TW200524973A

TW200524973A - Methods of processing nanocrystals, and compositions, devices and systems including same

Info

Publication number: TW200524973A
Application number: TW93126497A
Authority: TW
Inventors: Erik Scher; Mihai Buretea; Jeffery A Whiteford; Andreas Meisel
Original assignee: Nanosys Inc
Priority date: 2003-09-04
Filing date: 2004-09-02
Publication date: 2005-08-01

Abstract

Methods of processing nanocrystals to remove excess free and bound organic material and particularly surfactants used during the synthesis process, and resulting nanocrystal compositions, devices and systems that are physically, electrically and chemically integratable into an end application.

Description

200524973 九、發明說明：【發明所屬之^技術領域1 相關申請案之對照參考資料本申請案為非臨時發明專利申請案，其請求下列先前 5 臨時專利申請案之優先權以及優點：2004年2月11曰由 Scher等人提出之美國專利申請案第60/544,285號，標題為 "Methods of processing nanocrystals, compositions, devices and systems including same” ； 2003年9月 4 日由 Scher等人提出之美國專利申請案第10/656,910號，標題為 10 ''Nanostructure and nanocomposite based compositions and photovoltaic devices” ； 2003年9月 4日由Whiteford等人提出之美國專利申請案第10/656,802號，標題為“Organic species that facilitate charge transfer to or from nanostructures”，該等之全部揭示内容與目的在此併入本案以為參考。 15 發明領域本發明係有關奈米結構之領域。特別是，本發明有關加工奈米晶體之方法以及包括該加工的奈米晶體之組成物、元件與系統。 20 發明背景對於“奈米科技”領域，有一些人預示她的到來且視其發展為提供下一個重要的技術革命者，然同時有另一些人則嘲笑之，視奈米科技僅是吸引創投公司之最新的話題技術。雖然他們對於技術之願景的基本闡述相左，但兩方陣 200524973 營的成員均指出一些相同的議題，即奈米科技必須強調是否其冒經達到其願景。特別應注意的是，雖然兩方陣營均傾向於公認奈米材料通常具有如結構.、電氣、光電與熱電的獨特以及潛在價 5值特性’但科學家，甚至是使用者或消費者取得該等獨特與價值特性之能力，可能會對實現該等材料之完整的利益造成實質上的障礙。例如’雖然以奈米線為主的電路在電子工業上可能展現廣泛潛在利益，但與這些材料接合以產生此新穎且改良 10電路之界面還未非常成功的接合，具有一些顯著的例外：見如Duan et al·，Nature 425 : 274_278 (2003)。就奈米線電子學而言’無法取得該奈米材料之優點大部分是物理學上的問題，因為材料的尺寸非常小，以至於在強健的重複製造加工下製造實際的物理或電氣接點實質上變得更為困 15 難。相關地’儘管有非常具潛力的理論能量轉換效能，之前所述以奈米材料為主的光電元件仍未到達接近所期望的效旎，此大部分係由於無法成功地以及完全地將此材料整合入光電池以取得轉換的能量。在這個例子中，一般認為 2〇無法取得材料的特性可能（至少部分)是化學問題，其涉及需要透過奈米材料之表面取得通道以及奈米材料於其特定複合環境下有效作用之能力兩者。不官是奈米材料之電氣連接功能或化學整合，將可認知到存在有-個使加工方法能產生更容易整合的奈米晶體 200524973 以及該奈米晶體群落本身之需求。本發明符合這些以及其它各種需求。【發明内容】發明概要 5 為改善尤其是奈米晶體與其周遭環境間之電子與物理相互作用之效能，本發明概略而言有關於將奈米晶體加工更完全之方法。例如，本發明提供加工奈米晶體之方法，其可用於從奈米晶體上移除過量游離態和/或結合態界面活性劑。合併此加工的奈米晶體之組成物亦為本發明之特 10 徵。第一個實施例總類提供加工奈米晶體之方法。於該方法中，將奈米晶體配製於該奈米晶體可溶於其中之第一溶劑中。該奈米晶體具有一總數量與其連結之界面活性劑，該總數量之界面活性劑包括一數量之游離態界面活性劑與 15 一數量之奈米晶體結合的界面活性劑。該奈米晶體之沈澱係藉由添加具較高極性之第二溶劑於該第一溶劑中，產生一該奈米晶體不溶於其中之致沈澱溶劑混合物，以提供沈澱的奈米晶體。將該沈澱的奈米晶體從該致沈澱溶劑混合物中分開來，然後藉由添加該奈米晶體可溶於其中之第三 20 溶劑而再度溶解。該界面活性劑典型地可溶於至少該第二溶劑與該致沈澱溶劑混合物中。任擇地重複該沈澱、分開與再溶解步驟，如一選定的重複次數和/或直到該奈米晶體到達所欲之純度位準。例如，可重複該沈澱、分開與再溶解步驟2或更多次、3或更 200524973 多次、4或更多次、5或更多次或者甚至6或更多次。至於另 -範例，可重複該沈澱、分開與再溶解步驟，直至與該奈米晶體連結之游離態界面活性劑的數量低於與該奈米晶體連結之界面活性劑之總數量的5%、低於1%、低於〇.5%，甚至低於(U%。於狀實施例中，在至少—個再溶解步驟之後接著檢查該奈米晶體’以決定仍與該奈米晶體連結之游離態界面活性劑之數量。 10 15 於特定實施例中，該第一溶劑包含單一溶劑；於任擇地實施例巾，其㈣練與魏姉溶劑线合物。血型地，該極性溶劑與該第二溶劑相同。該極性溶劑基本上可為任何適合的極性溶劑，包括，但不限於，酒精(如甲醇或 ^醇）、醋義(如乙酸⑽）或酮(如_)士-實施例頰別中’該第二溶料具有至少二個碳原子之_(如異丙 ^醇）。相似地，該較低極性之關基本上可以是任何適合二劑’包7不限於，氯仿、甲苯、鏈卿)與笨。 =地’㈣[溶料較低純之溶劑龍高極性之落血二 “ x低極性之溶劑對較高極性之溶劑的比率 =大=、大於4:1或約4…相似地，於該4 =劑混合=較低極性之溶劑對較高極性之溶劑（即第一洛劑加上包含於該篦一、〜地介於約至約1:2 (體中之極性溶劑)的比率典型沈搬溶劑混合物中較低極性_)之間。例如’於該敎 ? . 1 , ' 之7合劑對較高極性之溶劑的比丰可為2.1或更低，如1:1或更低。 20 200524973 典型地，於該致沈澱溶劑混合物中，該第一溶劑對該第二溶劑之比率介於約2 : 1至約1 : 2 (體積：體積）之間。例如，於一實施例類別中，於該致沈澱溶劑混合物中，該第一溶劑對該第二溶劑之比率為2: 1或更低(如1: 1或更低）。 5 該第一溶劑基本上可為任何非極性或相對非極性之溶劑。適合的第一溶劑包括，但不限於，氯仿、甲苯、鏈烧(如己烷)與苯。相似地，該第二溶劑基本上可為任何極性或相對極性之溶劑。適合的第二溶劑包括，但不限於，酒精（如甲醇或較佳地具有至少二個碳原子之酒精，如乙醇、異丙 10 醇與丁醇）、醋酸酯（如乙酸乙酯）以及酮（如丙酮）。該第三溶劑可與該第一溶劑一致，但不必須為該第一溶劑。另一實施例總類提供從奈米晶體上移除過量結合態界面活性劑之方法。該方法中，提供一含有奈米晶體溶於其中之溶液。該奈米晶體具有一總數量與其連結之界面活性 15 劑，該總數量之界面活性劑包括一數量之游離態界面活性劑以及一數量之結合態界面活性劑。於該溶液中游離態界面活性劑之數量低於該總數量之界面活性劑之10%(如低於該總數量之界面活性劑之5%、1%或0.1%)。於該奈米晶體中加入鹼，該鹼與該結合態界面活性劑形成不溶性鹽。將 20 該不溶性鹽從溶於該溶液中之奈米晶體中分開來，以提供具有部分單層至二層結合於其上之界面活性劑之奈米晶體。該不溶性鹽可藉由，例如，離心該奈米晶體與不溶性鹽，且從不溶性鹽之沈澱丸中倒出溶於該溶液中之奈米晶 200524973 體，而從溶於該溶液之奈米晶體中分開來。各種適合的驗係此技藝中所熟知者。例如，包括，但不限於，°比σ定、苯胺、雙°比咬、旅咬、味唾、二乙胺、三乙胺與二-異丙胺。該鹼典型地以鹼對奈米晶體溶液比為大 5 於1 : 1 (體積：體積）之比率添加；如大於2: 1或甚至大於3 ·· 1 ° 又另一實施例總類提供加工奈米晶體之方法。於該方法中，該奈米晶體係配製於該奈米晶體可溶於其中之第一混合物中。該第一混合物包括一第一溶劑和/或該奈米晶體 10 於其中合成之反應混合物。該奈米晶體之沈澱係藉由添加一第二溶劑於該第一混合物中，產生一該奈米晶體不溶於其中之第二混合物，以提供沈澱的奈米晶體，之後從該第二混合物中分開來。該沈澱的奈米晶體藉由添加至少該第一溶劑而再度溶解，以提供一第三混合物。調整該第三混 15 合物之極性以提供一該奈米晶體不溶於其中之第四混合物，俾獲得沈澱的奈米晶體。將該沈澱的奈米晶體從該第四混合物中分開來。重複該再溶解、沈澱與分開步驟直到當該奈米晶體再溶解於該第一溶劑中時，游離態界面活性劑之數量低於總界面活性劑之總數量的5%，該界面活性劑 20 之總數量包含一數量之游離態界面活性劑以及一數量之奈米晶體結合的界面活性劑。較佳地，可重複該再溶解、沈澱與分開步驟直到該游離態界面活性劑之數量低於該界面活性劑之總數量的1%、低於0.5%或更佳地低於0.1%。例如，可重複該再溶解、沈澱與分開步驟2或更多次、3或更 10 200524973 多次、4或更多次、5或更多次或甚至6或更多次。於特定實施例中，在至少一個再溶解步驟之後接著檢查該奈米晶體，以決定游離態界面活性劑之數量。於一些實施例中，該第一混合物僅包括該第一溶劑和/ 5 或該反應混合物，然而於其它實施例中，該第一混合物亦可包括該第二溶劑。相似地，該奈米晶體之再溶解可藉由添加該第一溶劑至該沈澱的奈米晶體中，以提供該第三混合物，或藉由添加該第一溶劑與該第二溶劑。至於以上所述之實施例，於該第一和/或第三混合物中，該一溶劑對該 10 二溶劑之比率典型地介於約3 : 1至約10 : 1 (體積：體積）之間，然而於該第二和/或第四混合物中，該第一溶劑對該第二溶劑之比率典型地介於約2 : 1至約1 : 2之間。該第三混合物之極性典型地係藉由於該第三混合物中加入該第二溶劑來調整，但於該第三混合物包括該第一和該第二溶劑 15 之實施例中，該第三混合物之極性可藉由移除至少一部分之該第一溶劑（如藉由蒸發）來調整。典型地該第一溶劑之極性低於該第二溶劑（然而，於奈米晶體具有夠高位準之與其連結之增溶的界面活性劑，使其更溶於較高極性而不是較低極性之溶劑的實施例中，該第一溶劑之極性可高於該第 20 二溶劑）。如以上實施例之說明，許多第一和第二溶劑是此技藝中所熟知者。例如，該第一溶劑可以是氯仿、甲苯、鏈烷(如己烷）或苯，而該第二溶劑可以是酒精(如甲醇或較佳地具有至少二個碳原子之酒精，如乙醇、異丙醇或丁醇）、醋酸酯 11 200524973 (如乙酸乙酯）或酮（如丙酮）。其它實施例總類提供加工奈米晶體之方法。該方法中，將一包括該奈米結構可溶於其中之第一溶劑以及該奈米結構不溶其中之第二溶劑之溶劑混合物加至該奈米結構 5 中。該奈米結構之沈殺係藉由添加額外數量之第二溶劑，該額外數量足以將該奈米結構從該溶劑混合物中沈澱下來。之後將該奈米結構從該溶劑混合物中分開來(如藉由離心），藉此將過量之有機界面活性劑（其繼續存在該溶劑混合物中）從該奈米結構上移除。任擇地重複該添加、沈澱與分 10 開步驟2或更多次(如3或更多次、4或更多次、5或更多次或 6或更多次）。可在如沈殿之前、分開和再溶劑之後、在每一個沈澱與再溶解循環週期之後或一規定次數的循環週期之後分析該奈米結構，以決定界面活性劑存在的數量。任擇地重複該添加、沈澱與分開步驟直到界面活性劑存在的 15 量到達一所欲數量（如直到游離態界面活性之數量低於界面活性劑之總數量的10%、5%、1%或0.1%等等）。至於以上之實施例，一些第一和第二溶劑可以是選擇性的。例如，該第一溶劑可包含甲苯或氯仿，而該第二溶劑可包含含有多於二個碳原子之酒精（如異丙醇）或醋酸酯 20 (如乙酸乙S旨）。添加至該奈米結構中之溶劑混合物典型地包含比率介於1 : 1至10 : 1之間之該第一溶劑和該第二溶劑。作為一特定範例，添加至該奈米結構之該溶劑混合物可包含四部分的甲苯對一部分的異丙醇。 12 200524973 該方法任擇地包括額外的純化步驟，如移除甚至更多的過量界面活性劑。例如，可進行吡啶交換，以及可將所產生之有機鹽沈澱下來（以及移除，如在離心之後），而留下該奈米結構於溶液中。 5 又其它實施例總類提供加工奈米晶體之方法。於該方法中，結合該奈米晶體與該奈米晶體可溶於其中之第一溶劑以及該奈米晶體不溶於其中（如不溶的）之第二溶劑。允許該第一和第二溶劑形成一包含該第一溶劑與該奈米晶體之第一液相，以及包含該第二溶劑之第二液相，之後將該等 10相分開。因為該界面活性劑典型地可溶於該第一與第二溶 Μ兩者中（較佳地比該奈米晶體更溶於該第二溶劑中，更佳地其本身溶於該第二溶劑中之程度高於溶於該第一溶劑）’所以此加工法導致游離態界面活性劑於具有該奈米晶體之溶液中的數量減少。 15 任擇地重複此加工法以獲得所欲的純度位準。此重複的加工可進行一選定的重複次數，如已知欲獲得所欲純度之次數。例如，可重複該等步驟2或更多次、3或更多次、4 或更多次、5或更多次，甚至6或更多次。於特定的較佳態樣中，彳欢查所、，谷解之奈米晶體之純度，如以決定該界面活 20性劑之位準於該組成物中是否夠低。之後必要的話，任擇地重複該結合、相形成與分開步驟直到於該奈米晶體混合物中游離態界面活性劑的數量低於總界面活性劑濃度（游離態與結合態）的10%或低於5%，較佳地低於該界面活性劑總數量之1%，更佳地低於〇1%。 13 200524973 該第一和第二溶劑以及其等相對的比率典型地視該奈米晶體以及想要移除之有機雜質之本質而定，如存在之界面活性劑之類型。典型地，在清潔無機奈米晶體方面，該第一溶劑會比該二溶劑之極性低。於一特定實例中，以TOP 5 作為界面活性劑而製備成之奈米晶體係以作為第一溶劑之甲苯，以及作為第二溶劑之甲醇來處理。以在此所述方法之任一種加工之奈米晶體（如無過量游離態和/或結合態界面活性劑之奈米晶體）形成本發明之另一個特徵，即包括此加工的奈米晶體之組成物、系統與 10 元件。因此，一實施例總類提供包括溶於一第一溶劑中之奈米晶體群落之組成物。該奈米晶體與一總數量之界面活性劑連結，其於溶液中包括一數量之結合態界面活性劑以及一數量之游離態界面活性劑。該游離態界面活性劑之數量低於該界面活性劑總數量之5%，較佳地低於約1%、低於 15 約0.5%，更佳地低於約0.1%。如之前所述，該奈米晶體基本上可以是任何形成、尺寸和/或組成物。一相關實施例總類提供一種組成物，其包含一具有結合於奈米晶體上且溶於一第一溶劑中之奈米晶體群落。該奈米晶體包含少於二層與其連結的界面活性劑。較佳地， 20 該奈米晶體包含約單層或較少層與其連結的界面活性劑。其它相關實施例總類提供一種組成物，其包含一奈米晶體群落以及結合於其上之界面活性劑，其中該界面活性劑包含少於二層。例如，該界面活性劑較佳地包含約單層或更少層。 14 200524973 如所提到的，將以本發明之方法加工之奈米晶體任擇地併入各種組成物與元件中。因此，一實施例之範例種類提供一種複合物，其包含一有機聚合物基質以及一設置於該有機聚合物基質内之奈米晶體群落。該奈米晶體具有與 5 其連結之界面活性劑，該界面活性劑包含少於二層（如該界面活性劑可包含約單層或更少層）。另一實施例種類提供一種組成物，其包含一第一奈米晶體群落以及一第二奈米晶體群落。該第一奈米晶體群落具有與其連結之界面活性劑，該界面活性劑包含少於二層 10 (如約單層或更少層）。該第二奈米晶體群落具有不同於該第一奈米晶體群落之組成物，且與該第一群落一起散布於該組成物中。該第二群落任擇地亦包含少於二層之相同或相異之界面活性劑。該散布的第一與第二奈米晶體群落可，但不必須，設置於一基質（如有機聚合物基質）中。 15 圖式簡單說明第1圖是簡要地說明使用界面活性劑調控之合成方法之奈米晶體合成之流程圖。第2圖是簡要地說明本發明用於奈米晶體製品之後合成加工步驟之範例。 20 第3A-3G圖是在不同的清洗與加工步驟後，奈米晶體製品之31P-NMR光譜，其顯示與該等奈米晶體製品連結之游離態與結合態界面活性劑之位準。圖片G顯示圖片D(上面，清洗液4)、圖片E(中間，清洗液5)與圖片F(下面，清洗液6)之結合態界面活性劑波峰的放大圖。 15 200524973 【實施方式】定義除非有定義，否則所有在此使用之技術或科學術語具有與熟悉本發明相關技藝之人士一般所了解之相同音思。 5下列定義補充此技藝中術語之定義且係針對目前之申請案，而不能應用在任何相關或不相關之案例，如任何共同擁有的專利或申請案。雖然在用於測試本發明之實施時可使用任何與在此所述相似或相同之方法與材料，但較佳的材料與方法是在此所描述者。據此，在此所使用之術語之 10目的僅用於描述特別的實施例，而不欲做限制用。除非有特別清楚地指示，否則在此說明書以及隨附之申請專利範圍中所使用之“一，，與“該，，之單數形式包括複數對象。因此，例如“一奈米結構，，包括複數形式之奈米結構， “一溶劑”包括溶劑之混合，界面活性劑，，包括界面活性 15 劑之混合物等等。在此使用之術語“約，，指的是所給之數量的值之差異為所述值之+/- 10%或任擇地+/_ 5%或於一些實施例中為+/_ 1% 〇 20 士笊木結構方面時，意指該奈米結構典型地在該結構之一或多維上展現長程有序（kmg-range ordering)。熟悉此技藝人士很清楚該術語‘‘長程有序，，取決於特定奈米結構之絕對尺寸，因為單晶之有序無法延伸超出該晶體之邊界。既然這樣，“長程有序，，將意指該奈米結構之至少主要維度上實質上有序於某此 16 200524973 情況下，奈米結構可具有氧化物或其它包覆，或可由一核心與至少一個殼構成。於此情況下，可察知該氧化物、殼或其它包覆不必要展現此有序（其可為非晶型、多晶或其它）。於此情況下，“結晶”、“實質上結晶”、“實質上單晶” 5 或“單晶”片語指的是該奈米結構之核心（排除該包覆層或殼）。在此使用之術語“結晶”或“實質上結晶”亦意欲去含括包含各種缺陷、疊差、原子取代等之結構，只要該結構展現實質上長程有序（如有序超過該奈米結構或其核心之至少一個軸之長度的至少約80%)。此外，可知核心與奈米結 10 構外側之間、核心與鄰接殼之間或殼與第二鄰接殼之間的界面可包含非結晶區域且甚至可為非晶形。此不會妨礙該奈米結構成為在此所定義之結晶或實質上結晶。當術語“單晶’’用於奈米結構方面時，意指該奈米結構實質上是結晶的且實質上包含一單晶。當用於包含一核心 15 或一或多殼之奈米結構異質結構時，“單晶”意指該核心實質上是結晶的且實質上包含單晶。 “奈米結構”是一種具有至少一個區域或特徵維度具尺寸小於約500 nm之結構，如小於約200 nm、小於約100 nm、小於約50 nm或甚至小於約20 nm。典型地，該區域或特徵 20 維度經常沿著該結構之最小軸。此結構之例子包括奈米線、奈米棒、奈米管、分枝的奈米結構、奈米四足 (nanotetrapod)、三足、二足、奈米晶體、奈米點、量子點、奈米粒子等等。奈米結構可以是如實質上結晶、實質上單晶、多晶、非晶形或其組合。於一態樣中，該奈米結構之 17 200524973 三個維度中之每一個具有尺寸小於約500 nm，如小於約200 nm、小於約100nm、小於約50nm或甚至小於約20nm。 “奈米晶體”是一種實質上單晶之奈米結構。因此奈米晶體具有至少一個區域或特徵維度具有尺寸小於約500 5 nm，如小於約200 nm、小於約100 nm、小於約50 nm或甚至小於約20 nm。在材料特性方面，奈米晶體可以是實質上均質的，或特定實施例中可以是異質的（如異質結構）。術語 “奈米晶體”是意圖涵括實質上包含各種缺陷、疊差、原子取代等之單晶奈米 10 結構，以及實質上沒有此缺陷、誤差、取代之單晶奈米結構。至於包含一核心與一或多殼之奈米晶體異質結構，該奈米晶體之核心典型地實質上為單晶，但該殼不必須為單晶。該奈米晶體可由基本上任何合宜的材料製成。例如，該奈米晶體可包含無機材料、半導體材料(如第II-VI、III-V 15 或IV族半導體）、金屬、半金屬、導體材料、絕緣材料和/ 或類似的材料。於一態樣中，該奈米晶體之三個維度中之每一個具有尺寸小於約500 nm，如小於約200 nm、小於約 100 nm、小於約50 nm或甚至小於約20 nm。奈米晶體之例子包括，但不限於，實質上楕圓形奈米晶體、分枝的奈米 20 晶體以及實質上單晶奈米線、奈米棒、奈米點、量子點、奈米四足、三足、二足與分枝四足（如無機樹枝 (dendrimers)) ° “分枝的奈米晶體”是一種具有三或更多臂之奈米晶體，其中每一臂具有奈米棒之特徵，或是一種具有二或更 18 200524973 多臂之奈米晶體，其中每一臂具有奈米棒之特徵且發源於一中心區域，該中心區域具有與該等臂相異之晶體結構。例子包括，但不限於，二足、三足以及奈米四足（四足）。 “奈米四足，，一般是一種四面分枝的奈米結構，其具有 5 從中心區域或核心發出之四臂，其中任何二個臂間之角度為將近109.5。。典型地，該核心具有，種結晶結構，而該等臂具有另一種結晶結構(值得注意的是，此不會阻礙該奈米四足成為單晶，因為該等臂與該核心是藉由疊差而聯繫起來；例如具閃鋅礦結構之核心與具纖鋅礦結構之臂是藉由 10 疊差而聯繫起來，其不會瓦解該奈米結構之二個組成原子之四面鍵結）。 “實質上楕圓形奈米晶體”是具有長寬比（aspect ratio) 介於約0·8至約1·2間之奈米晶體。 “長寬比（aspect mtio)，，是奈米晶體之第一軸的長度除 I5以該奈米結構之第二與第三軸之長度的平均值，在這裡該苐一與苐二軸是其長度彼此最接近相等之二軸。例如，完美的棒狀之長寬比是其長軸之長度除以垂直於（法線）該長軸之橫斷面的直徑。 “奈米棒”是一種具有一個主軸比另二個主軸長之奈米 20結構。因此，奈米棒具有大於以長寬比。本發明之奈米棒典型地具有長寬比介於約I·5至約10之間，但可能具有長寬比大於約10、大於約20、大於約5〇或大於約湖或甚至大於約10,000。&長的奈米棒(如該等長寬比大於約10者)有時候心才曰示米線。奈米棒之直徑典型地小於約500 nm，較佳地 19 200524973 小於約200 nm，更佳地小於約150 nm，最佳地小於約1〇〇 nm、約50 nm或約25 nm，或甚至小於約1〇 nm或約5娜。奈米棒可具有可變的直徑或具有實質上一致的直徑，即在最尚變異度之區域的直徑顯示小於約20%之變異（如小於約 5 10%、小於約5%，或小於約1%)。奈米棒典型地為實質上結晶和/或實質上單晶，但可能為如多晶或非晶形。 “界面活性劑”是能夠與奈米結構之一或多個表面、正面4相互作用之分子。一或多種界面活性劑典型地用於奈米結構合成反應中，用以幫助所產生之奈米結構之尺寸和/ 10或形狀控制，抑制凝聚以及維持該奈米結構和/或相似物之溶解度。與奈米晶體(如配製於溶液中之奈米晶體群落)“連結之界面活性劑總數量，，包括一數量之游離態界面活性劑以及一數量之結合態界面活性劑。“結合態界面活性劑，，或“奈米 15晶體結合的界面活性劑，，是物理性地與奈米晶體連結（如共價地或非共價地與奈米結構表面連結，或共價地或非共價地與一分子連結，該分子本身共價地或非共價地與奈米結構表面連結）。“游離態界面活性劑，，沒有與奈米晶體結合。 “溶劑”是一種能夠溶解其它物質之液態物質。任何二 2〇種/谷劑之相對的極性可以藉由例如比較其等之極性指數來比較（見如 CRC Handbook of Chemistry and Physics，84th ed CRC Press) 〇在此使用之術語“基質，，意指材料，通常是聚合材料，於其中包埋有一第二材料（如奈米結晶組成物）或被_第二 20 200524973 材料包圍。該基質可能是導體組成物、半導體組成物或非導體組成物。各種額外的術語是經定義的或在此用別的方法特徵化。 5 詳細說明 I·本發明之一般說明本發明一般係針對加工奈米晶體群落之方法，以及針對由此方法產生之奈米晶體複合物與組成物，此奈米晶體群落與奈米晶體複合物提供增加的性能特徵，此係由於其荨經更元全的加工和/或由於更容易整合入其等最終之鹿用中。以在此所述之方法加工之奈米晶體，之後容易整合入包括有機聚合物基質之基質、包括其它具相同或相異組成物之奈米晶體之基質、溶膠-凝膠基質、陶曼基質、無機基質等等。 15 如之前所述，一個與確實利用奈米材料之有利特性相關且持續存在的困難是，有效地整合該等材料進入其等最終應用之能力。純粹以結構為基礎，奈米材料之定位與定向之實施必須不是以塊材為基礎，就是使用利用奈米材料特性(如化學、高能或磁)之自我對準、定位或對準技術。在 20其它結構整合不是關鍵性之應用方面，如奈米材料之塊材應用中，整合之問題仍可能是重要的。例如，利用争米材料作為塊材，但利用其等之光學或電子特性時，適當的整合該等材料於被選擇作為最適合所給定應用之基質中或基質上可能是關鍵性的。此適當的整合在有效地利用該奈米 21 200524973 材料之特性與浪費該等特性間產生差異。於至少一範例中，一般認為從奈米材料中，如以分開的電荷形式之電能的引出，明顯地會受該奈米材料與該奈米材料之周圍（電能欲傳送進去之處）間之化學整合的影 5響。如在以奈米晶體為主之光電元件(諸如光生伏打的）中使用的，特別感興趣是電荷從電荷傳導基質至該奈米晶體之傳送，或電荷從該奈米晶體出來至電荷傳導基質之傳送。特別地，奈米晶體已被使用且建議用作電荷分離組件，供用於一些包含光電元件之應用。簡言之，當光照射在奈米 10 aa體上時，其具有於該晶體内製造電子電洞對或“光激子 (exciton)”之作用。當容許於該晶體内再結合時，該光激子射出一光波，其係該晶體之尺寸與組成物之特徵。然而，當該電子（或洞）成功地從該晶體引出，且傳導至一對相反的電極之一者，則製造出可以被利用之電位。 15 此特性是奈米晶體組成物用於下一代光電電池中之根本基礎。明確地說，因為有提供該等材料於可撓性複合物中之能力、以低廉價格製造此複合物之潛能、此材料之相對鬲理論轉換效能以及該等材料之協調性，故期待以卉米曰曰體為主之光電元件此使此源的產生發生徹底變革。 2〇儘管對利用奈米晶體作為啟動組件之光電技術上之期待以及早期的成功，仍存在有實質改善的空間，如達致接近理論效能之目的。在不受限於特定操作原理之情況下，一般相信於原型系統中，目前所見之至少一部分的效能流失疋由電荷載體（如電子導電奈米晶體組件）與另—電荷載 22 200524973 體(如電洞傳導周圍的基質）之不良連接所造成，不管其為有機導電聚合物基質或具不同組成物之鄰接的奈米晶體。一般認為此不良連接會導致不完全的電荷引出以及與該奈米晶體分離，其依次被認為是低於理論效能之至少一個原因。 5 10 15 20 據此，於至少一個態樣中，本發明提供該奈米晶體之加工，以移除過量位準會影響此連結之污染材料。此污染物之例子包括於該奈米晶體之合成中使用和/或用於改善該奈米晶體之處理特徵(如其溶解性）之界面活性劑。特別地，在不受限於_㈣理論之情況下，—般認為上所提及之界面活性劑提供會妨礙該奈米晶體組件與其周遭基質間電荷的傳送之障礙層。然而不幸地，為提供該奈米晶體組件之合理的處理，-純準的界面活_之必須的。明確地說，假如該奈米晶體之界面活性劑的包覆不夠，則其會與其它奈米晶體㈣在—起而不會良好的分散於其最終的基質中’此將導致電荷引出之效能不佳，甚至產生沒有功能之複合物。因此，本發明之目標即是提供一種奈米晶體群落，㈣有足夠的界面活性劑包覆，以容許該奈米晶體具溶解性，但不會多到過度的妨礙從該奈米晶體之電荷的引出。在此使用之溶雜的概念，#其應祕奈米晶體群落時，-般是想像奈米晶體能夠呈實質上非凝集狀態存在於溶液中，如於-給定的群落中之奈米晶體超過7〇%、 80%或90%不會與在相同群、落中之其它奈米晶體凝集在一起，較佳地大於95%是不會凝集在—起的，更佳地大於_ 是不會凝集在-起的。同樣在不受限於特別操作理論之情 23 200524973 況下，一般認為此包覆需要足夠的界面活性劑存在，以提供該奈米晶體上具一部分單層至超過二層或甚至多層的界面活性劑包覆一奈米晶體。因此，於至少一態樣中，本發明提供用於加工奈米晶 5 體群落之方法與所產生之組成物，以移除過量有機材料以及特別是用於產生或溶解該等奈米晶體群落之界面活性劑，藉此提供該群落中奈米晶體與其周圍間，在電荷引出與物理性交互作用（如溶解度）方面，具有良好的交互作用。為方便討論，例示性系統係就設置於基質（如導體聚合物基 10 質）中之奈米晶體群落，以形成複合物材料方面作說明。然而，應很容易察知，本發明對想要改善奈米晶體與任何圍繞該奈米晶體之材料間之交互作用之情況具有廣泛的應用性，包括如其它奈米晶體、水性材料、固體，如基材、絕緣體等。例如，應很容易地察知，奈米晶體於廣泛各種光 15 電和/或冷光上的應用，係運用相同的電荷引入或取出之基本原理，其能因提高基質與奈米晶體間電荷的傳送而受惠，如奈米晶體為主之LEDs等等。一般而言，本發明提供用於減少奈米晶體群落中過量位準之界面活性劑之方法，該方法係藉由進行下列一者或 20 兩者都進行，即從包括該奈米晶體之混合物中移除過量非結合態界面活性劑以及移除過量位準之可與該奈米晶體物理性連結之界面活性劑（不管該連結的本質，在此一般指的是“結合態”界面活性劑）。經由實例，在此使用之“結合態” 界面活性劑包括共價連接，但亦包括諸如凡德瓦力、疏水/ 24 200524973 親水父互作用等之非-共價連結。一般而言，本發明之目的分別地經由下列方法來達成，清洗該奈米晶體群落以移除過量非結合態或游離態界面活性劑以及使用交換或滴定方法除去所產生奈米晶體之過量連結的結合態界面活性劑。 5 雖然先前的研究人員已有討論用於加工奈米晶體之清洗步驟（見如 Huynh et al·，Adv. Mater. 11(11): 923-927(1999);以及Greenham，et al.，Phys. Rev. B 54(24): 17628-17635(1996))，然而此步驟會導致具有相對高位準之污染性界面活性劑（結合態與游離態兩者)之奈米晶體。在不 10文限於特別的操作理論之情況下，一般認為此過量位準之 /亏染物是以此等材料為基礎之電氣或光電元件性能平凡 (相對於其理論電位）之至少部分原因。再者，該等早期文獻明確地揭示必須避免額外的清洗步驟，暗示進一步的清洗步驟會降低整個奈米晶體組件之溶解度，因此降低其 15整合性。額外地，雖然有討論清洗步驟，但總的來說，此清洗僅著重在清洗與再清洗沈澱的奈米晶體至將任何殘留的游離材料從該等沈澱的晶體上移除，其反覆的清洗與再清洗處理容易再沈澱與再懸浮相同的污染物。然而’相對於該等早期公開文獻之教示，本發明之目 2〇的明確地提供進一步加工的奈米晶體，特別是具有比該等之别所述更少污染的有機材料（如界面活性劑）之奈米晶體群落。此奈米晶體群落提供改善的性能特徵，一般認為某種私度係由於過量妨礙組份的移除。再者，儘管移除此過里界面活丨生剤，該等奈米晶體群落仍保留必須的溶解度， 25 200524973 以適合被加工於所欲的元件、應用或系統中。據此，於一第一態樣中，本發明提供透過反覆性清洗奈米晶體組件，以移除存在於該奈米晶體溶液中過量位準之游離態界面活性劑之加工法，該方法涉及重複的選擇性 5沈澱與再溶解該奈米晶體。移除過量位準之游離態界面活性劑意指於所產生的奈米晶體溶液組成物中之全部界面活性劑中，該游離態組份低於全部存在之界面活性劑的 10%，較佳低於5%，更佳低於1%以及於一些例子中較佳低於0.1%。相似地，該所產生之奈米晶體组成物易於併入供 10用於各種應用之複合物中，如於有機聚合物基質、混合的奈米晶體材料、溶膠-凝膠基質等等。游離態與結合態界面活性劑之數量的測定可藉由許多方法來進行’卩-顧轉別適合如含構之界面活性劑。特別地’第3A-3G圖顯示使用在此所述之方法對CdSe奈米棒 b進仃反覆清洗步驟之一系列標繪圖。如所顯示的，相對於結合態界面活性劑的數量（寬峰），每一個相繼的清洗步驟顯著地減少游離態界面活性劑的數量（尖峰)。四個清洗步驟之後’ 5亥含奈来晶體之溶液中差不多已經測量不到游離態界面活性劑的量（見第3〇圖）。由該寬峰稍微變平坦顯示出， 2〇額外的清洗步驟(如第5與第6次）亦開始進一步減少結合態界面活性劑的位準（第3E、3續则）。雜態與結合態界面活性劑之相對數量可藉由例如比較n M r標繪圖中於各自波峰下的區域來測定。如之前所述，減少含奈米晶體之溶液中游離態界面活 26 200524973 性劑之數量，以及因此併入任何所產生之元件、薄層或系統中之數量，任擇地係藉由反覆的清洗方法來進行，該方法涉及選擇性地將該奈米晶體部分從溶液中沈殿出來，離開主要的污染性游離態界面活性劑，將該奈米晶體再溶解 5以及重複該沈澱與再溶解步驟直至溶液中游離態界面活性劑的位準降低至所欲之位準。於本發明之第二態樣中，令如已經經過清洗以移除過量游離態界面活性劑之奈米晶體群落受額外的加工步驟處理，以減少與該奈米晶體連結之結合態界面活性劑之位 10準。如上所述，一般需要減少結合態界面活性劑之位準至將近一或一個早層於該晶體之表面上。典型地，此包括從約部分單層至約二層之界面活性劑。如以上之清洗步驟，一般是藉由沈澱與離心之方法來進行，然而於本發明此態樣中，過量的界面活性劑係選擇性地沈澱而離開該奈米晶 15 體。 II.奈米晶體之合成關於半導體奈米晶體之合成與其應用以前已有很詳細的說明。見如美國專利第6,322,901號、第6,207,229號、第 6,607,829號、第 6,617,583號、第 6,326，144號、第 6,225，198 20 號以及第6,306,736號（該等之全部内容與目的在此併入本案以為參考）。亦可見由Scher等人提申之美國專利申請案第 60/591,987 號，標題為 “Process for group III-V semiconductor nanostructure synthesis and compositions made using same”。在此使用之半導體奈米晶體包括各種廣 27 200524973 泛的以奈米粒子存在之材料，如具有至少一個橫斷維度小於約500 nm，以及較佳地小於1〇〇 nm。該等奈米晶體可由廣泛的半導體材料構成，包括如第m-v族、第Ι]μνι族與第 IV族半導體或該等材料之合金。奈米晶體實質上可為楕圓 5 形，如量子點，或可為痩長的，如奈米棒或奈米線’如具有長寬比為2、5、10或甚至20或更高，或可包含分枝的結構，如奈米四足。見如美國專利第6,322,901號；Pengetal， Nature 404(6773) ： 59-61 (2000) ； Manna et al.? J. Am. Chem. Soc. 122(51)： 12700-12706(2000)； Manna et al.5 J. Am. Chem. l〇 Soc. 124(24) : 7136-7145(2002);以及Duan et al·，Nature， 425 : 274·278(2〇03)，其等之全部内容與目的在此併入本案以為參考。此種奈米晶體可包含單一均質的組成物或包含異結構，如核心-殼構造，其中該核心材料是一第一組成物，而 15該殼材料為第二相異之材料，其與該第一材料之界面為清晰的刀界線或呈梯度的。額外地，一群落中之奈米晶體可呈各種大小或其等在其一或多橫斷面維度方面可為單分散的。同樣地，-奈米晶體之群落可包含單一類型之奈米晶體，如其中實質上該群落之每個部分具有相同的構造，如 20同或異結構，或該群落可為不同晶體類型之異質混合物。 ;一例子中有^貝值的奈米晶體係使用以溶液為主之方法製成，其靠界面活性劑調控成長，以產生所欲形狀與大小之奈米晶體，如奈米棒或分枝的奈米結構，如夺米四足。此界面活性劑調控之合成於: 28 200524973 404(6773) ： 59-61 (2000) ； Manna et al.? J. Am. Chem. Soc. 122(51): 12700-12706(2000)，以及Manna et al.，J. Am. Chem· Soc· 124(24) : 7136-7145(2002)中已有非常詳細地說明。第 1圖提供簡要地說明例示性奈米晶體合成方法之流程圖。 5 簡言之，如第1圖所示，半導體奈米晶體之合成典型地藉由將如第II族前趨物與第VI族前趨物（或如另一個實例，第III族與第V族前趨物）之半導體前趨物（104)導入高溫雙或協同溶劑混合物（102)，如，該混合具有高於該前趨物會反應之溫度之沸點，如介於200至400°C之間（104)。典型地， 10此雙溶劑混合物包括至少二種有機界面活性劑。此等界面活性劑典型地包括如三-辛基氧化膦（丁〇1>〇)、己基膦酸 (ΗΡΑ)與十四基膦酸（Tdpa);以及TOPO與十八基膦酸 (0DPA)或十六基膦酸(HDPA)。於該熱反應溶劑混合物中注入該前趨物會產生瞬爆之奈米晶體之均質成核（104)。快速 15降低與成核有關之試劑以及添加試劑使溫度下降均可有效地終止成核反應。加熱該反應混合物（106)，之後允許奈氺微晶之退火與成長，如成實質上單分散的粒子小大群落。之後藉由降低該反應混合物之溫度來停止該成長進移 (108)。該粒子之大小分佈的進一步精製可任擇地藉由從該 20溶劑混合物中以大小選擇性沈澱該奈米晶體來完成 (110)(見美國專利第6,322,9〇1號），其係於如下述之後續的加工步驟中之一者期間，使用如低分子量酒精來改變該反應混合物之極性，而將奈米晶體沈澱出來。令所產生之奈米晶體接著受進一步之加工（112)。 29 200524973 其它奈米晶體類型之合成方法為此技術領域所熟悉。見如 Rockenberger et al. (1999) “A new nonhydrolytic single-precursor approach to surfactant-capped nanocrystals of transition metal oxides” J Am Chem Soc 121: 11595-11596 5 以及Puntes et al· (2001) “Colloidal nanocrystal shape and size control : The case of cobalt” Science 291 : 2115-2117 〇 III.奈米晶體之加工 A.預先確定試劑之純度於至少一些情況下，奈米晶體群落之相對純度，至少 10 部分會受於此加工中使用之材料的相對純度所支配。特別地，雖然於該晶體合成步驟中使用之界面活性劑與其它溶劑規定要特別純的，但此純度常常是不準確的。因此，為確定有純的晶體製品結果，預先確定於合成步驟中使用之試劑的純度是有用的。於至少一態樣中，以如NMR測定以 15確定晶體合成步驟中使用之界面活性劑之純度為至少 99%、較佳地高於99%會是有用的。如果從供應商拿到之界面活性劑的純度不在所欲的位準，則可使用之後的純化步驟，如清洗、再結晶、昇華、蒸餾等，以提供所欲之純度位準。於許多例子中，此界面活性劑含有氧化的產物、起 20始材料反應物以及不完全酯水解之副產物。例如，膦酸，特別是ODPA以及TDPA，非常容易受此問題之影響，因時常拿到的是具有伴隨HC1與其它雜質之當量位準的酯形態。該酯形式之膦酸會引起嚴重的問題，因其能夠寡聚合成多齒狀結構，故使得所產生之奈米晶體的清潔特別的困 30 200524973 難。相似地，TOPO常包括膦酸與次膦酸二者，其會導致於合成期間反應速率以及酸：金屬比率的改變。 Β.減少游離態界面活性劑如在此所重複提及的，該典型的奈米晶體合成方法(如 5 在上文中所說明的）通常會產生具有相對大量污染材料（如與奈米晶體連結之有機界面活性劑）之奈米晶體群落。用於將奈米晶體從該合成反應混合物中回收之以沈澱為主之標準方法，在移除此過量污染物方面效果可能不彰。特別是，許多於此合成反應中使用之慣用界面活性劑常常是不溶於 10 致沈澱溶劑中的，因此與奈米晶體一起沈澱下來。事實上，即使在一些層度的進一步沈殿與加工後，此有機污染物仍殘留成為組成物的部分，此於此技藝之先前技術中已有說明，如具有游離態界面活性劑超過1或5或10%以及結合態界面活性劑遠超過所欲之部分單層至二層的界面活性劑。 15 額外地或選擇性地，之前所述之奈米晶體純化方法會阻擋縮短足夠產生所欲純度位準所須之反覆清洗次數。雖然主要是就奈米晶體合成期間使用之界面活性劑方面做說明，但希望試圖要移除之界面活性劑組份可包括於晶體合成期間使用的有機界面活性劑，如高溫耐性之有機界面活性 20 劑，如ΤΟΡΟ，或其可包括外來的界面活性劑（亦稱“配位體”），其加入該奈米晶體中（如與合成期間使用之界面活性劑交換或添加至該界面活性劑中）是為了要促進該奈米晶體之整合性（溶解度、電氣整合等）。後者之界面活性劑類型之例子於如2003年9月4日提申之美國專利申請案第 31 200524973 10/656,910號中有說明，之前已有將此案之全部内容與目的併入本案以為參考。根據本發明之特別態樣，在成長或合成步驟之後，藉由重複的沈澱、再溶解與沈澱之處理收集與清潔該奈米晶 5 體直至獲得所欲之純度位準。第2圖提供簡要地說明本發明之加工法之流程圖。特別地，首先將該奈米晶體群落配製於該奈米晶體與污染性界面活性劑二者均可溶於其中之溶劑混合物中，如衍生自該奈米晶體之合成（見第1圖）。之後改變該溶劑混合物，藉此該奈米晶體不再溶於所產生的溶 10 劑混合物中，回收該沈澱的奈米晶體。之後將該回收的奈米晶體再溶解且再沈澱許多次至達到所欲之純度位準。 1.雙溶劑方法於第一實施例中，該奈米晶體群落之清洗是使用混合的溶劑方法來進行，該方法使用包括至少二種具有不同極 15 性之溶劑之溶劑混合物，藉此該奈米晶體可溶於足夠濃度之非極性或較低極性之第一溶劑中，而該界面活性劑部分則溶於足夠濃度之較高極性之第二溶劑中。於第一或增溶溶劑混合物中，該較高極性與較低極性溶劑兩者均以此容許濃度存在，如晶體與界面活性劑兩者均溶於該一混合物 20 中。典型地，該混合物之奈米晶體部分係藉由提高該第二或較高極性溶劑之濃度（或降低該第一或較低極性溶劑之濃度）至該奈米晶體不再溶解之程度，而從該溶劑混合物中沈澱出來。如此技藝人士所希望的，反向處理亦可使用在當該奈米晶體具有足夠大量與其連結之增溶界面活性劑 32 200524973 日$，如使其更溶於較高極性之溶劑中，之後可藉由增加該混合物中較低極性之溶劑的濃度來指定沈澱。 5 10 15 20 之後藉由如離心、過濾或類似的方法將該沈澱的奈米晶體彳< 戎溶劑混合物中分開來，並將其再懸浮於額外量該奈米晶體與界面活性劑二者均會再次溶解之溶劑混合物中。任擇地重複此方法以產生所欲的純度位準。此重複的處理可進行-選定的重複次數，如已知產生所欲純度所需之人數。選擇性地’以及於特定較佳態樣中，之後典型地檢查該溶解的奈米晶體之純度，如以決定該組成物中界面活之位準低。之後任擇地重複該沈;殿與再溶解步驟直至該奈米晶體混合物中游離態界面活性劑的數量低於該全部界面活性劑濃度（游離態與結合態）_%或低於 5%，較佳地低於該界面活性劑總數量的丨％，更佳低於〇· 1 %。於增溶與致沈殺溶劑混合物中所使用之溶劑以及於每 -個混合物中其等相對之濃度，典型地隨著該奈米晶體以及欲移除之有機污染物(如存在之界面活性劑的類型）之本貝而改變、然而-般而言，該無機奈米晶體群落—般係溶於相對較低極性之溶射，諸如甲苯、苯或咏分枝與無分枝六碳舰之混合物）料，以及氣仿(其物—般為極性的，但相對極性低於如甲醇，且奈米晶體會溶於盆中）。相反地’有機材料以及特暇更高極性之有_料，即界面活性劑，典魏缺料較高歸之環❹，諸如相對低 =置酒精’如甲醇與乙醇，以及在特顺佳界面活性劑歹子中，具有大於二個碳原子之酒精’如異丙醇、丁醇 33 200524973 等。結果，根據本發明之特定態樣，該溶劑混合物之較低極性溶劑部分典型地包括諸如氯仿、甲苯、己烷、苯等之較低極性溶劑，以及諸如曱醇、乙醇、異丙醇、丁醇、乙酸乙酯、丙酮等之較高極性溶劑。該增溶溶劑混合物巾較低極輯較高極性溶劑之相對濃度典型地從約1〇: 1至約3 : 1之範圍，特佳的比率是將近 4 · ；1。在將該奈米晶體從該增溶溶劑混合物中沈殿出來方面，典型地可改變其比率至介於約2 :丨與丨：2之間。此比 10 15 20 率之改變典型地係藉由提高該較高極性溶劑之濃度來完成，如藉由添加較高極性溶劑至該混合物中，但亦可住擇地藉由降低該較低極性溶劑之濃度來完成，如藉由蒸發等。如所述的，沈澱任擇地是奈米晶體大小選擇性的。該奈米晶體一經沈澱，其典型地可藉由許多方法而與懸洋的液體部分分開，包括離心、過濾等。之後將該分開的不米日日體再溶解於該第一溶劑混合物（增溶溶劑混合物）重複4沈與分開步驟直至達到該所欲純度。如本於明’此典型地意指於該合成混合物中進行至少3次沈搬與再溶解循環，較佳地4或更多次循環，於一些例子中，於％成反應混合物中進行5或更多次或甚至6或更多次沈殿^ 溶解循環。可在任何或所有的重複清洗循環後，檢查該含奈米曰體之溶液中游離能w工、曰曰雕L界面活性劑之位準，以確定該溶液之純 X Ik查可n由任何會提供所須資訊之方法來進行， b括’但不限於31PNMR。此檢查可用作為繼續或停止重複 34 200524973 清洗步驟之基礎，或可用於設定所需清洗步驟的基準，以決定到達所欲純度需多少步驟。一旦該奈米晶體已藉由進行重複的沈澱與再溶解一預定的次數後達到所欲之純度位準，或藉由分析以決定純度 5已達到純度位準，則之後任擇地接受額外的加工步驟處理，如將於下文中更詳細地說明（見如“減少結合態界面活性劑”標題一節）。 2.單一溶劑交換方皇於一選擇性方法中，係使用接近完全溶劑交換方法來 10 降低奈米晶體製品中游離態界面活性劑之位準。此方法簡要地於第2圖所示之流程圖中說明。特別地，不是使用雙溶劑混合物，此奈米晶體係使用諸如低分子量酒精(如甲醇等）之較高溶劑而從其合成之起始反應混合物(202)中沈澱出來 (步驟204)。如上，沈澱之達成一般是藉由以反應混合物對 15 較高極性溶劑之比介於約2 : 1至1 : 2間之比率添加該極性組份，直至該奈米晶體從該溶液中沈澱出來。如之前所述，藉由選擇性沈澱該混合物，亦可於該起始混合物中進行一些程度的大小選擇’因為奈米晶體易於呈大小依賴性方式從該反應溶液中沈澱出來。一旦該所欲的奈米晶體已從該 20 溶液中沈澱出來，就以如離心與倒出液體、藉由過濾等將該奈米晶體從該液體中分開來（見步驟206與208)。之後將該奈米晶體再溶解於較低極性之溶劑中，如甲苯、氣仿等（步驟210)(或如之前所述之混合的溶劑）。然後必要的話，重複沈澱與再溶解步驟（步驟214)，以 35 200524973 產生與游離態界面活性有關之所欲的純度位準（212)。如上，沈澱之達成一般是藉由以較低極性對較高極性溶劑之比介於約2 ·· 1至1 : 2間之比率添加該較高極性組份，直至 δ亥奈米曰曰體從5亥 >谷液中沈;殿出來。如上述雙溶劑之方法， 5該沈殿與再溶解之循環典型地在該起始反應混合物中進行至少3次，較佳4或更多次、於某些例子中，5或更多次以及於某些例子中6或更多次。亦如上所述，最感興趣的不必然為所進行之重複沈澱步驟之次數，而是最後的沈澱步驟後界面活性劑之結果位準。如之前所述，反覆清洗處理之後， 10殘留於該含奈米晶體之溶液中的游離態界面活性劑，典型地低於界面活性劑總存在量（游離態與結合態）的10%，較佳低於5%，更佳低於1%，又更佳地低於〇1%。在此使用之殘留的界面活性劑之百分比一般是使用NMR來測定，如31p NMR。在此所述之百分比，例如，代表使用此系統，在分 15析100 配製於〇·75 ml甲苯中之奈米晶體後所測定之值，其於破NMR掃描11〇〇次後，沒有可偵測到之游離態界面活性劑之波峰。再掃描更多次可偵測到污染性界面活性劑，但預料位準會低於在此所述之百分比。第3A_G圖提供每一次反覆清洗步驟後，於奈米晶體製品中游離態與結合態界 20面’舌性劑的標繪點。如圖中所示，該溶液中游離態界面活性劑之位準於每一次清洗後明顯地降下來，且事實上在第四次清洗步驟後已偵測不到（第3D-3G圖）。後、’哭的沈殿步驟典型地以之前所述之比率添加較高極性之溶劑’如較低極性對較高極性之溶劑比率介於2 : 1至 36 200524973 1 : 2之間。此可以與在第一沈澱步驟中所使用之相同的位準，或其可以高於該第一步驟中使用之位準。特別地，如上所述，該第一沈澱步驟亦可用大小選擇方法，其需要嚴密控制所添加之較高極性溶劑，如以沈澱一些，但不是溶 5 液中所有的奈米晶體。另一方面，後續的沈澱步驟是著重於回收即使不是全部也是大部分的奈米晶體，而不是此大小選擇。據此，於許多情況下，於此後續的沈澱步驟中所添加之較高極性溶劑的數量將高於最初的沈澱。一旦該奈米晶體已藉由進行重複的沈澱與再溶解一預 10 定的次數後達到所欲之純度位準，或藉由分析以決定純度已達到純度位準，則之後任擇地接受額外的加工步驟處理，如將於下文中更詳細地說明（見如“減少結合態界面活性劑”標題一節）。 3.液態-液態萃取方法 15 於另一選擇性方法中，係使用液態_液態相分離方法減少該奈米晶體群落中游離態界面活性劑之位準。於此方法中，該奈米晶體係與一該奈米晶體可溶於其中之第一溶劑以及一該奈米晶體較不溶於其中之第二溶劑（如不溶的）合併。容許該第一與第二溶劑形成一包含該第一溶劑與該奈 20 米晶體之第一液相，以及包含該第二溶劑之第二液相，且之後將該等相分開（如用移液管、倒出等方法將一相移出另一相）。因為該界面活性劑典型地均可溶於該第一與第二溶劑兩者中（且較佳地比該奈米晶體更可溶於該第二溶劑，以及更佳地其本身溶於該第二溶劑中之程度高於溶於該第一 37 200524973 溶劑），此方法導致具有該奈米晶體之溶液中游離態界面活性劑數量的減少。任擇地重複此方法以產生所欲之純度位準。此重複的處理可進行一選定的重複次數，如已知要產生所欲純度所 5 需之次數。例如可重複此步驟2或更多次、3或更多次、4或更多次、5或更多次或甚至6或更多次。於特定較佳態樣中，典型地檢查該溶解的奈米晶體之純度，如以決定該組成物中界面活性劑之位準是否夠低。之後必要的話，任擇地重複該結合、相形成與分開步驟次數直至該奈米晶體混合物 10 中之游離態界面活性劑的數量低於該全部界面活性劑濃度 (游離態與結合態）之10%或5%，較佳地低於該界面活性劑總數量之1%，更佳地低於0.1%。需重複該循環時，可將新的第二溶劑與含該第一溶劑與奈米晶體之第一液相結合，或將該奈米晶體從該第一液 15 相中分開來(如藉由離心、過濾、沈澱等等）、再溶解於新的第一溶劑中且與新的第二溶劑結合。該第一與第二溶劑以及其等之相對比率，典型地隨著該奈米晶體以及要被移除之有機污染物（如所存在之界面活性劑類型）之本質而改變。典型地，在清潔無機奈米晶體 20 方面，該第一溶劑會比該第二溶劑之極性低。於一範例實施例中，以TOP作為界面活性劑（或界面活性劑之一種）製備成之奈米晶體（如Pd或InP)係藉由液態-液態萃取法，以曱苯作為該第一溶劑而甲醇作為該第二溶劑來加工。值得注意的是，該第一與第二溶劑僅於如欲移除 38 200524973 之界面活性劑存在時不互溶之條件下使之存在下，甲苯與甲醇會相混合且不會〜= 相，但在醫之存在下，其等不會混合在—起二柳 =個液相，因此可用於液態娜萃取，以移除此界= i ㈣方法任擇地此所述之液態·固態萃取步驟結合—起使用（如於標題 10 劑方法m劑交換方法’，之節段中所述之清2 法）。例如，該奈米晶體可以至少_個液態_液態萃取循及至少—觀澱與再溶_環處理，該等«依任何摩岸進行。、厅 -旦該奈米晶體已藉由進行重複的萃取—預定的後達到所欲之純度位準，或藉由分析以決定純度已達到純度位準，則之後任擇地接受額外的加工步驟處理，如將於 15下文中更詳細地說明（見如“減少結合態界面活性劑，，榡題二 λτ/r \ 即）。200524973 IX. Description of the invention: [Cross-reference to the relevant technical field of the invention 1 Reference application of this application This application is a non-provisional invention patent application, which claims the following priority and advantages of the previous 5 temporary patent applications: 2004 September 11, US Patent Application No. 60 / 544,285 filed by Scher et al., Entitled " Methods of processing nanocrystals, compositions, devices and systems including same "; U.S. filed by Scher et al. On September 4, 2003 Patent application No. 10 / 656,910, titled 10 `` Nanostructure and nanocomposite based compositions and photovoltaic devices "; US Patent Application No. 10 / 656,802, filed by Whiteford et al. On September 4, 2003, entitled" Organic species that facilitate charge transfer to or from nanostructures ", the entire disclosure and purpose of these are incorporated herein by reference. 15 Field of the Invention The present invention relates to the field of nanostructures. In particular, the present invention relates to a method for processing nanocrystals and compositions, components and systems including the processed nanocrystals. 20 BACKGROUND OF THE INVENTION In the field of "Nano Technology", some people heralded her arrival and regarded its development as providing the next important technological revolutionary, while others laughed at it, and regarded Nano Technology as merely attracting innovation. The latest topic technology for investment companies. Although their basic elaboration of the vision of technology is different, members of both sides of the battalion 200524973 battalion pointed out some of the same issues, that is, nanotechnology must emphasize whether it is adventurous to achieve its vision. In particular, it should be noted that although both camps tend to recognize that nanomaterials usually have such structures. , Electrical, optoelectronic, and thermoelectric unique and potential valence characteristics' But the ability of scientists, even users or consumers to obtain these unique and value characteristics, may have substantial impact on the full benefits of these materials obstacle. For example, 'Although nanowire-based circuits may show a wide range of potential benefits in the electronics industry, joining these materials to produce this novel and improved 10-circuit interface has not been very successful, with some notable exceptions: see Such as Duan et al., Nature 425: 274_278 (2003). As far as nanowire electronics is concerned, the inability to obtain the advantages of this nanomaterial is mostly a matter of physics, because the size of the material is so small that it makes practical physical or electrical contacts under robust repeated manufacturing processes It's actually getting harder and harder. Relevantly 'Although there is a very promising theoretical energy conversion efficiency, the previously mentioned photovoltaic materials based on nanomaterials have not yet reached the desired efficiency, mostly due to the inability to successfully and completely use this material. Integrated into photovoltaic cells to obtain converted energy. In this example, it is generally believed that the failure to obtain the properties of the material may be (at least in part) a chemical problem, which involves the need to obtain access through the surface of the nanomaterial and the ability of the nanomaterial to function effectively in its specific composite environment. . Unofficially, it is the electrical connection function or chemical integration of nanomaterials. It will be recognized that there is a need for nanocrystals 200524973 that enable the processing method to produce easier integration and the nanocrystal community itself. The present invention meets these and other needs. [Summary of the Invention] Summary of the Invention 5 In order to improve the efficiency of the electronic and physical interactions between nanocrystals and their surroundings, the present invention generally relates to a more complete method for processing nanocrystals. For example, the present invention provides a method for processing nanocrystals that can be used to remove excess free and / or bound surfactants from nanocrystals. The composition of the processed nanocrystals is also a feature of the present invention. The first embodiment provides a method for processing nanocrystals. In this method, nanocrystals are formulated in a first solvent in which the nanocrystals are soluble. The nanocrystal has a total number of surfactants connected to it. The total number of surfactants includes a number of free surfactants and 15 surfactants combined with a number of nanocrystals. The nanocrystals are precipitated by adding a second solvent having a higher polarity to the first solvent to produce a precipitation solvent mixture in which the nanocrystals are insoluble, to provide precipitated nanocrystals. The precipitated nanocrystals are separated from the precipitation-inducing solvent mixture, and then dissolved again by adding a third 20 solvent in which the nanocrystals are soluble. The surfactant is typically soluble in at least the second solvent and the precipitation-inducing solvent mixture. Optionally, the precipitating, separating, and re-dissolving steps are repeated, such as a selected number of repetitions and / or until the nanocrystals reach a desired level of purity. For example, the precipitation, separation and redissolution steps may be repeated 2 or more times, 3 or 200524973 times, 4 or more times, 5 or more times, or even 6 or more times. As for another example, the precipitation, separation, and re-dissolution steps can be repeated until the amount of free surfactants linked to the nanocrystals is less than 5% of the total amount of surfactants linked to the nanocrystals, which is low. At 1%, below 0. 5%, even lower than (U%. In the present example, after at least one re-dissolution step, the nanocrystals are then checked to determine the amount of free surfactant that is still bound to the nanocrystals. 10 15 In a specific embodiment, the first solvent includes a single solvent; in an optional embodiment, the solvent is a solvate with Wei Wei solvent. Blood type, the polar solvent is the same as the second solvent. The polar solvent is basically The above may be any suitable polar solvent, including, but not limited to, alcohol (such as methanol or alcohol), vinegar (such as acetic acid) or ketone (such as _) in the example-the second solvent _ (Such as isopropyl alcohol) having at least two carbon atoms. Similarly, the lower polarity can be basically any suitable two-dose 'pack 7 (not limited to, chloroform, toluene, chain) and benzene. = 地 '㈣ [Soluble solvent with lower purity, high-polarity falling blood II' x ratio of low-polarity solvent to higher-polarity solvent = Large =, greater than 4: 1, or about 4 ... Similarly, in this 4 = agent mix = lower polarity solvent to higher polarity solvent (ie, the first agent plus the solvent contained in the first, ~ to between about 1: 2 (polar solvent in the body) typical The lower polarity of the solvent mixture is between _). For example, '于此敎?. 1, the ratio of the mixture of 7 to higher polar solvents can be 2. 1 or lower, such as 1: 1 or lower. 20 200524973 Typically, in the precipitation-inducing solvent mixture, the ratio of the first solvent to the second solvent is between about 2: 1 to about 1: 2 (volume: volume). For example, in an embodiment category, the ratio of the first solvent to the second solvent in the precipitation-inducing solvent mixture is 2: 1 or lower (such as 1: 1 or lower). 5 The first solvent can be essentially any non-polar or relatively non-polar solvent. Suitable first solvents include, but are not limited to, chloroform, toluene, chain burner (e.g., hexane), and benzene. Similarly, the second solvent can be essentially any polar or relatively polar solvent. Suitable second solvents include, but are not limited to, alcohols (such as methanol or preferably alcohols having at least two carbon atoms, such as ethanol, isopropyl alcohol and butanol), acetates (such as ethyl acetate), and ketones (Such as acetone). The third solvent may be the same as the first solvent, but it need not be the first solvent. Another embodiment provides a method for removing excess bound surfactant from nanocrystals. In this method, a solution containing nanocrystals dissolved therein is provided. The nanocrystal has a total number of interfacial active agents connected to it. The total number of interfacial active agents includes a free interfacial active agent and a combined interfacial active agent. The amount of free surfactant in the solution is less than 10% of the total amount of surfactant (e.g., less than 5%, 1% or 0 of the total amount of surfactant). 1%). A base is added to the nanocrystals, and the base forms an insoluble salt with the bound surfactant. 20 The insoluble salt is separated from the nanocrystals dissolved in the solution to provide nanocrystals having a partially monolayer to two layers of a surfactant bound thereto. The insoluble salt can be obtained by, for example, centrifuging the nanocrystal and the insoluble salt, and pouring out the nanocrystal 200524973 dissolved in the solution from the pellet of the insoluble salt, and the nanocrystal dissolved in the solution. To separate. Various suitable systems are well known in the art. Examples include, but are not limited to, sigma, aniline, double sigma, travel bites, saliva, diethylamine, triethylamine, and di-isopropylamine. The base is typically added in a ratio of base to nanocrystalline solution of 5 to 1: 1 (volume: volume); such as greater than 2: 1 or even greater than 3. · 1 ° Yet another embodiment provides processing in general Nano crystal method. In the method, the nanocrystal system is formulated in a first mixture in which the nanocrystals are soluble. The first mixture includes a first solvent and / or a reaction mixture in which the nanocrystals 10 are synthesized. The nanocrystals are precipitated by adding a second solvent to the first mixture to generate a second mixture in which the nanocrystals are insoluble, to provide precipitated nanocrystals, and then from the second mixture. Separate. The precipitated nanocrystals are dissolved again by adding at least the first solvent to provide a third mixture. The polarity of the third mixed compound is adjusted to provide a fourth mixed compound in which the nanocrystals are insoluble, and precipitated nanocrystals are obtained. The precipitated nanocrystals were separated from the fourth mixture. Repeat the redissolving, precipitating, and separating steps until the nanocrystals are redissolved in the first solvent, the amount of free surfactant is less than 5% of the total amount of the total surfactant, and the amount of the surfactant is 20%. The total number includes a number of free surfactants and a number of nanocrystal-bound surfactants. Preferably, the steps of re-dissolution, precipitation and separation can be repeated until the amount of free surfactant is less than 1% of the total amount of the surfactant, and less than 0. 5% or better below 0. 1%. For example, the redissolving, precipitating, and separating steps may be repeated 2 or more times, 3 or 10 200524973 times, 4 or more times, 5 or more times, or even 6 or more times. In a particular embodiment, the nanocrystals are inspected after at least one re-dissolution step to determine the amount of free surfactant. In some embodiments, the first mixture includes only the first solvent and / 5 or the reaction mixture. However, in other embodiments, the first mixture may also include the second solvent. Similarly, the redissolution of the nanocrystals can be performed by adding the first solvent to the precipitated nanocrystals to provide the third mixture, or by adding the first solvent and the second solvent. As for the embodiments described above, in the first and / or third mixture, the ratio of the first solvent to the second solvent is typically between about 3: 1 to about 10: 1 (volume: volume) However, in the second and / or fourth mixture, the ratio of the first solvent to the second solvent is typically between about 2: 1 to about 1: 2. The polarity of the third mixture is typically adjusted by adding the second solvent to the third mixture, but in embodiments where the third mixture includes the first and the second solvent 15, the The polarity can be adjusted by removing at least a portion of the first solvent (eg, by evaporation). Typically the first solvent is less polar than the second solvent (however, nanocrystals have a sufficiently high level of solubilized surfactant to make them more soluble in higher polarity than lower polarity In an embodiment of the solvent, the polarity of the first solvent may be higher than that of the 20th second solvent). As illustrated in the examples above, many of the first and second solvents are well known in the art. For example, the first solvent may be chloroform, toluene, an alkane (such as hexane) or benzene, and the second solvent may be an alcohol (such as methanol or an alcohol preferably having at least two carbon atoms, such as ethanol, isopropyl, Propanol or butanol), acetate 11 200524973 (such as ethyl acetate) or ketones (such as acetone). Other embodiments generally provide methods for processing nanocrystals. In the method, a solvent mixture including a first solvent in which the nanostructure is soluble and a second solvent in which the nanostructure is insoluble is added to the nanostructure 5. The nanostructure is killed by adding an additional amount of a second solvent, which is sufficient to precipitate the nanostructure from the solvent mixture. The nanostructure is then separated from the solvent mixture (e.g., by centrifugation), thereby removing excess organic surfactant (which continues to be present in the solvent mixture) from the nanostructure. Optionally, repeat the adding, precipitating, and separating steps 2 or more times (such as 3 or more times, 4 or more times, 5 or more times, or 6 or more times). The nanostructure can be analyzed before, for example, Shen Dian, after separation and resolving, after each cycle of precipitation and redissolution, or after a predetermined number of cycles to determine the amount of surfactant present. Optionally, repeat the adding, precipitating, and separating steps until the amount of 15 surfactant present reaches a desired amount (e.g., until the amount of free surfactant is less than 10%, 5%, 1%, or 0. 1%, etc.). As for the above embodiments, some of the first and second solvents may be selective. For example, the first solvent may include toluene or chloroform, and the second solvent may include alcohol (e.g., isopropanol) or acetate 20 (e.g., ethyl acetate) containing more than two carbon atoms. The solvent mixture added to the nanostructure typically comprises the first solvent and the second solvent in a ratio between 1: 1 and 10: 1. As a specific example, the solvent mixture added to the nanostructure may include four parts of toluene to one part of isopropanol. 12 200524973 The method optionally includes additional purification steps, such as removing even more excess surfactant. For example, pyridine exchange can be performed, and the organic salt produced can be precipitated (and removed, such as after centrifugation), leaving the nanostructure in solution. 5 Still other embodiments provide a method for processing nanocrystals. In the method, the nanocrystal is combined with a first solvent in which the nanocrystal is soluble and a second solvent in which the nanocrystal is insoluble (eg, insoluble). The first and second solvents are allowed to form a first liquid phase containing the first solvent and the nanocrystal, and a second liquid phase containing the second solvent, and the 10 phases are then separated. Because the surfactant is typically soluble in both the first and second solvents (preferably more soluble in the second solvent than the nanocrystals, more preferably it is soluble in the second solvent itself) To a higher degree than in the first solvent) so this processing method results in a reduction in the amount of free surfactant in the solution with the nanocrystals. 15 Optionally repeat this process to achieve the desired level of purity. This repetitive processing can be performed a selected number of repetitions, such as the number of times it is known to obtain the desired purity. For example, such steps may be repeated 2 or more times, 3 or more times, 4 or more times, 5 or more times, or even 6 or more times. In a specific preferred aspect, the purity of the nanocrystals of the gluten solution is determined, for example, to determine whether the level of the interfacial active agent in the composition is sufficiently low. After that, if necessary, the steps of binding, phase formation and separation are optionally repeated until the amount of free surfactant in the nanocrystalline mixture is less than 10% or less than 5% of the total surfactant concentration (free and bound). %, Preferably less than 1% of the total amount of the surfactant, and more preferably less than 0.01%. 13 200524973 The first and second solvents and their relative ratios typically depend on the nature of the nanocrystals and the organic impurities to be removed, such as the type of surfactant present. Typically, the first solvent is less polar than the two solvents in cleaning inorganic nanocrystals. In a specific example, a nanocrystalline system prepared using TOP 5 as a surfactant is treated with toluene as a first solvent and methanol as a second solvent. Another feature of the present invention is that the nanocrystals processed by any of the methods described herein (such as nanocrystals without excessive free and / or bound surfactants) include the composition of the processed nanocrystals Objects, systems and 10 components. Accordingly, an embodiment provides a composition comprising a nanocrystal community dissolved in a first solvent. The nanocrystals are connected to a total amount of surfactants, and they include a quantity of bound surfactants and a quantity of free surfactants in solution. The amount of the free surfactant is less than 5% of the total amount of the surfactant, preferably less than about 1%, and less than about 15 to about 0.1. 5%, preferably less than about 0. 1%. As mentioned previously, the nanocrystals can be of essentially any formation, size, and / or composition. A related embodiment generally provides a composition comprising a nanocrystal community having nanocrystals bound to the nanocrystals and dissolved in a first solvent. The nanocrystal contains less than two layers of surfactants attached to it. Preferably, the nanocrystal comprises about a single layer or fewer layers of surfactants attached thereto. Other related embodiments generally provide a composition comprising a nanocrystal community and a surfactant bound thereto, wherein the surfactant comprises less than two layers. For example, the surfactant preferably comprises about a single layer or less. 14 200524973 As mentioned, nanocrystals processed by the method of the present invention are optionally incorporated into various compositions and components. Therefore, an exemplary type of an embodiment provides a composite including an organic polymer matrix and a nanocrystal community disposed within the organic polymer matrix. The nanocrystal has a surfactant attached to the nanocrystal, and the surfactant includes less than two layers (for example, the surfactant may include about a single layer or fewer layers). Another embodiment provides a composition including a first nano crystal community and a second nano crystal community. The first nanocrystal community has a surfactant attached thereto, the surfactant comprising less than two layers 10 (eg, about a single layer or less). The second nanocrystal community has a composition different from that of the first nanocrystal community, and is dispersed in the composition together with the first community. The second community optionally also contains less than two layers of the same or different surfactants. The interspersed first and second nanocrystal communities may, but need not be, disposed in a matrix (such as an organic polymer matrix). 15 Brief Description of the Schematic Figure 1 is a flow chart that briefly describes the synthesis of nanocrystals using a surfactant-controlled synthesis method. Fig. 2 is an example briefly explaining the synthetic processing steps after the present invention is applied to a nanocrystalline product. Figures 3A-3G are 31P-NMR spectra of nanocrystalline products after different cleaning and processing steps, which show the level of free and bound surfactants linked to these nanocrystalline products. Picture G shows enlarged views of the peaks of the surfactants in the bound state of picture D (top, cleaning solution 4), picture E (middle, cleaning solution 5), and picture F (bottom, cleaning solution 6). 15 200524973 [Embodiment] Definition Unless defined, all technical or scientific terms used herein have the same meaning as those generally familiar with those skilled in the art related to the present invention. 5 The following definitions supplement the definitions of terms in this technology and are for current applications, and should not be used in any related or unrelated cases, such as any jointly owned patents or applications. Although any methods and materials similar or equivalent to those described herein can be used in the practice of testing the present invention, the preferred materials and methods are those described herein. Accordingly, the purpose of the terminology used herein is to describe specific embodiments only and is not intended to be limiting. Unless specifically stated otherwise, the singular forms of "a," and "the," as used in this specification and the scope of the appended patent application, include plural objects. Thus, for example, "a nanostructure, including plural forms of nanostructures," a solvent "includes a mixture of solvents, a surfactant, a mixture including 15 surfactants, etc. The term" about, , Refers to the difference between the given value of the value is +/- 10% of the stated value or optionally + / _ 5% or in some embodiments + / _ 1% Means that the nanostructure typically exhibits kmg-range ordering on one or more of the structures. Those skilled in the art are well aware that the term ‘’ long-range ordering depends on the absolute size of a particular nanostructure, because the ordering of a single crystal cannot extend beyond the boundaries of the crystal. In this case, "long-range ordering" will mean that at least the main dimension of the nanostructure is substantially ordered in a certain 16 200524973 case. The nanostructure may have an oxide or other coating, or may be a core and At least one shell composition. In this case, it can be seen that the oxide, shell or other coating need not exhibit this order (which may be amorphous, polycrystalline or otherwise). In this case, "crystalline", The phrase "substantially crystalline", "substantially single crystal" 5 or "single crystal" refers to the core of the nanostructure (excluding the coating or shell). The terms "crystalline" or "substantially" used herein "Crystalline" is also intended to include structures containing various defects, overlaps, atom substitutions, etc., as long as the structure exhibits substantially long-range ordering (if order exceeds at least the length of at least one axis of the nanostructure or its core) (Approximately 80%). In addition, it can be seen that the interface between the core and the outer side of the nanostructure, the core and the adjacent shell, or the interface between the shell and the second adjacent shell may include amorphous regions and may even be amorphous. Would hinder the nanostructure Is defined herein as the crystalline or substantially crystalline. When the term "single crystal 'structure for nm, meaning that the nanostructure is substantially crystalline and comprises substantially a single crystal. When used in a nanostructure heterostructure comprising a core 15 or one or more shells, "single crystal" means that the core is substantially crystalline and contains substantially single crystals. A "nano structure" is a structure having at least one region or characteristic dimension with a size of less than about 500 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Typically, the area or feature 20 dimensions are often along the smallest axis of the structure. Examples of this structure include nanowires, nanorods, nanotubes, branched nanostructures, nanopods (nanotetrapod), tripods, bipods, nanocrystals, nanodots, quantum dots, nano Rice particles and more. The nanostructure may be, for example, substantially crystalline, substantially single crystalline, polycrystalline, amorphous, or a combination thereof. In one aspect, each of the three dimensions of the nanostructure has a size of less than about 500 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. A "nanocrystal" is a substantially single crystal nanostructure. Nanocrystals therefore have at least one region or characteristic dimension with a size of less than about 500 5 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. In terms of material properties, nanocrystals may be substantially homogeneous, or may be heterogeneous (such as heterostructures) in specific embodiments. The term "nanocrystal" is intended to encompass a single crystal nano 10 structure that substantially contains various defects, overlaps, atom substitutions, and the like, and a single crystal nano structure that is substantially free of such defects, errors, substitutions. As for a nanocrystal heterostructure comprising a core and one or more shells, the core of the nanocrystal is typically substantially single crystal, but the shell need not be a single crystal. The nanocrystals can be made from essentially any suitable material. For example, the nanocrystals may include inorganic materials, semiconductor materials (such as Group II-VI, III-V 15 or Group IV semiconductors), metals, semi-metals, conductive materials, insulating materials, and / or the like. In one aspect, each of the three dimensions of the nanocrystal has a size of less than about 500 nm, such as less than about 200 nm, less than about 100 nm, less than about 50 nm, or even less than about 20 nm. Examples of nanocrystals include, but are not limited to, substantially 楕 round nanocrystals, branched nano20 crystals, and substantially single crystal nanowires, nanorods, nanodots, quantum dots, nanoquads Foot, Tripod, Biped and Branched Tetrapods (such as dendrimers) ° "Branched nanocrystals" are nanocrystals with three or more arms, each of which has a nanorod It is also a nanocrystal with two or 18 200524973 multi-arms, in which each arm has the characteristics of a nanorod and originates from a central region that has a crystal structure different from the arms. Examples include, but are not limited to, two-legged, three-legged, and nano-quadruped (quadruped). "Nanotetrapods, generally a four-sided branched nanostructure, have five arms that exit from the central area or core, and the angle between any two arms is approximately 109. 5. . Typically, the core has a crystalline structure, and the arms have another crystalline structure (It is worth noting that this does not prevent the nanotetrapods from becoming single crystals, because the arms and the core are stacked by For example, the core with a sphalerite structure and the arm with a wurtzite structure are connected by a 10-stack difference, which does not disrupt the four-sided bond of the two constituent atoms of the nanostructure). A "substantially rounded nanocrystal" is a nanocrystal having an aspect ratio between about 0.8 and about 1.2. "Aspect mtio" is the average of the length of the first axis of the nanocrystal divided by I5 by the length of the second and third axes of the nanostructure. Here the first and second axes are Its length is closest to the two axes that are equal to each other. For example, the perfect aspect ratio of a rod is the length of its major axis divided by the diameter of the cross-section perpendicular to (the normal line) to that major axis. A nano-20 structure having one major axis longer than the other two major axes. Therefore, the nanorods have a length to width ratio. The nanorods of the present invention typically have an aspect ratio between about 1.5 and about 10. But may have an aspect ratio greater than about 10, greater than about 20, greater than about 50, or greater than about lake, or even greater than about 10,000. &Amp; Long nanorods (such as those with aspect ratios greater than about 10) have The heart is called the noodle. The diameter of the nanorod is typically less than about 500 nm, preferably 19 200524973 less than about 200 nm, more preferably less than about 150 nm, most preferably less than about 100 nm, about 50 nm or about 25 nm, or even less than about 10 nm or about 5 nanometers. Nanorods can have a variable diameter or have a substantially uniform Diameter, that is, the diameter in the area with the most variation shows a variation of less than about 20% (such as less than about 5 10%, less than about 5%, or less than about 1%). Nanorods are typically substantially crystalline and / Or substantially single crystal, but may be, for example, polycrystalline or amorphous. A "surfactant" is a molecule capable of interacting with one or more surfaces of the nanostructure, the front side 4. One or more surfactants are typically used In the synthesis of nanostructures, it is used to help control the size and / or shape of the nanostructures produced, inhibit aggregation and maintain the solubility of the nanostructures and / or analogs. The total number of nanometer crystal communities in the solution "connected surfactants, including a quantity of free surfactants and a quantity of bound surfactants. A "bound state surfactant," or "nano 15 crystal-bound surfactant, is physically attached to the nano crystal (such as covalently or non-covalently attached to the surface of the nanostructure, or covalently). Ground or non-covalently attached to a molecule, the molecule itself is covalently or non-covalently attached to the surface of the nanostructure). "Free surface active agent, not bound to nano crystals." Solvent "is a liquid substance capable of dissolving other substances. The relative polarity of any of the 20 species / cereals can be determined by, for example, comparing their polar indices. Comparison (see, eg, CRC Handbook of Chemistry and Physics, 84th ed CRC Press). The term "matrix," as used herein, means a material, usually a polymeric material, in which a second material (such as a nanocrystalline composition is embedded) ) Or surrounded by _second 20 200524973 material. The substrate may be a conductive composition, a semiconductor composition, or a non-conductive composition. Various additional terms are defined or otherwise characterized herein. 5 Detailed description I. General description of the present invention The present invention is generally directed to a method for processing a nanocrystal community, and to a nanocrystal complex and composition produced by this method. This nanocrystal community and nanocrystal complex provide Increased performance characteristics due to its more complete processing and / or easier integration into its final deer application. Nanocrystals processed by the methods described herein are then easily integrated into a matrix including an organic polymer matrix, a matrix including other nanocrystals having the same or different composition, a sol-gel matrix, and a Taumann matrix , Inorganic matrix, and so on. 15 As mentioned earlier, a continuing difficulty associated with actually utilizing the beneficial properties of nanomaterials is the ability to effectively integrate these materials into their end use applications. Purely structure-based, the positioning and orientation of nanomaterials must be implemented either on a block basis or using self-alignment, positioning, or alignment techniques that take advantage of nanomaterial characteristics (such as chemical, high-energy, or magnetic). In other applications where structural integration is not critical, such as nanomaterial block applications, integration issues may still be important. For example, when using rice materials as blocks, but using their optical or electronic properties, proper integration of these materials may be critical in the matrix or matrix selected as the most suitable for a given application. This proper integration creates a difference between effectively using the properties of the nano 21 200524973 material and wasting those properties. In at least one example, it is generally believed that the extraction of electrical energy from nanomaterials in the form of separate charges is obviously affected by the nanomaterial and the surroundings of the nanomaterial (where the electrical energy is to be transmitted). Impact of Chemical Integration. As used in photovoltaic devices based on nanocrystals, such as photovoltaics, of particular interest is the transfer of charge from a charge-conducting matrix to the nanocrystal, or charge from the nanocrystal to charge conduction Matrix transmission. In particular, nanocrystals have been used and are proposed as charge separation components for some applications that include photovoltaic elements. In short, when light is irradiated on the nano 10 aa body, it has the effect of creating an electron hole pair or "exciton" in the crystal. When allowed to recombine within the crystal, the photoexciton emits a light wave that is characteristic of the size and composition of the crystal. However, when the electron (or hole) is successfully extracted from the crystal and conducted to one of a pair of opposite electrodes, a potential that can be used is created. 15 This characteristic is the fundamental basis for the use of nanocrystalline compositions in the next generation of photovoltaic cells. Specifically, because of the ability to provide these materials in flexible composites, the potential to manufacture this composite at a low price, the relative theoretical conversion efficiency of this material, and the coordination of these materials, we look forward to Mi Yueyue's body-based optoelectronic components have revolutionized the generation of this source. 20 Despite the expectations and early successes of optoelectronic technology using nanocrystals as start-up components, there is still room for substantial improvement, such as achieving the goal of approaching theoretical efficiency. Without being limited to a specific operating principle, it is generally believed that in prototype systems, at least part of the efficiency loss currently seen is caused by charge carriers (such as electronically conductive nanocrystalline components) and another—charge carriers 22 200524973 bodies (such as Hole conduction around the matrix), regardless of whether it is an organic conductive polymer matrix or adjacent nanocrystals with different compositions. It is generally believed that this poor connection will lead to incomplete charge extraction and separation from the nanocrystal, which in turn is considered to be at least one reason below the theoretical efficiency. 5 10 15 20 Accordingly, in at least one aspect, the present invention provides processing of the nanocrystal to remove excessive levels of contaminating materials that would affect the connection. Examples of such contaminants include surfactants used in the synthesis of the nanocrystals and / or used to improve the processing characteristics of the nanocrystals, such as its solubility. In particular, without being limited to the theory, it is generally believed that the surfactants mentioned above provide a barrier layer that hinders the transfer of charge between the nanocrystalline component and its surrounding matrix. Unfortunately, in order to provide a reasonable treatment of the nanocrystalline module, a pure interface is necessary. To be clear, if the nanocrystal's surfactant is not sufficiently coated, it will be lumped together with other nanocrystals and will not be well dispersed in its final matrix. This will lead to the performance of charge extraction Poor and even produce non-functional complexes. Therefore, the object of the present invention is to provide a nano crystal community, which is coated with sufficient surfactant to allow the nano crystal to be soluble, but not to excessively hinder the charge from the nano crystal. Lead out. The concept of miscellaneous used here, #when it should secrete a nanocrystal community, it is like imagining that nanocrystals can exist in solution in a substantially non-aggregated state, such as nanocrystals in a given community More than 70%, 80% or 90% will not agglomerate with other nano crystals in the same group and fall, preferably more than 95% will not agglomerate, more preferably greater than _ is not Will agglomerate. Also without being limited to a particular operating theory 23 200524973, it is generally believed that this coating requires sufficient surfactant to be present in order to provide a portion of the monocrystalline to more than two or even multiple layers of interfacial activity on the nanocrystal The agent coats a nanocrystal. Therefore, in at least one aspect, the present invention provides a method for processing nanocrystalline five-body communities and the resulting composition to remove excess organic materials and, in particular, for generating or dissolving such nanocrystalline communities. Surfactant, which provides a good interaction between nanocrystals in the community and their surroundings in terms of charge extraction and physical interactions (such as solubility). For the sake of discussion, the exemplary system is described in terms of nanocrystal communities arranged in a matrix (such as a conductive polymer matrix) to form a composite material. However, it should be readily apparent that the present invention has broad applicability to situations where it is desired to improve the interaction between a nanocrystal and any material surrounding the nanocrystal, including, for example, other nanocrystals, water-based materials, solids such as Substrate, insulator, etc. For example, it should be easy to see that the application of nanocrystals to a wide variety of photoelectric and / or cold light uses the same basic principle of charge introduction or extraction, which can improve the charge transfer between the substrate and the nanocrystals. And benefit, such as LEDs based on nano crystals and so on. In general, the present invention provides a method for reducing excess levels of a surfactant in a nanocrystal community by performing one or both of the following, i.e., from a mixture including the nanocrystal Remove excess unbound surfactants and remove excess levels of surfactants that can be physically linked to the nanocrystal (regardless of the nature of the link, this is generally referred to as the "bound" surfactant) ). By way of example, the "bound state" surfactants used herein include covalent linkages, but also include non-covalent linkages such as van der Waals, hydrophobic / 24 200524973 hydrophilic parent interactions, and the like. In general, the objects of the present invention are achieved by cleaning the nanocrystal community to remove excess unbound or free surfactants, and using exchange or titration methods to remove the excessively bonded nanocrystals. Bound state surfactant. 5 Although previous researchers have discussed the washing steps used to process nanocrystals (see e.g. Huynh et al., Adv. Mater. 11 (11): 923-927 (1999); and Greenham, et al. , Phys. Rev. B 54 (24): 17628-17635 (1996)), however, this step results in nanocrystals with relatively high levels of contaminating surfactants (both bound and free). Without being limited to a particular theory of operation, this excess level / defective substance is generally considered to be at least part of the reason for the ordinary (relative to its theoretical potential) performance of electrical or optoelectronic components based on these materials. Furthermore, these early literatures clearly revealed that additional cleaning steps must be avoided, suggesting that further cleaning steps would reduce the solubility of the entire nanocrystalline component and therefore reduce its integration. In addition, although the cleaning steps are discussed, in general, this cleaning only focuses on washing and rewashing the precipitated nanocrystals to removing any remaining free material from the precipitated crystals, and the repeated cleaning It is easy to re-precipitate and re-suspend the same pollutants as re-washing. However, 'as opposed to the teachings of these early publications, heading 20 of the present invention explicitly provides further processed nanocrystals, especially organic materials (such as surfactants) that have less pollution than those described. ) Of nano crystal community. This nanocrystalline community provides improved performance characteristics and it is generally believed that a certain degree of privacy prevents the removal of components due to excessive amounts. Furthermore, despite the removal of the interface activity, these nanocrystalline communities still retain the necessary solubility, 25 200524973, to be suitable for processing in desired components, applications or systems. Accordingly, in a first aspect, the present invention provides a processing method for repeatedly cleaning a nanocrystalline component to remove excess levels of free surfactants present in the nanocrystalline solution. The method involves repeating the process. Selective 5 precipitates and redissolves the nanocrystals. Removal of excess levels of free surfactant means that in all the surfactants in the nanocrystal solution composition produced, the free component is less than 10% of the total surfactant present, preferably less than 5%, more preferably less than 1%, and in some cases preferably less than 0. 1%. Similarly, the resulting nanocrystalline composition is easily incorporated into composites for various applications, such as organic polymer matrices, mixed nanocrystalline materials, sol-gel matrices, and the like. The determination of the amount of free and bound surfactants can be carried out by a number of methods. In particular, Figures 3A-3G show a series of plots of a repeated cleaning step of the CdSe nanorod b using the method described herein. As shown, each successive washing step significantly reduces the amount of free surfactant (spike) relative to the amount of bound surfactant (broad peak). After four washing steps, the amount of free-surface surfactant was almost unmeasured in the '5Nellite-containing solution (see Figure 30). A slight flattening of the broad peak shows that 20 additional cleaning steps (e.g., 5th and 6th times) also began to further reduce the level of bound surfactants (3E, 3 continued). The relative amounts of hetero and bound surfactants can be determined, for example, by comparing the areas under the respective peaks in the n M r plot. As mentioned earlier, reducing the amount of free interfacial activity in nanocrystal-containing solutions 26 200524973, and therefore the amount incorporated into any resulting component, layer or system, optionally by repeated cleaning The method is carried out, which involves selectively removing the nanocrystalline portion from the solution, leaving the main contaminating free-state surfactant, redissolving the nanocrystalline 5 and repeating the precipitation and redissolution steps until the solution The level of free surfactant in the medium is reduced to the desired level. In a second aspect of the present invention, the nanocrystal community that has been washed to remove excess free surfactant is subjected to additional processing steps to reduce the amount of bound surfactant that is bound to the nanocrystal. Bit 10 level. As mentioned above, it is generally necessary to reduce the level of bound surfactant to nearly one or one early layer on the surface of the crystal. Typically, this includes from about a portion of a single layer to about two layers of a surfactant. The cleaning step as described above is generally performed by precipitation and centrifugation. However, in this aspect of the present invention, an excessive amount of surfactant is selectively precipitated to leave the nanocrystalline 15 body. II. Synthesis of Nano Crystals The synthesis of semiconductor nano crystals and their applications have been explained in detail before. See, for example, U.S. Patent Nos. 6,322,901, 6,207,229, 6,607,829, 6,617,583, 6,326,144, 6,225,198 20, and 6,306,736 (the entire contents and purpose of these are hereby incorporated into the present case as if reference). See also US Patent Application No. 60 / 591,987 filed by Scher et al. Entitled "Process for group III-V semiconductor nanostructure synthesis and compositions made using same". The semiconductor nanocrystals used herein include a wide variety of nanoparticle-based materials, such as having at least one transverse dimension less than about 500 nm, and preferably less than 100 nm. These nanocrystals can be composed of a wide range of semiconductor materials, including, for example, m-v, I] μνι and Group IV semiconductors or alloys of these materials. Nanocrystals may be substantially cymbal-shaped, such as quantum dots, or may be cymbal-length, such as nanorods or nanowires, such as having an aspect ratio of 2, 5, 10, or even 20 or higher, Or may include branched structures, such as nano-quadruped. See, e.g., U.S. Patent No. 6,322,901; Pengetal, Nature 404 (6773): 59-61 (2000); Manna et al. J. Am. Chem. Soc. 122 (51): 12700-12706 (2000); Manna et al. 5 J. Am. Chem. l〇 Soc. 124 (24): 7136-7145 (2002); and Duan et al., Nature, 425: 274.278 (2003), the entire contents and purpose of which are incorporated herein by reference. Such nanocrystals may include a single homogeneous composition or a heterostructure, such as a core-shell structure, where the core material is a first composition and 15 the shell material is a second different material, which is different from the The interface of the first material is a clear knife boundary or gradient. Additionally, nanocrystals in a community may be of various sizes or they may be monodisperse in one or more of their cross-sectional dimensions. Similarly, a community of nanocrystals may include a single type of nanocrystals, such as where substantially every part of the community has the same structure, such as 20 identical or different structures, or the community may be heterogeneous of different crystal types mixture. ; In one example, the nanometer crystal system with ^ shell value is made by solution-based method, which is controlled by surfactants to produce nanocrystals of desired shape and size, such as nanorods or branches. Nano structure, such as winning four feet. Synthesized by this surfactant: 28 200524973 404 (6773): 59-61 (2000); Manna et al. J. Am. Chem. Soc. 122 (51): 12700-12706 (2000), and Manna et al. , J. Am. Chem. Soc. 124 (24): 7136-7145 (2002) has been described in great detail. Figure 1 provides a flowchart that briefly illustrates an exemplary nanocrystal synthesis method. 5 In short, as shown in Figure 1, the synthesis of semiconductor nanocrystals is typically performed by combining a Group II precursor with a Group VI precursor (or, as another example, a Group III with a Group V Semiconductor precursor (104) into a high temperature bi-or synergistic solvent mixture (102), for example, the mixture has a boiling point higher than the temperature at which the precursor reacts, such as between 200 and 400 ° C Between (104). Typically, this two-solvent mixture includes at least two organic surfactants. These surfactants typically include, for example, tri-octylphosphine oxide (butanol> 0), hexylphosphonic acid (HPA) and tetradecylphosphonic acid (Tdpa); and TOPO and octadecylphosphonic acid (ODPA) Or hexadecylphosphonic acid (HDPA). Injecting the precursor into the thermal reaction solvent mixture results in homogeneous nucleation of instant burst nanocrystals (104). Quickly reducing the nucleation-related reagents and adding reagents to reduce the temperature can effectively terminate the nucleation reaction. The reaction mixture is heated (106), and then the nanocrystallites are allowed to anneal and grow, such as to form small monolithic clusters of substantially monodisperse particles. The growth advancement is then stopped by lowering the temperature of the reaction mixture (108). Further refinement of the particle size distribution can optionally be accomplished by size selective precipitation of the nanocrystals from the 20 solvent mixture (110) (see U.S. Patent No. 6,322,910), which is based on During one of the subsequent processing steps described below, the polarity of the reaction mixture is changed using, for example, low molecular weight alcohol, to precipitate nanocrystals. The resulting nanocrystals are then subjected to further processing (112). 29 200524973 Synthetic methods of other nano crystal types are familiar in this technical field. See e.g. Rockenberger et al. (1999) “A new nonhydrolytic single-precursor approach to surfactant-capped nanocrystals of transition metal oxides” J Am Chem Soc 121: 11595-11596 5 and Puntes et al. (2001) “Colloidal nanocrystal shape and size control: The case of cobalt "Science 291: 2115-2117 〇III. Processing of nanocrystals Predetermining the purity of reagents In at least some cases, the relative purity of the nanocrystal community will be at least 10% dominated by the relative purity of the materials used in this process. In particular, although the surfactant and other solvents used in this crystal synthesis step are specified to be particularly pure, this purity is often inaccurate. Therefore, in order to determine the result of a pure crystalline product, it is useful to determine the purity of the reagent used in the synthesis step in advance. In at least one aspect, it may be useful to determine that the purity of the surfactant used in the crystal synthesis step is at least 99%, preferably higher than 99%, as measured by NMR at 15. If the purity of the surfactant obtained from the supplier is not at the desired level, subsequent purification steps, such as washing, recrystallization, sublimation, and distillation, can be used to provide the desired level of purity. In many cases, this surfactant contains products of oxidation, starting materials reactants, and by-products of incomplete ester hydrolysis. For example, phosphonic acids, especially ODPA and TDPA, are very susceptible to this problem, because they are often obtained in the form of esters with equivalent levels of HC1 and other impurities. Phosphonic acid in the ester form causes serious problems because it can oligomerize into a multidentate structure, which makes the cleaning of the resulting nanocrystals particularly difficult. 30 200524973 Similarly, TOPO often includes both phosphonic and phosphinic acids, which results in changes in the reaction rate and acid: metal ratio during synthesis. Β. Reducing Free State Surfactants As repeatedly mentioned here, this typical method of synthesizing nanocrystals (as described above 5) typically produces relatively large amounts of contaminating materials (such as organic interfaces linked to nanocrystals) Active agent) of nanocrystalline communities. The standard precipitation-based method used to recover nanocrystals from the synthetic reaction mixture may not be effective in removing this excess contaminant. In particular, many of the customary surfactants used in this synthesis are often insoluble in 10-precipitation solvents and therefore precipitate together with nanocrystals. In fact, even after further immersion and processing in some layers, the organic pollutants still remain as part of the composition, which has been explained in the prior art of this technology, such as having free surfactants exceeding 1 or 5 or 10% and bound surfactants far exceed the desired monolayer to bilayer surfactants. 15 Additionally or alternatively, the previously described nanocrystal purification method can prevent shortening the number of iterations necessary to produce the desired level of purity. Although the explanation is mainly about the surfactant used during the synthesis of nanocrystals, it is hoped that the surfactant component to be removed may include the organic surfactant used during the crystal synthesis, such as the high-temperature-resistant organic interface activity. 20 agents, such as TOPO, or they may include foreign surfactants (also known as "ligands"), which are added to the nanocrystals (eg, exchanged with or added to the surfactant used during synthesis) (Middle) is to promote the integration (solubility, electrical integration, etc.) of the nanocrystal. An example of the latter type of surfactant is described in US Patent Application No. 31 200524973 10 / 656,910 filed on September 4, 2003. The entire contents and purpose of this case have been incorporated into this case for reference . According to a particular aspect of the present invention, after the growth or synthesis step, the nanocrystal 5 body is collected and cleaned by repeated precipitation, redissolution, and precipitation treatments until the desired purity level is obtained. Fig. 2 provides a flowchart briefly explaining the processing method of the present invention. In particular, the nanocrystal community is first formulated in a solvent mixture in which both the nanocrystal and the polluting surfactant are soluble, such as derived from the synthesis of the nanocrystal (see Figure 1). The solvent mixture is then changed, whereby the nanocrystals are no longer soluble in the resulting solvent mixture, and the precipitated nanocrystals are recovered. The recovered nanocrystals were then redissolved and reprecipitated many times until the desired purity level was reached. 1. Two-solvent method In the first embodiment, the cleaning of the nanocrystal community is performed using a mixed solvent method. The method uses a solvent mixture including at least two solvents having different polarities, whereby the nanocrystals are cleaned. Soluble in a sufficient concentration of a non-polar or less polar first solvent, while the surfactant portion is soluble in a sufficient concentration of a more polar second solvent. In the first or solubilizing solvent mixture, both the higher-polarity and lower-polarity solvents are present at this allowable concentration, such as both crystals and surfactants are dissolved in the one mixture 20. Typically, the nanocrystalline portion of the mixture is increased by increasing the concentration of the second or higher polar solvent (or reducing the concentration of the first or lower polar solvent) to such an extent that the nanocrystals no longer dissolve, and Precipitation from the solvent mixture. As the skilled person hopes, reverse processing can also be used when the nanocrystal has a sufficient amount of the solubilizing surfactant 32 200524973 $, if it is more soluble in higher polarity solvents, it can be used later Precipitation is specified by increasing the concentration of the less polar solvent in the mixture. After 5 10 15 20, the precipitated nanocrystals can be centrifuged, filtered, or similar. < The solvent mixture is separated and resuspended in an additional amount of the solvent mixture in which both the nanocrystals and the surfactant will be dissolved again. This method is optionally repeated to produce the desired level of purity. This iterative process can be performed-a selected number of iterations, as many as is known to produce the desired purity. Optionally 'and in a specific preferred mode, the purity of the dissolved nanocrystals is typically checked afterwards, for example, to determine the low level of interfacial activity in the composition. After that, the step is optionally repeated; the step of re-dissolving and re-dissolving until the amount of free surfactant in the nanocrystal mixture is lower than the total surfactant concentration (free and bound) _% or less than 5%, preferably It is lower than 丨% of the total amount of the surfactant, and more preferably lower than 0.1%. The solvents used in the solubilizing and sinking solvent mixtures and their relative relative concentrations in each mixture typically follow the nanocrystals and the organic pollutants to be removed (such as the presence of surfactants) Type), but in general, the inorganic nanocrystalline community is generally soluble in relatively low-polar solvents such as toluene, benzene, or a mixture of branched and unbranched six-carbon ships. ), And aerosol (its thing is generally polar, but the relative polarity is lower than methanol, and nano crystals will dissolve in the pot). On the contrary, organic materials and special materials with higher polarity are surfactants, that is, surfactants, and Dian Wei lacks more materials, such as relatively low = alcohol, such as methanol and ethanol, and at the Teshunjia interface. Among the active agents, gardenia, alcohols having more than two carbon atoms, such as isopropanol, butanol 33 200524973, and the like. As a result, according to a particular aspect of the present invention, the lower-polarity solvent portion of the solvent mixture typically includes lower-polarity solvents such as chloroform, toluene, hexane, benzene, and the like, and such solvents as methanol, ethanol, isopropanol, butanol Higher polar solvents such as alcohol, ethyl acetate, acetone, etc. The relative concentration of the lower polar solvent and the higher polar solvent of the solubilizing solvent mixture typically ranges from about 10: 1 to about 3: 1, and a particularly preferred ratio is approximately 4 ·; 1. With respect to the nanocrystals emerging from the solubilizing solvent mixture, the ratio can typically be changed to between about 2: and 1: 1. The change in the ratio of 10 15 20 is typically accomplished by increasing the concentration of the higher polarity solvent, such as by adding a higher polarity solvent to the mixture, but optionally by lowering the lower polarity. The concentration of the solvent is used, such as by evaporation. As mentioned, the precipitate is optionally nanocrystal size selective. Once the nanocrystals are precipitated, they can typically be separated from the liquid portion of the ocean by many methods, including centrifugation, filtration, and the like. After that, the separated feminine body is redissolved in the first solvent mixture (solubilizing solvent mixture), and the steps of 4 precipitation and separation are repeated until the desired purity is achieved. As in Ben Yuming, this typically means that the synthesis mixture is subjected to at least 3 cycles of sinking and re-dissolving, preferably 4 or more cycles, and in some examples, 5 or More times or even 6 or more Shen Dian ^ Dissolution cycle. After any or all of the repeated cleaning cycles, the level of free energy in the nano-containing solution can be checked, and the level of the surfactant can be determined to determine the purity of the solution. The method will be provided with the required information, including 'but not limited to 31PNMR. This check can be used as a basis for continuing or stopping repetitive cleaning steps, or it can be used as a benchmark for the required cleaning steps to determine how many steps are required to reach the desired purity. Once the nanocrystal has reached the desired purity level by repeating the precipitation and redissolution a predetermined number of times, or by analysis to determine the purity 5 has reached the purity level, then optionally accept additional Processing step processing, as will be explained in more detail below (see, eg, the section entitled "Reducing bound surfactants"). 2. Single solvent exchange method In a selective method, a nearly complete solvent exchange method is used to reduce the level of free surfactants in nanocrystalline products. This method is briefly explained in the flowchart shown in FIG. In particular, instead of using a two-solvent mixture, this nanocrystal system uses a higher solvent such as a low molecular weight alcohol (e.g., methanol, etc.) to precipitate from the starting reaction mixture (202) for its synthesis (step 204). As mentioned above, precipitation is generally achieved by adding the polar component at a ratio of the reaction mixture to 15 higher polar solvents ranging from about 2: 1 to 1: 2 until the nanocrystals precipitate out of the solution. . As mentioned earlier, by selectively precipitating the mixture, some degree of size selection can also be performed in the starting mixture because the nanocrystals tend to precipitate out of the reaction solution in a size-dependent manner. Once the desired nanocrystals have precipitated from the 20 solution, the nanocrystals are separated from the liquid by, for example, centrifugation and decantation of the liquid, by filtration or the like (see steps 206 and 208). The nanocrystals are then redissolved in a less polar solvent, such as toluene, aerosol, etc. (step 210) (or a mixed solvent as previously described). Then, if necessary, repeat the precipitation and redissolution steps (step 214) to produce the desired purity level related to the free interface activity at 35 200524973 (212). As mentioned above, precipitation is generally achieved by adding the higher polarity component at a ratio of lower polarity to higher polarity solvents ranging from about 2 ·· 1 to 1: 2 until δHennai Come out from the hall of the 5th valley. As in the two-solvent method described above, the cycle of Shen Dian and redissolution is typically performed at least 3 times in the starting reaction mixture, preferably 4 or more times, in some examples, 5 or more times and in 6 or more times in some examples. As also mentioned above, what is of most interest is not necessarily the number of repeated precipitation steps performed, but the level of surfactant results after the last precipitation step. As mentioned before, after repeated cleaning treatments, 10 free surfactants remaining in the nanocrystal-containing solution are typically less than 10% of the total surfactant (free and bound) surfactants, preferably low. At 5%, more preferably less than 1%, and even more preferably less than 0.1%. The percentage of residual surfactant used here is generally determined using NMR, such as 31p NMR. The percentages mentioned here, for example, represent the values measured after analyzing 100 nanocrystals prepared in 0.75 ml toluene using this system, which are not available after breaking the NMR scan 11,000 times. Detected peaks of free surfactant. Scanning more times can detect contaminating surfactants, but the levels are expected to be lower than the percentages described herein. Figures 3A-G provide plots of the 20-side 'tongue agent in the free and bound states in the nanocrystalline product after each repeated cleaning step. As shown in the figure, the level of free surfactant in this solution dropped significantly after each wash and was virtually undetectable after the fourth wash step (Figures 3D-3G). Later, the 'crying Shen Dian step' typically adds a higher polarity solvent at the ratio previously described, such as a solvent ratio of lower polarity to higher polarity between 2: 1 to 36 200524973 1: 2. This may be the same level as used in the first precipitation step, or it may be higher than the level used in the first step. In particular, as mentioned above, the first precipitation step can also use a size selection method, which needs to strictly control the higher polarity solvent added, such as to precipitate some, but not all nanocrystals in the solution. On the other hand, the subsequent precipitation step is focused on recovering most, if not all, of the nanocrystals, rather than this size choice. Accordingly, in many cases, the amount of higher polarity solvents added in this subsequent precipitation step will be higher than in the initial precipitation. Once the nanocrystals have reached the desired purity level by repeating the precipitation and redissolution a predetermined number of times, or by analysis to determine that the purity has reached the purity level, then optionally accept additional Processing steps, as will be explained in more detail below (see eg the section entitled "Reducing bound surfactants"). 3. Liquid-liquid extraction method 15 In another selective method, a liquid-liquid phase separation method is used to reduce the level of free surfactants in the nanocrystalline community. In this method, the nanocrystal system is combined with a first solvent in which the nanocrystals are soluble and a second solvent (such as insoluble) in which the nanocrystals are less soluble. Allow the first and second solvents to form a first liquid phase containing the first solvent and the 20-meter crystal, and a second liquid phase containing the second solvent, and then separate the phases (such as by using Liquid pipe, pouring, etc. to move one phase out of the other). Because the surfactant is typically soluble in both the first and second solvents (and preferably more soluble in the second solvent than the nanocrystals, and more preferably itself in the first solvent The degree in the two solvents is higher than that in the first 37 200524973 solvent), and this method results in a reduction in the amount of free-state surfactant in the solution having the nanocrystals. This method is optionally repeated to produce the desired level of purity. This iterative process can be performed for a selected number of iterations, as many times as necessary to produce the desired purity. For example, this step can be repeated 2 or more times, 3 or more times, 4 or more times, 5 or more times, or even 6 or more times. In a particular preferred aspect, the purity of the dissolved nanocrystals is typically checked, for example, to determine if the level of the surfactant in the composition is sufficiently low. If necessary thereafter, optionally repeat the steps of combining, phase forming and separating until the amount of free surfactant in the nanocrystal mixture 10 is less than 10% of the total surfactant concentration (free and bound) or 5%, preferably less than 1% of the total amount of the surfactant, and more preferably less than 0.1%. When the cycle needs to be repeated, a new second solvent can be combined with the first liquid phase containing the first solvent and nanocrystals, or the nanocrystals can be separated from the first liquid 15 phase (such as by Centrifugation, filtration, precipitation, etc.), redissolved in a new first solvent and combined with a new second solvent. The relative ratio of the first and second solvents, and the like, typically varies with the nature of the nanocrystals and the organic pollutants to be removed (such as the type of surfactant present). Typically, the first solvent is less polar than the second solvent in cleaning the inorganic nanocrystals 20. In an exemplary embodiment, nanocrystals (such as Pd or InP) prepared using TOP as a surfactant (or one of the surfactants) are prepared by using liquid-liquid extraction method with toluene as the first solvent. And methanol is processed as the second solvent. It is worth noting that the first and second solvents are only present under the condition that the surfactants to be removed are not miscible in the presence of 38 200524973. Toluene and methanol will be mixed without ~ = phase, but In the presence of the medicine, they will not be mixed in-since Erliu = a liquid phase, so it can be used for liquid Na extraction to remove this world = i ㈣ method optional combination of the liquid and solid extraction steps described here -Use (as described in the heading 10-dose method m-dose exchange method ', Qing 2 method described in the paragraph). For example, the nanocrystals can be subjected to at least one liquid-liquid extraction followed by at least one guandian and redissolving ring treatment. Once the nano crystals have been repeatedly extracted—predetermined to reach the desired purity level, or by analysis to determine that the purity has reached the purity level—then optionally accept additional processing steps. The treatment, as will be explained in more detail below 15 (see eg "reducing the binding state of the surfactant," Question 2 λτ / r \ ie).

C.減少結合態界面活性齋J 一旦過里之游離怨界面活性劑在如最後的沈殿與分門步驟後從该奈米晶體中移除，則可進一步加工所產生的齐 20米晶體以減少在該奈米晶體之表面上的結合態界面活性劑之位準。一般而言，該結合態界面活性劑之移除係轉由滴定該結合態界面活性劑，使其離開該奈米晶體之表面來進行。因為於晶體合成與加工中使用之界面活性劑包含有機酸，因此其一般可使用適當的有機鹼來滴定，使其離開該 39 200524973 奈米晶體’該有機驗可溶混於含該奈米晶體之有機溶劑中:特別適合與該界面活性劑錯合之社例子包括該等會亥界面讀細彡成不雜鹽者，因此沈殿而離開該溶液以及脫離化學平衡式。一些特別有用之有機鹼包括如哌咬、苯胺、雙对、㈣、咪唾、二乙胺、三乙胺、二-異丙胺以及其它燒胺等。特佳m用㈣作為驗，因為其容易滴定該較佳界面活性劑（如odpa、hdpa等）上之酉夂基團Μ產生不溶於含該奈米晶體之溶液(如較低極性組份，如甲笨）中之鹽。 1〇在加工方面，再次沈澱已經純化而除去過量游離態界面活之奈米晶體(步驟216)，之後再溶解於較低極性容液與驗(如°辰咬)之組合中（步驟218)，以及任擇地於提高的溫度下培育（步驟220)。 ^、 15 20 典型地，添加過量之驗以便有效地滴定晶體表面結合的界面活性劑。一般而言，此過量意指驗係以高於^ 更典型地2 : 1或更高，以及於—些案例中為3 : 1或更高之體積比加入含該奈米晶體之溶液中。同在滴定過量之表面結合的界面活性劑後，典型地藉由離心來移除該不溶部分(步驟222)。之後藉由添加額外^溶劑（如曱醇或己烷），將此刻於混合的溶劑（如曱笨^比定）中办奈米晶體從該吡啶中沈澱出來（步驟224)。之後晶體從該溶液中分開來，並再懸浮於另外如較低 (如甲笨）中（步驟226)，以及進行濃度和/或純度分析：澱的界面活性劑鹽從該溶解的奈米晶體中分開來=沈實免上 40 200524973 背離公開的合成流程，該公開的合成流程僅沈澱該奈米晶體以及任何一起接受之後的清洗之鹽類，因此妨礙該等材料之足夠的分離。如之前所述，根據本發明一般需要提供僅夠該奈米晶 5 體溶解與分散於其最終混合物或溶液中所需要之結合至該奈米晶體表面的界面活性劑。亦如之前所述，一般認為此位準包括在該奈米晶體之表面上超過部分單層之界面活性劑，但不超過約二層之界面活性劑，如二層。與該奈米晶體連結之界面活性劑的數量之決定一般係以上述之方法進 10 行，如31P-NMR。31P-NMR中，適合位準之結合態界面活性劑產生顯示單一寬峰或駝峰或具微小肩狀之單一主要駝峰之NMR光譜(似乎指出部分二層，見第3D-3G圖）。 IV.組成物以任何在此所述之方法加工成之奈米晶體（如缺少過 15 量游離態和/或結合態界面活性劑之奈米晶體）形成本發明之另一特徵，如包括此加工的奈米晶體之組成物、系統與元件。例如，一實施例類型提供一種組成物，其包括溶於一第一溶劑中之奈米晶體群落。該奈米晶體與一總數量之界 20 面活性劑連結，其於溶液中包括一數量之結合態界面活性劑以及一數量之游離態界面活性劑。該游離態界面活性劑的數量低於該界面活性劑總數量的約5%，較佳低於約1%、低於約0.5%以及更佳地低於約0.1%。如上所述，該奈米晶體基本上可呈任何形狀、大小和/組成物。 41 200524973 一實施例之相關類型提供一種組成物，其包含具有界面活性劑結合於其上且溶於一第一溶劑中之奈米晶體群落。該奈米晶體包含少於二層之與其連結的界面活性劑。較佳地，該奈米晶體包含約單層或更少層之與其連結的界 5 面活性劑。如上所述，結合至該奈米晶體之界面活性劑的數量大於零，因此一些界面活性劑的存在是該奈米晶體之溶解度和/或分散性所必須的。實施例之另一相關類型提供一種組成物，其包括一奈米晶體群落與一結合至奈米晶體之界面活性劑，其中該界 10 面活性劑包含少於二層。例如，該界面活性劑較佳包含約一層或更少層。如所提到的，將以本發明之方法加工之奈米晶體任擇地併入各種組成物與元件中。因此，本發明提供組成物，其包括以本發明之方法加工之奈米晶體且設置於一基質 15 (如有機、無機、聚合、非聚合、導體、半導體和/或非導體基質）中。因此，一實施例類型提供一種複合物，其包含一有機聚合物基質以及一設置於該有機聚合物基質中之奈米晶體群落。該奈米晶體具有與其連結之界面活性劑，該界面活性劑包含少於二層（如該界面活性劑可包含約單層或 20 更少層）。廣泛各種適合的基質，如有機聚合物為此技藝所熟悉者。基質材料之例子包括，但不限於，無機聚合物[如聚矽烧、聚碳石夕氧烧（polycarbonessiloxane)(石夕氧烧與碳棚烧 (carborane)之共聚物）或聚膦腈(polyphosphazene)]、有機金 42 200524973 [如 N，N’-二二苯基-N，N，_雙(3_甲基苯基)_(u，C. Reduction of bound state interfacial activity J Once the free interfering surfactant has been removed from the nanocrystal after the final sinking and separation steps, the resulting 20-meter crystal can be further processed to reduce The level of bound surfactant on the surface of the nanocrystal. Generally speaking, the removal of the bound surfactant is performed by titrating the bound surfactant to remove it from the surface of the nanocrystal. Because the surfactant used in crystal synthesis and processing contains organic acids, it can generally be titrated with an appropriate organic base to leave it. 39 200524973 Nano crystals' The organic test is miscible with the nano crystals Among organic solvents: Examples of companies that are particularly suitable for the interaction with the surfactant include those who read the interface to form non-heterosalt, so Shen Dian left the solution and escaped from the chemical equilibrium. Some particularly useful organic bases include, for example, piperazine, aniline, double-pair, pyrene, saliva, diethylamine, triethylamine, di-isopropylamine, and other amines. Tejiam uses osmium as a test because it is easy to titrate the osmium group M on the better surfactant (such as odpa, hdpa, etc.) to produce a solution insoluble in the nanocrystals (such as lower polar components, Such as Jiaben). 10 In terms of processing, re-precipitate the nanocrystals that have been purified to remove excess free interfacial active crystals (step 216), and then re-dissolve in a combination of a lower-polarity solution and a test solution (such as ° biting). And optionally growing at an elevated temperature (step 220). ^, 15 20 Typically, an excess is added to effectively titrate the surfactant bound on the crystal surface. Generally speaking, this excess means that the test is added to the solution containing the nanocrystals at a volume ratio higher than ^ more typically 2: 1 or higher, and in some cases 3: 1 or higher. After titrating an excess of surface-bound surfactant, the insoluble portion is typically removed by centrifugation (step 222). Thereafter, by adding an additional solvent (such as methanol or hexane), the nanocrystals are precipitated from the pyridine in a mixed solvent (such as ethanol) (step 224). The crystals are then separated from the solution and resuspended in another (e.g., methylbenzyl) (step 226), and a concentration and / or purity analysis is performed: the precipitated surfactant salt from the dissolved nanocrystals Separation from the middle = Shen Shi Mian 40 200524973 Departs from the public synthesis process, which only precipitates the nano crystals and any washed salts after accepting them together, thus preventing sufficient separation of these materials. As mentioned earlier, according to the present invention, it is generally necessary to provide only a surfactant that is required to dissolve and disperse the nanocrystals in the final mixture or solution to bind to the surface of the nanocrystals. As also mentioned previously, this level is generally considered to include more than a single layer of surfactant on the surface of the nanocrystal, but no more than about two layers of surfactant, such as two layers. The determination of the amount of the surfactant to which the nanocrystal is linked is generally performed by the method described above, such as 31P-NMR. In 31P-NMR, a suitable-level bound surfactant produces an NMR spectrum showing a single broad peak or hump or a single main hump with tiny shoulders (seems to point out some two layers, see Figures 3D-3G). IV. The nanocrystals of the composition processed by any of the methods described herein (such as nanocrystals lacking more than 15 free and / or bound surfactants) form another feature of the invention, such as including this processing Composition, system and components of nano crystals. For example, an embodiment type provides a composition comprising a nanocrystalline population dissolved in a first solvent. The nanocrystals are connected to a total amount of a boundary 20 surfactant, which includes a quantity of a bound surfactant and a quantity of a free surfactant in a solution. The amount of free surfactant is less than about 5%, preferably less than about 1%, less than about 0.5%, and more preferably less than about 0.1% of the total amount of surfactant. As mentioned above, the nanocrystals can be of essentially any shape, size, and / or composition. 41 200524973 A related type of an embodiment provides a composition comprising a nanocrystalline group having a surfactant bound thereto and dissolved in a first solvent. The nanocrystal contains less than two layers of surfactants attached to it. Preferably, the nanocrystal comprises about a single layer or fewer layers of surfactants attached thereto. As mentioned above, the amount of surfactants bound to the nanocrystals is greater than zero, so the presence of some surfactants is necessary for the solubility and / or dispersibility of the nanocrystals. Another related type of embodiment provides a composition that includes a nanocrystal community and a surfactant that is bound to nanocrystals, wherein the surfactants include less than two layers. For example, the surfactant preferably contains about one or less layers. As mentioned, nanocrystals processed by the method of the present invention are optionally incorporated into various compositions and components. Accordingly, the present invention provides a composition comprising nanocrystals processed by the method of the present invention and disposed in a substrate 15 (such as an organic, inorganic, polymeric, non-polymeric, conductive, semiconductor, and / or non-conductive substrate). Accordingly, an embodiment type provides a composite comprising an organic polymer matrix and a nanocrystal community disposed in the organic polymer matrix. The nanocrystal has a surfactant attached to it, and the surfactant includes less than two layers (for example, the surfactant may include about a single layer or 20 fewer layers). A wide variety of suitable substrates, such as organic polymers, are familiar to this art. Examples of the matrix material include, but are not limited to, inorganic polymers [such as polysilicon, polycarbonessiloxane (copolymer of stone and carborane) or polyphosphazene )], Organic gold 42 200524973 [such as N, N'-diphenyl-N, N, _bis (3-methylphenyl) _ (u,

/物(如—茂鐵聚合物、翻聚合物或把聚合物）、小分子 ’二苯基)-4,4-二 •5-叔丁基苯基_1，2,4_三、苯酸、笨二酸、安息香、 5 I基苯紛、硝絲齡、氯絲紛、氯絲胺或氯基苯並酿胺]或有機聚合物[例如，聚(m_苯樓異鄰苯二甲醯胺）、聚(對 T甲醯胺）、聚(燒基異腈）、聚異氰咖旨]、熱塑性聚合物(如 I稀t酉曰I石夕氧燒、聚丙烯腈樹脂、聚苯乙烯樹脂、聚氯乙烯、聚偏二氯乙稀、聚乙歸乙酸樹脂或氣塑料）、熱 10固性聚合物(如酚醛樹脂、尿素樹脂、美耐盟樹脂、環氧樹脂、聚氨酯樹脂、工程塑料、聚醯胺、聚丙烯酸酯樹脂、聚酮、聚醯亞胺、聚;e風、聚碳酸酯或聚曱酸）、液晶聚合物，包括主鏈液晶聚合物（如聚（羥萘酸))或側鏈液晶聚合物（如聚<n-((4’(4”-氰苯基)苯氧基)烷基）乙烯醚；>)、或導體聚合物 15 (如聚（3_己基噻吩XP3HT)、聚[2-甲氧基，5_(2，_乙基_己氧基)_p-苯撐·乙烯撐](MEH-PPV)、聚（苯撐乙烯撐)(ppv)、聚芴或聚苯胺）。見如美國專利申請案第1〇/656,916與 10/778,009 號；Demus et al· (1998) Handbook of Liquid Crystals > Four Volume Set, John Wiley and Sons, Inc.； 20 Johannes Brandrup (1999) Polymer Handbook, John Wiley and Sons, Inc. ； Charles A. Harper (2002) Handbook of Plastics, Elastomers， and Composites， 4th edition， McGraw-Hill ； T. A. Skatherin, ed. (1986) Handbook of Conductipff Polymers L Marcel Dekker，new York ;以及 43 200524973(Such as—ferrocene polymer, polymer or polymer), small molecule 'diphenyl) -4,4-di • 5-tert-butylphenyl1,2,4_triphenyl Acid, adipic acid, benzoin, 5 I-phenylbenzene, nitrocellulose, clozam, closamine or chlorobenzamine] or organic polymers [for example, poly (m_benzene building isophthalate Formamidine), poly (p-T-methylammonium), poly (carbamoyl isonitrile), polyisocyanocyanine], thermoplastic polymers (such as dilute t-methyl isocyanide, polyacrylonitrile resin, Polystyrene resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate resin or aeroplastic), thermosetting polymers (such as phenolic resin, urea resin, Miner resin, epoxy resin, polyurethane Resins, engineering plastics, polyamides, polyacrylate resins, polyketones, polyimides, poly; e-wind, polycarbonate, or polyacid), liquid crystal polymers, including main chain liquid crystal polymers (such as poly ( Hydroxynaphthoic acid)) or a side chain liquid crystal polymer (such as poly < n-((4 '(4 "-cyanophenyl) phenoxy) alkyl) vinyl ether; >), or a conductive polymer 15 ( Such as poly (3-hexylthiophene XP3HT), poly [2-methoxy 5_ (2, _ethyl_hexyloxy) _p-phenylene · vinylene] (MEH-PPV), poly (phenylenevinylene) (ppv), polyfluorene, or polyaniline). See, for example, the US patent application 10 / 656,916 and 10 / 778,009; Demus et al. (1998) Handbook of Liquid Crystals > Four Volume Set, John Wiley and Sons, Inc .; 20 Johannes Brandrup (1999) Polymer Handbook, John Wiley and Sons, Inc .; Charles A. Harper (2002) Handbook of Plastics, Elastomers, and Composites, 4th edition, McGraw-Hill; TA Skatherin, ed. (1986) Handbook of Conductipff Polymers L Marcel Dekker, new York; and 43 200524973

Skotheim et al. (1998) Handbook of Conducting Polymers, 2nd ED· Marcel Dekker : New York ;以及其它例子Ronald Archer (2001) Inorganic and Organometallic Polvmers,Skotheim et al. (1998) Handbook of Conducting Polymers, 2nd EDMarcel Dekker: New York; and other examples Ronald Archer (2001) Inorganic and Organometallic Polvmers,

Wiley-VCH。 5 如所提到的，此組成物可用於光電元件，LEDs以及其它元件。見美國專利申請案第10/656,916與10/778,009號。其它實施例類型提供一種組成物，其包含一第一奈米晶體群落與一第二奈米晶體群落。該第一奈米晶體群落具有與其相連結之界面活性劑，該界面活性劑包含少於二層 1〇 (如約單層或更少層）。該第二奈米晶體群落具有不同於該第一奈米晶體群落之組成物，且與該第一群落一起散置於該組成物中。該第二群落任擇地亦包含少於二層之相同或相異之界面活性劑。該散置的第一與第二奈米晶體群落可，但不必須，設 15置於基質（如有機聚合物基質、無機基質、小分子基質等）内。各種廣泛之適合的基質材料為此技藝所熟知者。見如上述作為例子之參考文獻。如所提到的，此組成物可用於光電與其它元件，見美國專利申請案第1〇/788,〇〇9號 V.宜教下列提出一系列實驗說明在此所述本發明之奈米晶體加工法。很清楚此等在此所述之範例與實施例僅供例示性用途’而各種依據該範例與實施例之改質物或改變係熟悉此技藝人士所能聯想到的且包含於此申請案之本義與範圍以及隨附之申請專利範圍之範疇内。據此，下列範例係供 44 200524973 例示用，而不是用於限制本發明之請求範圍。範例1 高純度奈米晶體係以下列步驟合成。由於製造商與製造商間之變異很大，所以首先要使用標準NMR檢查用於合 5 成過程中之界面活性劑（如ΗΡΑ、TOPO與TDPA)之純度。若發現純度低於90%，則藉由以CHC13清洗以及使用CHC13與己烷溶解與再結晶，來純化該界面活性劑直至達到所欲之純度。一旦得到夠純之試劑，將該界面活性劑 TOP〇(3.54g)、TDPA(0.33g)與HPA(0.13g)加熱至 120°C，此 10 時添加鎘前趨物(Cd(Me)2，0.5g之貯存溶液，其於TBP中包括32重量％之Cd(Me)2)至該混合物中。之後將該混合物加熱至360 °C並加入2.5 g之第二前趨物貯存溶液（如Se ·· TBP(7_78重量％))，其使得反應溫度降至290。至300°C之間。之後使晶體於此溫度下成長5分鐘。之後將該反應混合 15物冷卻至6〇-70°C，以停止晶體之成長。將4毫升之曱苯加入該冷卻的混合物中，之後將該混合物分開倒入兩個相同體積的小瓶内，該等小對被送入控制氛圍下的手套箱中。之後每一小瓶接受2 ml之甲醇，以沈澱出奈米晶體，旋渦授拌該等小槪並於〜3000 rpm下離心。倒出上清液且將沈澱 20丸再溶解於1 ml之甲苯中並旋渦攪拌。之後加入1 ml之甲醇於该奈米晶體中，使其再次沈殿，旋涡授拌該小瓶且再次離心。重複此過程4次，同時於完成每一清洗後以3ip_nmr 分析（見第3A-3G圖）。NMR係使用P31探針，於162MHz下於 Bruker 400 MHz NMR上進行（質子去偶合的P31 NMR，如對 45 200524973 於配製於0.75 ml D8曱苯中之100 mg奈米晶體上進行11〇〇掃描）。在最後一次清洗步驟後，將該沈澱丸溶於〇·5 mi之甲苯中’且加入lm卜比啶來滴定過量之結合態界面活性劑。旋渴 5攪拌該混合物，然後加熱至150°C歷時17個小時。之後令該加熱的混合物冷卻至室溫，旋渦攪拌然後在〜3〇〇〇rpm下離心’以移除該沈澱鹽。倒出含該奈米晶體之上清液，使其與沈澱丸分開來’且再次將每一小瓶分開成二個個別的小瓶。之後每一小瓶接受7·5 ml之己烷，其將奈米晶體沈澱下 10 來。彡疋渦擾摔該混合物並於〜3000 rpm下離心。倒出該上清液使其與沈澱丸分開，之後將該沈澱丸再溶解於甲苯中並分析奈米晶體之濃度。實例2 諸如三辛基膦(TOP)、三-辛基氧化膦(TOP〇)、十四基 15膦酸(HDPA)、十六基膦酸(〇DPA)和三-η-丁基膦(ΤΒΡ)之過量的有機界面活性劑一般存在於以在此所述之標準技術或美國專利申請案第10/656,802號中所述之方法所製備成之奈米結構製品中。任擇地，任何過量之有機界面活性劑係於使用該奈米結構之前，從該奈米結構製品中移除，例如， 20在其與導體組成物連結之前（述於美國專利申請宰第 10/656,802號中）。此可藉由例如添加由一奈米結構可溶於其中之第一溶劑（如曱苯或氯仿）以及一該奈米結構於不溶於其中之第二溶劑（如異丙醇或更長鏈之酒精，或諸如乙酸乙酯之醋酸酯）所製備成之溶劑混合物來達成。雖然於該溶 46 200524973 劑混合物中第一 10:1之範圍間，分的異丙醇。〆公劑對第二溶劑之比率典型地在1 : 1至但較佳的溶劑混合物是4部分的甲苯對1部之後加入足夠將該奈米結構(但不是該過量的界面活性劑)從該溶航合物巾歧ώ來讀量的第二溶劑。之後將錢㈣奈米結構從該溶似合物巾分開來（如藉由離心），精此從該奈米結構中移除過量之有機界面活性劑。任擇地如Lx經分析測定該奈米結構製品仍含*欲數量之過篁界面活性劑，則可以該溶韻合物額外清洗該沈澱的 10 奈米結構一或多次。額外地，可藉由於該奈米晶體反應混合物中之奈米晶體上進行吡啶交換，以及沈澱該有機鹽而留下該奈米晶體於溶液中’來將任何過量的有機鹽從該奈米晶體反應混合物中移除。該啦啶交換之進行係藉由例如加熱該奈米晶體 15 反應混合物至150°C歷時約1個小時。實例3 此實例說明包含二個混雜之加工的奈米晶體群落， CdSe奈米晶體與CdTe奈米晶體，之光電元件之製造。見美國專利申請案第10/656,910號。 20 基材清洗使用如下列步驟清潔基材（如ITO於玻璃上，得自Thin Film Devices, Inc·· www.tfdinc.com) ° 以異丙醇擦拭該基材且於異丙醇中超音波振盪、於2% Hellmanex™去離子水中超音波振盪、於流動的去離子水中充份沖洗、於去離子水 47 200524973 中超音波振盈、於半導體級之丙酮中超音波振盪以及於半導體級異丙醇中超音波振盪。每一次振盪歷時15分鐘。之後以氧電漿清潔該基材，於200 W(l%反射功率）下歷時10 分鐘，氧在將近4〇OmTorr下導入80mTorr真空中。 5 PEDOT層虚理透過孔大小0·2 μηι之纖維素醋酸酯過濾器過濾 PEDOT/PSS聚(3,4·乙浠二氧基嗟吩)聚（苯乙烯續酸g旨)(如η. C. Starck之Baytron® P VP ΑΙ 4083)。將PEDOT以3000 rpm 旋轉塗覆於該基材上，歷時60秒。之後藉由於大氣壓下， 10 120°C熱盤上烘烤該旋轉塗佈之基材歷時60分鐘，以固化該 PEDOT層。 · CdTe雙結晶換合物溶液之製備於具氬氣氛圍之手套箱中製備CdSe : CdTe雙結晶掺合物溶液。CdTe奈米晶體之清洗係藉由將其溶解於甲苯中且 15以異丙醇沈澱，重複3次；CdSe奈米晶體之清洗係藉由將其溶解於甲苯中且以甲醇沈澱，重複3次。在表面處理方面，將CdSe與CdTe奈米晶體兩者均於甲苯與苯基膦酸(ppA)之溶液中，於110°c下攪拌20個小時。（該表面處理步驟不是必須的，可以省略，或可以不同的奈米晶體清潔步驟取代 20此表面處理步驟，如使用吡啶，接著以PPA或其它配位體處理）。在以異丙醇沈澱之後，將該等奈米晶體分別以如95 mg/ml(CdTe)以及11〇 mg/mi(cdSe)之濃度溶於甲苯中。將該 CdTe·甲苯溶液與CdSe:甲苯溶劑合併於151111玻璃瓶中，藉此該CdTe : CdSe之重量比率為50 ·· 50，以及奈米晶體於 48 200524973 最終溶液中之濃度介於約80-100 mg/ml之間。例如，假如 CdTe於曱笨中之濃度為95 mg/ml，而CdSe於甲苯中之濃度為Π0 mg/mi，則混合5〇〇…之以^奈米晶體溶液以及432 μΐ之CdSe奈米晶體溶液會產生cdTe ·· cdSe之比率為5〇 ·· 5 50 ’而所產生之奈米晶體之濃度為102 mg/ml。旋渦攪拌該溶液2分鐘，於56它下加熱1〇分鐘以及超音波振盪15分鐘。將该溶液轉送至微離心管後，於微離心機中以11,000 rpm離心2分鐘。Wiley-VCH. 5 As mentioned, this composition can be used in photovoltaics, LEDs and other components. See U.S. Patent Application Nos. 10 / 656,916 and 10 / 778,009. Other embodiment types provide a composition comprising a first nanocrystal community and a second nanocrystal community. The first nanocrystal community has a surfactant attached to it, the surfactant comprising less than two layers 10 (such as about a single layer or less). The second nanocrystal community has a composition different from that of the first nanocrystal community, and is dispersed in the composition together with the first community. The second community optionally also contains less than two layers of the same or different surfactants. The interspersed first and second nanocrystal communities may, but not necessarily, be placed in a matrix (such as an organic polymer matrix, an inorganic matrix, a small molecule matrix, etc.). A wide variety of suitable matrix materials are known in the art. See references above as examples. As mentioned, this composition can be used in photovoltaics and other components, see U.S. Patent Application No. 10 / 788,009. V. Yi teaches the following to propose a series of experiments to illustrate the nanometers of the present invention described herein Crystal processing method. It is clear that the examples and embodiments described herein are for illustrative purposes only, and various modifications or changes based on the examples and embodiments are those that can be conceived by those skilled in the art and are included in the original meaning of this application. And the scope and scope of the accompanying patent application. Accordingly, the following examples are provided for illustrative purposes only and are not intended to limit the scope of the claimed invention. Example 1 A high-purity nanocrystal system was synthesized by the following steps. Due to the large variability between manufacturers and manufacturers, the purity of the surfactants (such as HPA, TOPO, and TDPA) used in the synthesis process must first be checked using standard NMR. If the purity is found to be less than 90%, the surfactant is purified by washing with CHC13 and dissolving and recrystallizing with CHC13 and hexane until the desired purity is achieved. Once a sufficiently pure reagent is obtained, heat the surfactant TOP0 (3.54g), TDPA (0.33g) and HPA (0.13g) to 120 ° C. At this time, add the cadmium precursor (Cd (Me) 2 0.5 g of a storage solution, which includes 32% by weight of Cd (Me) 2) in the TBP into the mixture. The mixture is then heated to 360 ° C and 2.5 g of a second precursor storage solution (such as Se ·· TBP (7-78% by weight)) is added, which reduces the reaction temperature to 290. To 300 ° C. The crystal was then allowed to grow at this temperature for 5 minutes. The reaction mixture was then cooled to 60-70 ° C to stop crystal growth. 4 ml of toluene was added to the cooled mixture, and then the mixture was poured into two vials of the same volume, and the small pairs were sent to a glove box under a controlled atmosphere. After each vial received 2 ml of methanol to precipitate nanocrystals, the small maggots were vortexed and centrifuged at ~ 3000 rpm. The supernatant was decanted and 20 pellets of the pellet were redissolved in 1 ml of toluene and vortexed. 1 ml of methanol was then added to the nanocrystals to allow them to sink again. The vial was vortexed and centrifuged again. Repeat this process 4 times while analyzing with 3ip_nmr after each wash (see Figures 3A-3G). NMR is performed on a Bruker 400 MHz NMR using a P31 probe at 162 MHz (proton decoupled P31 NMR, such as 45 200524973 on a 100 mg nanocrystal prepared in 0.75 ml D8 toluene). ). After the last washing step, the pellet was dissolved in 0.5 mi of toluene 'and lm bibidin was added to titrate the excess bound surfactant. Xuanxi 5 Stir the mixture, then heat to 150 ° C for 17 hours. The heated mixture was then cooled to room temperature, vortexed and then centrifuged at ~ 3000 rpm to remove the precipitated salt. The supernatant liquid containing the nanocrystals was decanted to separate it from Shendian Pill 'and each vial was again divided into two individual vials. Each vial then received 7.5 ml of hexane, which precipitated the nanocrystals. The mixture was vortexed and centrifuged at ~ 3000 rpm. The supernatant was decanted to separate it from Shendian Pill, and then the pellet was re-dissolved in toluene and the concentration of nanocrystals was analyzed. Example 2 such as trioctylphosphine (TOP), tri-octylphosphine oxide (TOP0), tetradecyl 15phosphonic acid (HDPA), cetylphosphonic acid (ODPA) and tri-n-butylphosphine TBP) excess organic surfactants are generally present in nanostructured articles prepared by standard techniques described herein or by the methods described in US Patent Application No. 10 / 656,802. Optionally, any excess organic surfactant is removed from the nanostructured article prior to using the nanostructure, for example, 20 before it is attached to the conductor composition (described in US Patent Application No. 10 / 656,802). This can be achieved, for example, by adding a first solvent (e.g. toluene or chloroform) in which a nanostructure is soluble and a second solvent (e.g. isopropyl alcohol or longer chain) in which the nanostructure is soluble. Alcohol, or solvent mixtures such as ethyl acetate). Although the range of the first 10: 1 in the solvent mixture is 2005 to 200524973, the isopropyl alcohol is divided. The ratio of the common agent to the second solvent is typically from 1: 1 to but the preferred solvent mixture is 4 parts of toluene to 1 part. After adding enough to remove the nanostructure (but not the excess surfactant) from the The amount of the second solvent of the solvate was ambiguous. The chalcogenide nanostructure is then separated from the lysate complex (eg, by centrifugation), and the excess organic surfactant is removed from the nanostructure. Optionally, if Lx analysis determines that the nanostructured product still contains the desired amount of peroxosurfactant, the dissolved compound can be used to additionally clean the precipitated 10nm structure one or more times. Additionally, any excess organic salt can be removed from the nanocrystals by leaving the nanocrystals in solution due to pyridine exchange on the nanocrystals in the nanocrystal reaction mixture, and precipitation of the organic salt. The reaction mixture was removed. The pyridine exchange is performed by, for example, heating the nanocrystal 15 reaction mixture to 150 ° C for about 1 hour. Example 3 This example illustrates the fabrication of a photovoltaic element containing two mixed processed nanocrystal communities, CdSe nanocrystals and CdTe nanocrystals. See U.S. Patent Application No. 10 / 656,910. 20 Substrate cleaning Use the following steps to clean the substrate (such as ITO on glass, available from Thin Film Devices, Inc. www.tfdinc.com) ° Wipe the substrate with isopropanol and sonicate in isopropanol Ultrasonic oscillation in 2% Hellmanex ™ deionized water, full rinse in flowing deionized water, ultrasonic vibration in deionized water 47 200524973, ultrasonic oscillation in semiconductor-grade acetone, and ultrasonic oscillation in semiconductor-grade isopropanol Sound waves oscillate. Each shaking lasted 15 minutes. The substrate was then cleaned with an oxygen plasma for 10 minutes at 200 W (1% reflected power), and oxygen was introduced into a 80 mTorr vacuum at approximately 400 mTorr. 5 PEDOT layer virtual through a cellulose acetate filter with a pore size of 0.2 μm to filter PEDOT / PSS poly (3,4 · ethoxydioxophene) poly (styrene continuous acid g) (such as η. C. Starck's Baytron® P VP AI 4083). PEDOT was spin-coated on the substrate at 3000 rpm for 60 seconds. Then, the PEDOT layer was cured by baking the spin-coated substrate on a hot plate at 10 120 ° C under atmospheric pressure for 60 minutes. · Preparation of CdTe double crystal interchange solution CdSe: CdTe double crystal blend solution was prepared in a glove box with an argon atmosphere. CdTe nano crystals were washed 3 times by dissolving them in toluene and 15 were precipitated with isopropanol; CdSe nano crystals were washed 3 times by dissolving them in toluene and precipitated with methanol . In terms of surface treatment, both CdSe and CdTe nanocrystals were stirred in a solution of toluene and phenylphosphonic acid (ppA) at 110 ° C for 20 hours. (This surface treatment step is not necessary, it can be omitted, or it can be replaced by a different nano crystal cleaning step, such as using pyridine, followed by PPA or other ligands). After precipitation with isopropanol, these nanocrystals are dissolved in toluene at concentrations of, for example, 95 mg / ml (CdTe) and 110 mg / mi (cdSe). Combine the CdTe · toluene solution with the CdSe: toluene solvent in a 151111 glass bottle, whereby the weight ratio of the CdTe: CdSe is 50 ·· 50, and the concentration of the nanocrystals in the final solution of 48 200524973 is about 80- 100 mg / ml. For example, if the concentration of CdTe in fluorene is 95 mg / ml, and the concentration of CdSe in toluene is Π0 mg / mi, then mix 500… with a nanocrystalline solution and 432 μΐ CdSe nanocrystals. The ratio of cdTe ·· cdSe produced by the solution was 50 ·· 5 50 'and the concentration of nanocrystals produced was 102 mg / ml. The solution was vortexed for 2 minutes, heated at 56 ° C for 10 minutes, and ultrasonically shaken for 15 minutes. This solution was transferred to a microcentrifuge tube and centrifuged at 11,000 rpm for 2 minutes in a microcentrifuge.

GdSe · CdTe奈来晶體換合物溶液之旋轉塗佈 0 將Cdse : CdTe溶液旋轉塗佈於ITO/PEDOT : PSS基材上(於手套箱中）。典型地，每一個基材使用120 μΐ之溶液，旋轉速度為950 rpm歷時40秒。以氣仿擦拭除去該基材背側上任何的溶液。蒸發 5 在沒有曝露於氧的情況下將該奈米晶體-PEDOT塗覆的基材轉送進蒸發器中。於低於lxl0_7 torr之真空下，以5 A/s之速率將鋁（純度99.999%)蒸發至該基材上，厚度將近20 nm 〇 lljyi 除去該ιτο電極接觸梢頭上任何的奈米晶體和/或 PED0T薄層。施與銀黏貼以與IT〇梢建立電氣連結。之後將所產生之元件如所欲的特徵化。雖然為了解之目的而說明了有點詳細，但請求的範圍不會限制於此揭示内，或任何相關的專利或申請案，包括 49 200524973 無任何連續案，整個或部分，分割案、再發證、再審案等之限制，而僅受隨附之申請專利範圍之限制。對熟悉此技藝人士而言，很清楚在閱讀此揭露内容後，可在沒有背離本發明之真正_之情況下，製成純形式與細部之改 5變。例如’以上所述之所有的技術與組成物可用於各種組合。於本申請案中所引述之所有公開案、專利案、專利申請案和/或其它文獻之全部内容與目的均併入本案以為參考，範圍相同如每一個個別的公開案、專利案、專利申請案和/或其它文獻，個別地被指示併入其所有目的以為參 10 考。 ’Spin Coating of GdSe · CdTe Nylon Crystal Exchange Solution 0 Spin coating Cdse: CdTe solution on ITO / PEDOT: PSS substrate (in glove box). Typically, a 120 μΐ solution is used for each substrate, and the rotation speed is 950 rpm for 40 seconds. Any solution on the backside of the substrate was removed by wiping with aerosol. Evaporation 5 The nanocrystalline-PEDOT coated substrate was transferred into an evaporator without being exposed to oxygen. Under a vacuum below lxl0_7 torr, aluminum (99.999% purity) is evaporated onto the substrate at a rate of 5 A / s, with a thickness of nearly 20 nm. Llllyi remove any nanocrystals and / Or a thin layer of PED0T. Apply silver paste to establish electrical connection with IT0 tip. The resulting components are then characterized as desired. Although it is explained in detail for the purpose of understanding, the scope of the request will not be limited to this disclosure, or any related patent or application, including 49 200524973 without any consecutive cases, whole or part, division, re-certification , Retrial cases, etc., but only by the scope of the accompanying patent application. It is clear to those skilled in the art that after reading this disclosure, changes in pure form and detail can be made without departing from the true meaning of the present invention. For example, all of the techniques and compositions described above can be used in various combinations. The entire content and purpose of all publications, patents, patent applications, and / or other documents cited in this application are incorporated into this case for reference, with the same scope as each individual public case, patent case, patent application Documents and / or other documents, are individually instructed to incorporate all of their purposes for reference. ’

t fSQ 第1圖是簡要地說明使用界面活性劑調控之合成方法之奈米晶體合成之流程圖。第2圖是簡要地說明本發明用於奈米晶體製品之後合 15 成加工步驟之範例。第3A-3G圖是在不同的清洗與加工步驟後，奈米晶體製品之31P-NMR光譜，其顯示與該等奈米晶體製品連結之游離態與結合態界面活性劑之位準。圖片G顯示圖片D(上面，清洗液4)、圖片E(中間，清洗液5)與圖片F(下面，清洗 2〇液6)之結合態界面活性劑波峰的放大圖。【主要元件符號說明】 102…加熱協同溶劑 104···注入半導體前趨物/引發成核反應 106···再提高溫度以成長晶體 50 200524973 108…停止成長，如藉由降低溫度 110…大小選擇，如藉由沈澱 112…繼續加工，如見第2圖 202…於合成反應混合物中之合成的奈米晶體 204.. .添加極性溶劑，如甲醇，以沈澱奈米晶體 206…旋渦攪拌與離心 208.. .保留沈澱丸 210…再溶解於非極性溶劑中 212.. .奈米晶體無過量的結合態界面活性劑？ 216.. .添加極性溶劑，如MeOH，以沈澱奈米晶體 218…再溶解奈米晶體於非極性溶劑與鹼中，如吡啶 220.. .於提高的溫度下培育，如120°C，15分鐘 222…離心並丟棄沈澱丸 224.. .添加極性溶劑，如己烧，以沈澱奈米晶體 226…再溶解奈米晶體於非極性溶劑中，且決定濃度 51t fSQ Figure 1 is a flow chart that briefly describes the synthesis of nanocrystals using a surfactant-controlled synthesis method. Fig. 2 is an example briefly explaining the processing steps for synthesizing the nanocrystalline product after the present invention is applied. Figures 3A-3G are 31P-NMR spectra of nanocrystalline products after different cleaning and processing steps, which show the level of free and bound surfactants linked to these nanocrystalline products. Picture G shows enlarged views of the combined surfactant peaks of picture D (top, cleaning solution 4), picture E (middle, cleaning solution 5), and picture F (bottom, cleaning solution 6). [Description of Symbols of Main Components] 102 ... Heating and co-solvent 104 ... Injection of semiconductor precursors / Initiation of nucleation reaction 106 ... Increase temperature to grow crystals 50 200524973 108 ... Stop growth, such as by reducing temperature 110 ... Size selection If you continue to process by precipitation 112 ..., see Figure 2 202 ... Synthetic nano crystals 204 in the synthesis reaction mixture ... Add a polar solvent such as methanol to precipitate nano crystals 206 ... Vortex and centrifuge 208 .. Preserve the pellet 210 ... Redissolve in a non-polar solvent 212 .. Nano crystals without excess bound surfactant? 216 .. Add a polar solvent, such as MeOH, to precipitate the nanocrystals 218 ... Redissolve the nanocrystals in a non-polar solvent and a base, such as pyridine 220.... Incubate at an elevated temperature, such as 120 ° C, 15 Minute 222 ... Centrifuge and discard the pellet 224 .. Add a polar solvent, such as hexane, to precipitate the nanocrystals 226 ... Re-dissolve the nanocrystals in a non-polar solvent, and determine the concentration of 51

Claims

200524973 10. Scope of patent application: 1. A method for processing nano crystals, comprising: providing the nano crystals, which are formulated in a first solvent in which the H. solani is soluble, and the nano crystals have _ The total number of surfactants connected to it, the total amount of surfactants includes the amount of free-state interfacial activity [Surfactant combined with the nanocrystals of si; surfactants, Shen Dian, by adding— A second solvent with a higher polarity is used in the first dissolution to provide a mixture of Shen Dian solvent in which the nano-day solar body is insoluble, to provide a nano crystal of Shen; a nano crystal of Shen Dian; Separate from the Shen Dian solvent mixture; and ~ re-dissolve the nano crystals, which is stored by adding a second solvent in which the nano crystals are soluble to the nano crystals of Shen Dian. 2. For the method of applying for item No. 丨, the further step includes repeating the steps of precipitation, separation and re-dissolution until the amount of free surfactants connected to the nanocrystal is lower than that of the nanocrystal. Steps of 1% of total surfactant. 3. The method according to item 2 of the patent application, wherein the nanocrystals are inspected after at least one of the re-dissolution steps to determine the amount of free surfactant that is still bound to the nanocrystals. "As the oldest method in the scope of patent application, in which the heart temple, separation and re-dissolution steps are repeated 3 or more times. 5. The method of claim 1 in the scope of patent application, wherein the Shen Dian, separation and re-dissolution steps are repeated 4 or more times. 52 200524973 6. The method according to item 1 of the patent application scope, wherein the precipitation, separation and redissolution steps are repeated 5 or more times. 7. A method as claimed in claim 1 wherein the precipitation, separation and re-dissolution steps are repeated 6 or more times. 5 8. The method of claim 1 in which the first solvent comprises a mixture of a polar and a less polar solvent. 9. The method as claimed in claim 8 wherein the polar solvent is an alcohol having at least two carbon atoms. 10. The method as claimed in claim 9 wherein the alcohol having at least two carbon atoms includes ethanol, isopropanol or butanol. 11. The method according to item 8 of the patent application, wherein the polar solvent is selected from the group consisting of alcohol, methanol, acetate, ethyl acetate, ketone, and acetone. 12. The method of claim 8 in which the lower polarity solvent 15 is selected from the group consisting of chloroform and toluene. 13. The method of claim 8 in which the lower polarity solvent is selected from the group consisting of paraffin, hexane and benzene. 14. The method according to item 8 of the patent application, wherein the ratio of the less polar solvent to the polar solvent in the first solvent is greater than 3: 1. 20 15. The method according to item 8 of the patent application, wherein the ratio of the less polar solvent to the polar solvent in the first solvent is greater than 4: 1. 16. A method as claimed in claim 8 wherein the ratio of the less polar solvent to the more polar solvent in the precipitation-inducing solvent mixture is 2: 1 or less. 53 2D0524973 • Zhanshan, patent application, item § ▲, Naifa, where the ratio of the less polar solvent in the precipitation-inducing solvent mixture to the polar solvent in Samu ^ y is 1: 1 or more low. 5 10 15 n to η number of methods, wherein the precipitation-inducing solvent is mixed. 19 The ratio of the first solvent to the second solvent is 2: 1 or lower. The method of item 1 of the patent scope, wherein the precipitation-inducing solvent is mixed = the ratio of the first solvent to the second solvent is ι: ι or less. For example, the method of claim 1 in which the third solvent is the same as the first solvent. 21. The method according to the scope of patent application (1), wherein the first solvent is selected from the group consisting of: aerobic, toluene, chain burning, hexane and benzene. A The method as the oldest in the scope of patent application, wherein the second solvent is selected from the group consisting of alcohol, ethanol, isopropanol and butanol having at least two carbon atoms. 23. The method as claimed in the oldest application, wherein the second solvent is selected from the group consisting of alcohol, methanol, acetic acid, ethyl acetate, ketone and acetone. Formula 24 of bound state surfactants—A method for removing excess from nanocrystals, which includes: 3 a solution in which the mirisol is dissolved, and the nanocrystals have interfacial activity linked to them Agent, the total amount of surfactants includes a quantity of free surfactants and a quantity of combined surfactants, and the solution has the amount of free surfactants less than 10% of the total amount of surfactants 54 200524973 adding a base to the nanocrystal, the base and the bound surfactant forming an insoluble salt; and separating the insoluble salt from the nanocrystal dissolved in the solution to provide From a partially monolayer to a two-layer nanocrystal with 5 surfactants bound to the nanocrystal. 25. The method of claim 24, wherein the amount of the free surfactant is less than 5% of the total amount of the surfactant. 26. The method of claim 24, wherein the amount of the free surfactant is less than 1% of the total amount of the surfactant. 10 27. The method of claim 24, wherein the separating step includes centrifuging the nanocrystals and the insoluble salt, and gently pouring the nanocrystals dissolved in the solution from the pellets of the insoluble salt. 28. The method of claim 24, wherein the base is selected from the group consisting of pyridine, aniline, bispyridine, piperidine, imidazole, 15 diethylamine, triethylamine, and di · Isopropylamine. 29. The method of claim 24, wherein the base is added at a ratio of a base to a nanocrystalline solution of greater than 1: 1. 30. A method for processing nanocrystals, comprising: a) providing the nanocrystals formulated in a first mixture in which the nanocrystals are soluble, the first mixture comprising one or more of: A first solvent or reaction mixture; b) precipitating the nanocrystals by adding a second solvent to the first mixture to provide a second mixture in which the nanocrystals are insoluble to provide precipitation 55 200524973 C) separating the precipitated nanocrystals from the second mixture; d) redissolving the nanocrystals by adding at least the first solvent to the precipitated nanocrystals In the crystal to provide a third mixture; e) adjusting the polarity of the third mixture to provide a fourth mixture in which the nanocrystals cannot be / combined to provide precipitated nanocrystals; Nano crystals are separated from the fourth mixture; and g) when steps d, e, and / or f are repeated until the nano crystals are re-dissolved in the first solvent, the amount of free surfactant is lower than the interfacial activity AJ Total 5% i of the total amount of the surfactant comprises a surfactant of the number of free surfactant in combination with a number of nano-crystals. 31. The method of claim 30, wherein steps d and ^ f are repeated until the nanocrystals are re-dissolved in the first solvent, and the number of free interface activity 14 9 畺 is lower than the surfactant 1% of the total amount. 32. The method of claim 30, wherein steps d, ^ f2 or more, 3 or more, 4 or more, 5 or more, or 6 or more are repeated. The method for declaring item 3G of the patent scope, wherein the m-body is inspected after at least one of the re-dissolution steps to determine the amount of the _ state surfactant. 34. The method of claim 30, wherein the first mixture comprises the first solvent and the second solvent. 5. The method of claim 3G in the patent scope, wherein the nanocrystal 56 200524973 body is redissolved by adding at least the first solvent to the precipitated nanocrystal to provide a third mixture. The step includes adding the first solvent and the second solvent to the precipitated nanocrystals to provide the third mixture. 5 36. The method of claim 30, wherein adjusting the polarity of the third mixture includes adding the second solvent to the third mixture. 37. The method of claim 30, wherein the polarity of the first solvent is lower than that of the second solvent. 38. The method of claim 37, wherein the first solvent is selected from the group consisting of chloroform, toluene, paraffin, hexane, and benzene. 39. The method of claim 37, wherein the second solvent is selected from the group consisting of alcohol, methanol, ethanol, alcohol having at least two carbon atoms, isopropanol, butanol Alcohols, acetates, ethyl acetate, ketones and acetone. 15 40. A method for processing nanocrystals, comprising: adding a solvent mixture to the nanostructure, the solvent mixture comprising a first solvent in which the nanostructure is soluble and the nanostructure is insoluble The second solvent therein; precipitating the nanostructure by adding an additional amount of the second solvent, the additional amount being sufficient to precipitate the nanostructure from the solvent mixture; and removing the nanostructure from the solvent mixture; The solvent mixture was separated. 41. The method of claim 40, comprising repeating the adding, depositing, and separating steps 2 or more times. 57 200524973, the method of applying for patent No. 40, which involves dividing the nanostructure to determine the amount of surfactants present. A method for applying for a patent, wherein the first solvent comprises methylbenzene or chloroform. 42. The method of 5 10 15 20 44. The method of claim 40, wherein the second solvent comprises isopropanol, alcohol containing more than two carbon atoms, ethyl acetate or ethyl acetate. 5. If the method of applying for a patent is Gu Digang, the residual solvent structure is added, and the solvate inclusion ratio is between the first solvent and the second solvent. ^ 46. The method of claim 40, wherein the solvent mixture added to the nanostructure comprises 4 parts of toluene and 1 part of isopropyl alcohol. 47. The method according to item 40 of the scope of patent application, which further comprises performing a sterilization exchange and Shen Dian organic salt while leaving the nanostructure in solution. 48 · —A method for processing nano crystals, comprising: a) combining the nano crystals, a first solvent in which the nano crystals are soluble in |, and a second solvent in which the nano crystals are less soluble. The nanocrystal has a total amount of surfactants connected to it, the amount of surfactants includes a quantity of free surfactants and a quantity of surfactants combined with nanocrystals; /, b) allows the The first and second solvents form a first liquid phase with nanocrystals, and include the first phase; and a second liquid containing the first solvent and two solvents c) the first liquid phase from the second liquid phase To separate. 49. The method of claim 48, which includes repeating steps a, b and 58 200524973 c2 or more. For example, the method of claim 48 of Patent No. π includes repeating steps & until the amount of free evil surfactant is less than 1% of the total amount of the surfactant. • The method described in item 48 of the patent application, wherein the nanocrystals are examined after at least-separation step to determine the amount of free surfactant. The method of affirming Patent No. 48 item is that the polarity of the first solvent is lower than that of the second solvent. 53 ·: The method according to the 48th aspect of the application, wherein the first solvent is toluene, the second solvent is methanol, and the surfactant is TOP. 54. A composition comprising: a nanocrystal community dissolved in a first solvent; wherein the nanocrystal has a total amount of surfactants connected to it, and the total amount of surfactants in solution includes For a quantity of interfacial surfactant and a quantity of free surfactant, the amount of free surfactant is less than about 10/0 of the total quantity of surfactant. '55. The composition of claim 54 in which the amount of the free surface active agent is less than about 0.5% or less than about 0.1% of the total amount of the surface active agent. 6. A composition comprising a nanocrystal community dissolved in a first solvent, wherein the nanocrystal has a surfactant bound thereto, and wherein the nanocrystal contains less than two layers of interfacial activity bound to it Agent. 57. The composition according to item 56 of the patent application, wherein the nanocrystal comprises 59 200524973 about a single layer or fewer layers of a surfactant connected thereto. 58. A composition comprising a nanocrystal community and a surfactant combined therewith, wherein the surfactant comprises less than two layers. 59. The community of claim 58, wherein the surfactant comprises about a single layer or less. 60. A composite comprising: an organic polymer matrix; and a nanocrystal community disposed in the organic polymer matrix, the nanocrystal having a surfactant connected thereto, the surfactant containing less On the second floor. 61 · A composition comprising: a first nanocrystal community having a surfactant connected thereto, the surfactant comprising less than two layers; and a second nanocrystal community having a A composition different from the first nano crystal community, and the second nano crystal community is dispersed in the composition together with the first community. 62. The composition according to item 61 of the application, wherein the scattered first and first nanocrystal communities are arranged in an organic polymer matrix. 60