之成核。簇化合物用作晶種或成核點，奈米粒子可於其上起始生長。以此方式，不需要高溫成核步驟來起始奈米粒子生長，此乃因於系統中已由分子簇提供適宜成核位點。藉由提供較上述方法中採用之成核位點更均勻之成核位點，合成提供基本上單分散之QD群體。分子種晶方法之顯著優勢在於其可容易地放大。
種晶專利中所述之種晶方法可用於製造II-VI族QD且亦可用於製造III-V族及IV-VI族QD。但如上文所提及，III-V族及IV-VI族QD可能難以一起作用。由於高表面積對體積比率，小QD之表面上之原子往往自較小粒子之表面擴散至較大粒子之表面，即稱作奧斯瓦爾德熟化之過程。III-V族材料(例如InP及其合金)之QD由於奧斯瓦爾德熟化往往尤其不穩定。由於奧斯瓦爾德熟化分解較小QD且促進較大QD之生長，故此過程使得難以獲得於較短波長下發射、即在可見光譜之藍色及綠色區中發射之QD。
因此，業內需要產生發射可見光之較短波長之無鎘QD的經改良之合成方法。
本文揭示之方法及組合物藉由提供無重金屬之QD材料克服上述問 題，該QD材料在光譜之綠色區中發光但較業內已知之基於InP之QD對奧斯瓦爾德熟化更穩定。藉由向QD核心中納入諸如鋅、鋁或鎂等離子獲得QD組合物。
上述概述並不意欲概述本發明之每一潛在實施例或每個態樣。
100:核心-殼量子點
101:核心
102:殼
圖1係具有包括銦、鎂及磷離子之核心之核心-殼QD的示意性剖視圖。
圖2係圖解說明具有包括銦、鎂及磷離子之核心之核心-殼QD之合成的簡化流程圖。
圖3係含有銦、鎂及磷離子之核心QD之吸收光譜。
相關申請案之交叉參考
本申請案主張於2014年1月6日提出申請之美國臨時申請案第61/924,031號之權益。
關於由聯邦政府贊助之研究或開發之聲明：不適用
圖1圖解說明具有包括銦、鎂及磷離子之半導體材料之核心101之核心-殼QD 100。可除鎂外包括諸如鋅及/或鋁等離子，或包括該等離子代替鎂。核心可進一步包括其他離子，例如硒及/或硫。核心101經一個(或多個)半導體材料殼包覆。殼半導體材料可基本上為業內已知作為QD之殼材料之任何半導體材料。實例性殼半導體材料包括含有鋅、硫、硒、鐵及/或氧離子之半導體。
儘管圖1圖解說明核心101與殼102之間之清晰邊界，但應瞭解，該清晰邊界可不存在。相反，核心與殼材料之間可存在可感知之合金化，使得 在邊界處存在材料之梯度，此時核心材料運輸至最內殼之材料。同樣，若QD含有多個殼，則可在殼之間之邊界處發生顯著合金化。亦應瞭解，QD100之最外表面最可能經封端配體包覆，如上文有關技術之說明部分中所論述。
如上文所解釋，向基於InP之核心中納入鎂為半導體核心提供容積，而不顯著改變其帶結構。因此，由於較低表面/體積比率，核心材料之穩定性增強，但光學性質(即，吸收/發射)仍對應於較小InP核心之光學性質。
通常，業內闡述用於合成基於InP之QD之任何方法皆可適於向半導體材料中納入鎂。一種合成基於InP之核心之尤其適宜方法係上文提及之種晶專利中所述之分子種晶方法。簡言之，該方法涉及在分子種晶化合物存在下使核心材料前體反應，如圖2之步驟201中所圖解說明。基於InP之核心之適宜前體化合物應提供銦源及磷源。舉例而言，銦源可為肉豆蔻酸銦且磷源可為叁(三甲基矽基)膦。應瞭解，可使用其他銦及磷源。
此外，需要鎂源以向基於InP之核心中納入鎂。適宜鎂源係係肉豆蔻酸鎂。
核心形成反應可在分子種晶化合物存在下實施。適宜分子種晶化合物詳盡地闡述於上文提及之共有專利中。適宜分子種晶化合物之一個實例係基於硫化鋅之分子種晶化合物，其闡述於美國專利第8,062,703號(其整個內容皆以引用方式併入)中。
在種晶專利及於2009年8月7日提出申請之美國專利公開案第2010/0068522號(其整個內容皆以引用方式併入本文中)中所述之條件下在溶劑中加熱核心前體化合物及分子種晶化合物。通常，使用非供電子溶劑 進行反應。適當溶劑之一個實例係THERMINOL®66熱轉移流體(Solutia公司，St.Louis,Missouri 63141)，其包含氫化聯三苯。
如圖2中圖解說明，可期望在核心之合成期間監測QD核心之光學性質202。舉例而言，可隨著QD核心生長監測吸收光譜，且在核心達到適當大小時可停止反應以產生期望吸收及/或發射光譜。一旦獲得期望光學值且停止反應，可藉由(例如)過濾分離核心203。可期望向反應混合物中添加非溶劑以誘導核心沈澱。一旦分離核心，可使其與殼前體反應204以在核心上生長一或多個半導體殼。可期望(例如)在使核心與殼前體反應之前自核心蝕刻少量材料預處理核心。可使用諸如氫氟酸等酸以蝕刻核心。
以下實例闡釋用於製備QD之方法之代表性實施例，如本文所揭示。
實例 實例1：含有鎂之核心.
藉由在真空下將乙酸鎂四水合物(2.92g)及肉豆蔻酸(12.4g)加熱至110℃直至溶液變澄清且不再放出液體來製備肉豆蔻酸鎂。此肉豆蔻酸鎂如製備樣用於以下合成中：將肉豆蔻酸銦(4.55g)、肉豆蔻酸鎂(2.33mL)、肉豆蔻酸(0.76g)及Therminol 66(50mL)放置於配備有空氣冷凝器、氮入口、suba封口、熱電偶及攪拌棒之乾燥之250mL圓底燒瓶中並在真空下於100℃下脫氣1小時。隨後將反應物放置於氮氣氛下並添加硫化鋅簇(1.35g，如美國專利第8,062,703中所述製備)。隨後將反應物在真空下再脫氣½小時且隨後放置於氮氣氛下。逐份逐滴添加叁(三甲基矽基)膦之溶液(1M，於二苯基醚中)，同時如下增加溫度：於100℃下添加2.25mL，於160℃下添加3mL，且於230℃下添加4mL。將反應物於此溫度下保持24小時且隨後使其冷卻至室溫。隨後將其再加熱至300℃並保持½ 小時，之後冷卻至室溫。所得含有鎂之基於InP之核心的吸收光譜圖解說明於圖3中。
將反應溶液用氯仿(100mL)稀釋並經26小時之時段用氫氟酸光蝕刻。藉由添加甲醇分離經蝕刻之奈米粒子。
隨後如下用硫化鋅及氧化鋅殼外包覆由此獲得之經蝕刻之核心：將經蝕刻之核心(0.2g)、Therminol 66(20mL)及癸二酸二丁酯(20mL)放置於配備有空氣冷凝器、氮入口、suba封口、熱電偶及攪拌棒之乾燥之250mL圓底燒瓶中並在真空下於80℃下脫氣1小時。隨後將反應物放置於氮氣氛下並添加乙酸鋅(4.12g)。隨後將反應物在真空下再脫氣½小時且隨後放置於氮氣氛下。將反應物加熱至210℃，保持2小時，加熱至230℃，添加十二烷硫醇(2.6mL)，並保持反應1小時。此後，將溫度降至180℃，添加辛醇(1.7mL)，保持反應½小時，且冷卻至60℃。藉由添加丙酮(40mL)分離產物，藉由離心(4000rpm，3分鐘)分離，且隨後用甲醇洗滌並溶解於甲苯中。所得奈米粒子之光學性質係：發射最大值523nm，FWHM 57nm及量子產率74%。
實例2：含有鋅及鎂之核心
將肉豆蔻酸銦(11.74g)、乙酸鋅(0.734g)、硬脂酸鎂(0.591g)及肉豆蔻酸(1.507g)於100mL Therminol 66中攪拌並加熱至100℃。添加硫化鋅簇(2.7g，如美國專利第8,062,703中所述製備)。以7.2mL/小時之速率添加三甲基矽基膦(18.5mmol)且將反應混合物加熱至195℃並使其退火140小時。
實例3：含有鋅及鋁之核心
將肉豆蔻酸銦(11.74g)、乙酸鋅(0.734g)、硬脂酸鋁(0.877g)及肉 豆蔻酸(1.507g)於100mL Therminol 66中攪拌並加熱至100℃。添加硫化鋅簇(2.7g，如美國專利第8,062,703中所述製備)。以7.2mL/小時之速率添加三甲基矽基膦(18.5mmol)且將反應混合物加熱至195℃並使其退火140小時。
實例4：含有鋅之核心.
將肉豆蔻酸銦(11.74g)、乙酸鋅(0.734g)及肉豆蔻酸(1.507g)於100mL Therminol 66中攪拌並加熱至100℃。添加硫化鋅簇(2.7g，如美國專利第8,062,703中所述製備)。以7.2mL/小時之速率添加三甲基矽基膦(18.5mmol)且將反應混合物加熱至195℃並使其退火140小時。
實例5：含有鋅及鈣之核心
將肉豆蔻酸銦(11.74g)、乙酸鋅(0.734g)、乙酸鈣(0.607g)及肉豆蔻酸(1.507g)於100mL Therminol 66中攪拌並加熱至100℃。添加硫化鋅簇(2.7g，如美國專利第8,062,703中所述製備)。以7.2mL/小時之速率添加三甲基矽基膦(18.5mmol)且將反應混合物加熱至250℃並使其退火40小時。
較佳及其他實施例之上述說明並不意欲限制或約束由申請者設想之發明概念之範疇或適用性。應瞭解，藉助本發明之益處，根據所揭示標的物之任何實施例或態樣之上述特徵可單獨或與所揭示標的物之任何其他實施例或態樣中之任何其他所述特徵組合使用。彼等熟習此項技術者應瞭解，可進行各種改變及修改，此並不背離如由以下申請專利範圍逐字及等效涵蓋之本發明之範疇。
100:核心-殼量子點
101:核心
102:殼

Claims (8)

  1. 一種量子點奈米粒子，其包含：包含半導體材料之核心，該半導體材料包含：銦；磷；鋅；硒或硫；及至少一種選自由鎂、鈣及鋁組成之群之元素，其中該量子點奈米粒子係經組態以吸收具有第一波長之光及發射具有對應於綠光之波長的光。
  2. 如請求項1之量子點奈米粒子，其進一步包含至少一個設置於該核心上且包含半導體材料之殼。
  3. 如請求項2之量子點奈米粒子，其中該至少一殼的半導體材料包含至少一種選自由鋅、硫、硒、鐵及氧組成之群之元素。
  4. 如請求項2之量子點奈米粒子，其中在該核心與最內部之殼之間之邊界處存在材料之梯度。
  5. 如請求項4之量子點奈米粒子，其中存在複數個殼且在毗鄰殼之間之邊界處存在材料之梯度。
  6. 如請求項2之量子點奈米粒子，其進一步包含至少一種封端配體。
  7. 一種量子點奈米粒子，其包含：包含半導體材料之核心，該半導體材料包含銦、磷及至少一種選自由鎂、鋅、鈣及鋁組成之群之元素，其中在該核心與最內部之殼之間之邊界處存在材料之梯度，及其中該量子點奈米粒子係經組態以吸收具有第一波長之光及發射具有對應於綠光之波長的光。
  8. 一種量子點奈米粒子，其包含：包含半導體材料之核心，該半導體材料包含：銦；磷；鋅；硒或硫；及至少一種選自由鎂、鈣及鋁組成之群之元素，其中在該核心與最內部之殼之間之邊界處存在材料之梯度，及其中該量子點奈米粒子係經組態以吸收具有第一波長之光及發射具有對應於綠光之波長的光。
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