TW201634504A - 嵌段共聚物 - Google Patents

嵌段共聚物 Download PDF

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Publication number
TW201634504A
TW201634504A TW104132192A TW104132192A TW201634504A TW 201634504 A TW201634504 A TW 201634504A TW 104132192 A TW104132192 A TW 104132192A TW 104132192 A TW104132192 A TW 104132192A TW 201634504 A TW201634504 A TW 201634504A
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Taiwan
Prior art keywords
block copolymer
group
structural formula
atom
block
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TW104132192A
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English (en)
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TWI612066B (zh
Inventor
李美宿
金廷根
具世真
朴魯振
李濟權
崔銀英
尹聖琇
柳亨周
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Lg化學股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00388Etch mask forming
    • B81C1/00428Etch mask forming processes not provided for in groups B81C1/00396 - B81C1/0042
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/002Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005Spin coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007After-treatment
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    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F216/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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Abstract

本申請案提出嵌段共聚物和其用途。本申請案之嵌段共聚物展現極佳的自組性質或相分離性質,且可以無限制地被賦予各種所需的功能。

Description

嵌段共聚物
本發明係關於嵌段共聚物和其用途。
嵌段共聚物所具有的分子結構中,各具有不同化學結構的聚合物嵌段藉共價鍵彼此連接。嵌段共聚物可藉相分離形成規則排列的結構,如球、圓柱和層狀結構。因嵌段共聚物的自組現象而形成的結構所具有的區段的尺寸可在寬範圍內調整,且該區段可製成各種形式,這些形式可用於各種下一代的奈米裝置、磁性儲存介質、和圖案(藉蝕刻之類):特定言之,製造高密度磁性記錄介質、奈米線、量子點、金屬點之類。
本申請案提供嵌段共聚物和其用途。
除非特定指明,否則本說明書中的“烷基”是指具1至20個碳原子,1至16個碳原子,1至12個碳原子,1至8個碳原子或1至4個碳原子的烷基。以上烷基可為直鏈型、支鏈型或環型,且其可經一或更多個取代基任意地部分取代。
除非特定指明,否則本說明書中的“烷氧基”是指具1至20個碳原子,1至16個碳原子,1至12個碳原子,1至8個碳原子或1至4個碳原子的烷氧基。以上烷氧基可為直鏈型、支鏈型或環型,且其可經一或更多個取代基任意地部分取代。
除非特定指明,否則本說明書中的“烯基”或“炔基”是指具2至20個碳原子,2至16個碳原子,2至12個碳原子,2至8個碳原子或2至4個碳原子的烯基或炔基。以上烯基或炔基可為直鏈型、支鏈型或環型,且其可經一或更多個取代基任意地部分取代。
除非特定指明,否則本說明書中的“伸烷基”是指具1至20個碳原子,1至16個碳原子,1至12個碳原子,1至8個碳原子或1至4個碳原子的伸烷基。以上伸烷基可為直鏈型、支鏈型或環型,且其可經一或更多個取代基任意地部分取代。
除非特定指明,否則本說明書中的“伸烯基”或“伸炔基”是指具2至20個碳原子,2至16個碳原子,2至12個碳原子,2至8個碳原子或2至4個碳原子的伸烯基或伸炔基。以上伸烯基或伸炔基可為直鏈型、支鏈型 或環型,且其可經一或更多個取代基任意地部分取代。
除非特定指明,否則本說明書中的“芳基”或“伸芳基”是指單羥基或二羥基部分,其係衍生自具有苯環結構的化合物或者二或更多個苯環彼此連接(藉共享一或兩個碳原子或藉任何鏈接物)的結構之化合物或衍生自以上化合物的衍生物。除非特定指明,否則以上芳基或伸芳基是指具有,例如,6至30個碳原子,6至25個碳原子,6至21個碳原子,6至18個碳原子,或6至13個碳原子的芳基或伸芳基。
本申請案中,“芳族結構”是指以上芳基或伸芳基。
本說明書中,除非特定指明,否則“脂環狀環結構”是指,芳環結構以外的環型烴原子結構。除非特定指明,否則以上脂環狀環結構是指具有,例如,3至30個碳原子,3至25個碳原子,3至21個碳原子,3至18個碳原子,或3至13個碳原子的脂環狀環結構。
本申請案中,“單鍵”是指特別的原子不存在於對應區域中之情況。例如,B代表A-B-C所示結構中的單鍵時,可視為沒有特別的原子存在於標記為B的區域,造成介於A和C之間直接連接而形成A-C所示結構。
本申請案中,可任意取代烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基、芳基、伸芳基、鏈、芳族結構之類的一或更多個部分的取代基的例子可包括,但不限於,羥基、鹵原子、羧基、環氧丙基、丙烯醯 基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、巰基、烷基、烯基、炔基、伸烷基、伸烯基、伸炔基、烷氧基、和芳基等。
本申請案之嵌段共聚物可含有含以下結構式1所示結構單元之嵌段(下文中稱為嵌段1)。該嵌段1可以僅由以下結構式1所示結構單元所組成或除了以上結構式1所示結構單元以外亦含有另一結構單元。
結構式1中,R代表氫原子或烷基;X代表單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;Y代表單羥基取代基,其包括含括8或更多個成鏈原子的直鏈連接至彼的環結構。
另一例子中,結構式1的X代表單鍵、氧原子、羰基、-C(=O)-O-、-O-C(=O)-、或-C(=O)-O-,雖未限於此。
結構式1的Y所示單羥基取代基包括藉至少8個成鏈原子所構成的鏈結構。
本申請書中,“成鏈原子”是指形成預定鏈之 直鏈結構的原子。此鏈可為直鏈型或支鏈型,但成鏈原子數僅以形成最長直鏈的原子數計,且鍵結至以上成鏈原子的其他原子(如,當成鏈原子係碳原子時,鍵結至碳原子的氫原子之類)不列入計算。在支鏈型鏈的情況中,成鏈原子數為形成最長鏈之成鏈原子數。例如,鏈是正戊基時,所有的成鏈原子是碳且成鏈原子數是5,而當鏈是2-甲基戊基時,所有的成鏈原子是碳且成鏈原子數是5。成鏈原子的例子可包括碳、氧、硫、和氮;適當的成鏈原子可為碳、氧和氮中之任一者,或碳和氧中之任一者。在鏈中的成鏈原子數可為8或更多,9或更多,10或更多,11或更多,或12或更多。鏈中的成鏈原子數亦可為30或更少,25或更少,20或更少,或16或更少。
結構式1所示結構單元可提供所屬的以上嵌段共聚物極佳的自組性質。
一個例子中,上述鏈可為直鏈烴鏈,如直鏈烷基。此處,該烷基可為具8或更多個碳原子,8至30個碳原子,8至25個碳原子,8至20個碳原子,或8至16個碳原子的烷基。以上烷基中的一或更多個碳原子各者可被氧原子任意地取代,且烷基中的至少一個氫原子可被另一取代基任意地取代。
結構式1中,Y可包括環結構,且以上鏈可連接至環結構。此環結構可用以進一步改良該單體所屬嵌段共聚物的自組性質等。該環結構可為芳族結構或脂環狀結構。
以上鏈可直接或藉連接物連接至以上環結構。連接物的例子可包括氧原子、硫原子、-NR1-、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-和-X1-C(=O)-,其中R1代表氫原子、烷基、烯基、炔基、烷氧基或芳基,且X1代表單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基,其中R2代表氫原子、烷基、烯基、炔基、烷氧基、或芳基。適當連接物的例子包括氧原子和氮原子。以上鏈可連接至芳族結構,例如,藉氧原子或氮原子。此處,以上連接物可為氧原子或-NR1-(其中R1代表氫原子、烷基、烯基、炔基、烷氧基、或芳基)。
一個例子中,結構式1的Y可為以下結構式2所示者。
[結構式2]-P-Q-Z
結構式2中,P代表伸芳基;Q代表單鍵、氧原子或-NR3-,其中R3代表氫原子、烷基、烯基、炔基、烷氧基或芳基;且Z代表具8或更多個成鏈原子的前述鏈。當結構式1的Y是結構式2所示取代基時,結構式2的P可直接連接至結構式1的X。
結構式2的P的適當例子包括,但不限於,具6至12個碳原子的伸芳基,例如,伸苯基。
結構式2的Q的適當例子包括氧原子和-NR1-(其中R1代表氫原子、烷基、烯基、炔基、烷氧基、或 芳基)。
結構式1之結構單元的適當例子可包括結構式1的結構單元,其中R代表氫原子或烷基(如,具1至4個碳原子的烷基),X代表-C(=O)-O-,且Y為結構式2所示者,其中P代表伸苯基或具6至12個碳原子的伸芳基,Q代表氧原子,且Z代表含8或更多個成鏈原子的前述鏈。
因此,結構式1之適當的例示結構單元可包括以下結構式3所示結構單元。
結構式3中,R代表氫原子或具1至4個碳原子的烷基,X代表-C(=O)-O-,P代表具6至12個碳原子的伸芳基,Q代表氧原子,且Z代表含8或更多個成鏈原子的前述鏈。
另一例子中,嵌段1的結構單元(結構式1所示者)亦可為以下結構式4所示者。
結構式4中,R1和R2各者獨立地代表氫原子或具1至4個碳原子的烷基;X代表單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;T代表單鍵或伸芳基;Q代表單鍵或羰基;且Y代表含有8或更多個成鏈原子的鏈。
結構式4中,X代表單鍵、氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
結構式4的Y的鏈的特定例子可類似於關於結構式1所述者。
另一例子中,嵌段1的任一結構單元(結構式1、3和4所示者)中所含的鏈(具8或更多個成鏈原子)的至少一個成鏈原子之陰電性為3或更高。另一例子中,以上原子的陰電性可為3.7或更低。陰電性為3或更高之以上原子的例子可包括,但不限於,氮原子和氧原子。
與嵌段1一起含於嵌段共聚物中的嵌段2,其含有上述結構單元,可至少含有以下結構式5所示的結構單元。
結構式5中,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;R1至R5各者獨立地代表氫原子、烷基、鹵烷基、鹵原子或以下結構式6所示取代基,其中標記為R1至R5的位置中所含之結構式6所示取代基的數目為1或更多。
結構式6中,Y代表烷基,且X3代表氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
嵌段2可以僅由結構式5所示結構單元所構成或含有一或更多個將述於本說明書下文中的額外結構單 元。嵌段2除了結構式5所示結構單元以外,含有一或更多個額外的結構單元時,各結構單元可在嵌段2中形成獨立的次嵌段,或可不規則地位於嵌段2中。
如前述者,結構式5所示結構單元含有至少一個結構式6所示的前述取代基。藉由含有此取代基,嵌段共聚物可以更有效地形成自組結構並實現較細的相分離結構,因此,在形成圖案的期間內,形成微圖案的效率獲顯著改良。
對於可含於結構式5所示結構單元中之取代基(結構式6所示者)的類型沒有特別的限制,只要滿足以上結構式即可。以上取代基的例子可為結構式6所示結構單元,其中X3代表氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
此外,代表以上取代基之結構式6的Y可為具1至20個碳原子,1至16個碳原子,1至12個碳原子,或1至8個碳原子的支鏈型烷基。
結構式5所示結構單元可含有1或更多個結構式6所示取代基;例如,至少R3代表結構式6所示的以上取代基。
除了結構式6所示的以上取代基之外,結構式5所示結構單元可含有1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子(如,氟原子)。結構單元所含鹵原子(如氟原子)的數目亦可為10或更少,9或更少,8或更少,7或更少,或6或更少。
結構式5所示結構單元中,R1至R5中之至少一,1至3或1至2者可代表結構式6所示的以上取代基。
結構式5所示結構單元中,1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子含於標記為R1至R5的位置。含於標記為R1至R5的位置處之鹵原子的數目亦可為10或更少,9或更少,8或更少,7或更少,或6或更少。
嵌段2除了結構式5所示結構單元以外,含有額外結構單元時,結構式5所示結構單元的比例可調整至可維持或改良嵌段共聚物之自組性質的範圍內。例如,以上結構單元(結構式5所示者)在嵌段2中的比例可為約0.1mol%至5mol%,0.5mol%至5mol%,1mol%至5mol%,1.5mol%至5mol%,1.5mol%至4mol%,或1.5mol%至3mol%,此以嵌段2中之結構單元的總莫耳數計。可取決於嵌段共聚物中所含結構單元或嵌段的類型而調整此比例。
嵌段共聚物的嵌段2除了結構式5所示結構單元以外,可含有另一結構單元。此處,未特別限制額外含有之結構單元的類型。
例如,嵌段2可額外含有聚乙烯基吡咯啶酮結構單元、聚乳酸結構單元、聚(乙烯基吡啶)結構單元、聚苯乙烯結構單元(如聚苯乙烯和聚(三甲基矽基苯乙烯))、聚伸烷化氧結構單元(如聚伸乙化氧)、聚丁 二烯結構單元、聚異戊烯結構單元、或聚烯烴結構單元(如聚乙烯)。
一個例子中,嵌段2除了結構式5所示結構單元以外,可含有具一或更多個鹵原子之芳族結構的結構單元。
嵌段2的此第二結構單元可為,例如,以下結構式7所示結構單元。
結構式7中,B代表具有具一或更多個鹵原子的芳族結構之單羥基取代基。
藉由與其他嵌段(如嵌段1)具有極佳的交互作用,含有以上結構單元的嵌段可賦予所屬嵌段共聚物極佳的自組性質。
結構式7中,芳族結構可為,例如,具6至18個碳原子或6至12個碳原子的芳族結構。
結構式7的鹵原子的例子可為氟原子或氯原子,且較佳地選擇氟原子,雖未限於此。
一個例子中,結構式7的B可為具有含有6至12個碳原子且經1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子部分取代的芳族結構之單羥基取代基。以上描述中,對於鹵原子數沒有特別的限制,且 可以有,例如,10或更少,9或更少,8或更少,7或更少,或6或更少個鹵原子存在。
此處,以上結構單元(結構式7所示者)亦可為以下結構式8所示者。
結構式8中,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;且W代表包括至少一個鹵原子的芳基。W可為經至少一個鹵原子部分取代的芳基;例如,其可為具6至12個碳原子且經2或更多,3或更多,4或更多,或5或更多個鹵原子部分取代的芳基。
另一例子中,以上結構單元(結構式7所示者)亦可為以下結構式9所示者。
結構式9中,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;且R1至R5各者獨立地代表氫原子、烷基、鹵烷基或鹵原子,其中標示為R1至R5的位置所含的鹵原子數為1或更多。
另一例子中,結構式9的X2可代表單鍵、氧原子、伸烷基、-C(=O)-O-、或-O-C(=O)-。
結構式9中,R1至R5各者獨立地代表氫原子、烷基、鹵烷基或鹵原子,且有1或更多,2或更多,3或更多,4或更多,或5或更多個鹵原子(如,氟原子)含於標記為R1至R5的位置。標記為R1至R2的位置所含的鹵原子(如,氟原子)數亦可為10或更少,9或更少,8或更少,7或更少,或6或更少。
嵌段2除了結構式5所示結構單元以外,含有以上具有一或更多個鹵原子的芳族結構之結構單元 (如,結構式7至9之任一者所示結構單元)時,以上具有一或更多個鹵原子的芳族結構之結構單元的莫耳數(DH)對結構式5所示結構單元的莫耳數(D5)之比(DH/D5)可為約35至65,約40至60,或約40至50。
本申請案之嵌段共聚物係由前述嵌段1和嵌段2各者中之一或更多者所構成的嵌段共聚物。其可為僅由兩種類型的嵌段所構成的二嵌段共聚物,或其可為三嵌段或多嵌段(具有超過三種類型的嵌段)共聚物,其含有嵌段1和嵌段2之一或二者中之二或更多者或除了嵌段1和嵌段2以外另含有其他類型的嵌段。
以上嵌段共聚物可固有地展現極佳的相分離或極佳的自組性質。藉由適當地選擇和合併嵌段及滿足本發明書中將於以下描述的一或更多個參數,可進一步改良此相分離或自組性質。
嵌段共聚物含有2或更多個藉共價鍵彼此連接的聚合物鏈,並因此發生相分離。本申請案之嵌段共聚物展現相分離性質且,必要時,經由微相分離,可形成奈米尺寸結構。此奈米結構的形式和尺寸可由嵌段共聚物的尺寸(分子量之類)或嵌段間的相對比控制。可經由相分離而形成之結構的例子可包括球、圓柱、螺旋二十四面體(gyroid)、層狀物和反轉結構,且可將該嵌段共聚物形成此結構的能力稱為“自組(self-assembling)”。本發明者識別出,在本說明書之前述各種嵌段共聚物中,嵌段共聚物滿足本說明書中以下將描述的各種參數中之至少一者 時,此嵌段共聚物固有地展現顯著改良的自組性質。本申請案之嵌段共聚物滿足任一參數,或同時滿足2或更多個參數。特別地,識別出藉由滿足一或更多個適當的參數,嵌段共聚物可展現垂直定向。本申請案中,“垂直定向(vertical orientation)”是指嵌段共聚物定向的方向且是指嵌段共聚物所形成的奈米結構之定向垂直於基板方向。用於控制嵌段共聚物之自組結構水平或垂直於各種基板上的技術大多仰賴嵌段共聚物的實際施用。嵌段共聚物膜中的奈米結構之定向通常由構成嵌段共聚物之嵌段中的嵌段暴於表面或在空氣中決定。通常,基板大多為極性且空氣為非極性;因此,構成嵌段共聚物中之具有較高極性的嵌段潤濕基板,而具有較低極性的嵌段潤濕與空氣之界面。因此,提出數種技巧以有助於嵌段共聚物之各具有不同性質之不同類型的嵌段同時潤濕基板面,最具代表性的是製造中性表面以控制定向。但是,在本申請案的一方面中,適當地控制以下參數時,嵌段聚合物亦垂直定向於未以任何方法(如表面中和化處理,此為此領域中習知者)事先處理過的基板上。本申請案的另一方面中,藉由熱退火,亦可在短時間內在大面積上誘發以上的垂直定向。
本發明的一方面之嵌段共聚物能夠形成膜,其在低掠角小角度X射線散射(grazing-incidence small-angle X-ray scattering)(GISAXS)期間內,在疏水表面上製造平面內繞射圖。以上嵌段共聚物能夠形成膜,該膜在GISAXS期間內,在疏水表面上製造平面內繞射圖(in- p1ane diffraction pattern)。
本申請案中,在GISAXS期間內,製造平面內繞射圖是指在GISAXS分析期間內,在GISAXS繞射圖中,出現垂直於x-分量的峰。此峰因為嵌段共聚物的垂直定向而被察覺。因此,嵌段共聚物製造平面內繞射圖代表垂直定向。另一例子中,在GISAXS繞射圖的x-分量上觀察到的前述峰的數目可為至少2,且當有數個峰存在時,所觀察到的峰的散射向量(q值)具有整數比,各情況中,可進一步改良嵌段共聚物的相分離效率。
本申請案中,“垂直”可以有誤差;例如,此詞彙的定義可包括在±10度,±8度,±6度,±4度,或±2度範圍內的誤差。
能夠形成在親水表面和疏水表面二者上製造平面內繞射圖的膜之嵌段共聚物可在未經任何特別的方法事先處理以誘發垂直定向的各種表面上展現垂直定向。本申請案中,“親水表面”是指對於經純化的水的潤濕角度在5度至20度範圍內的表面。親水表面的例子包括,但不限於,以氧電漿、硫酸或食人魚溶液(piranha solution)進行過表面處理的矽表面。本申請案中,“疏水表面”是指對於經純化的水的潤濕角度在50度至70度範圍內的表面。疏水表面的例子可包括,但不限於,以氧電漿進行過表面處理的聚二甲基矽氮烷(PDMS)表面、以六甲基二矽氮烷(HMDS)進行過表面處理的矽表面,及以氟化氫(HF)進行過表面處理的矽表面。
除非特定指明,否則可視本申請案中之溫度而改變的性質(如潤濕角度)的數值係於室溫測得。“室溫”是指於其未加熱或冷卻的常態溫度,且可以是指約10℃至30℃,約25℃,或約23℃的溫度。
形成於親水或疏水表面上且在GISAXS期間內製造平面內繞射圖的膜可為已進行過熱退火處理的膜。用於GISAXS測定的膜可藉由,例如,以上嵌段共聚物以約0.7重量%濃度溶於溶劑(如,氟苯)中而製得的溶液以約25nm厚度和2.25cm2(寬:1.5cm,長:1.5cm)塗覆面積施於親水或疏水表面上及熱退火此塗層而形成。此熱退火可藉例如使得以上的膜維持於約160℃溫度約1小時的方式進行。GISAXS可藉以前述方式製得的膜上的X-射線入射測定,其入射角度在約0.12至0.23度範圍內。膜散射的繞射圖藉本領域習知的測定裝置(如2D mar CCD)得到。使用繞射圖證實平面內繞射圖之存在與否之方法為本領域習知者。
觀察到在GISAXS期間內具有前述峰之嵌段共聚物展現極佳的自組性質,其亦可取決於目的而經有效地控制。
在X-射線繞射(XRD)分析期間內,本申請案之嵌段共聚物有至少一個峰出現於預定的散射向量q範圍內。
例如,在XRD分析期間內,以上嵌段共聚物具有至少一個峰在0.5nm-1至10nm-1的散射向量q範圍 內。另一例子中,出現以上峰的散射向量q可為0.7nm-1或更高,0.9nm-1或更高,1.1nm-1或更高,1.3nm-1或更高,或1.5nm-1或更高。另一例子中,出現以上峰的散射向量q亦可為9nm-1或更低,8nm-1或更低,7nm-1或更低,6nm-1或更低,5nm-1或更低,4nm-1或更低,3.5nm-1或更低,或3nm-1或更低。
在以上散射向量q範圍內觀察到的峰的半高寬(FWHM)在0.2至0.9nm-1範圍內。另一例子中,以上FWHM可為0.25nm-1或更高,0.3nm-1或更高,或0.4nm-1或更高。另一例子中,以上FWHM亦可為0.85nm-1或更低,0.8nm-1或更低,或0.75nm-1或更低。
本申請案中,“FWHM”是指最大峰於最大高度一半處的寬度(即,兩個極端散射向量q值之間的差)。
XRD分析中的以上散射向量q和FWHM係將施用最小平方回歸之數值分析法用於XRD分析結果而得到的數值。以上方法中,將對應於XRD繞射圖之最低強度的部分設定為基線且最低強度設定為零,之後對以上XRD圖的峰型進行Gaussian擬合,自擬合結果得到前述散射向量q和FWHM。進行以上的Gaussian擬合時,R-平方值是至少0.9或更高,0.92或更高,0.94或更高,或0.96或更高。自XRD分析得到資訊之方法,如前述者,為本領域習知者;例如,可使用數值分析程式,如Origin。
在前述散射向量q範圍中製造具有前述 FWHM值的峰之嵌段共聚物具有適用於自組的晶狀區域。已證實在前述散射向量q範圍中之嵌段共聚物能夠展現極佳的自組性質。
XRD分析可藉由使得X-射線穿透嵌段共聚物試樣及之後測定散射強度與散射向量的關係而得。XRD分析可以在此嵌段共聚物上進行,無須任何特別的前處理;例如,可藉由在適當條件下乾燥該嵌段共聚物及之後以X-射線穿透的方式進行。可使用垂直尺寸為0.023mm且水平尺寸為0.3mm的X-射線。經由擷取得自試樣散射的2D繞射圖(其係藉由使用測量裝置(如2D mar CCD)及以前述方法擬合所得的繞射圖之影像形式),可得到散射向量和FWHM。
構成嵌段共聚物之嵌段中之至少一者含有本說明書將於以下描述的前述鏈時,該鏈中的成鏈原子數n滿足散射向量q(其自前述XRD分析得到)和以下數學式1二者。
[數學式1]3nm-1至5nm-1=nq/(2×π)
在數學式1中,n代表前述成鏈原子數,而q代表在以上嵌段共聚物進行XRD分析的期間內,可偵測到的峰的最小散射向量或觀察到具有最大峰面積之峰的散射向量。此外,數學式1中,π代表圓周對其直徑的比。
代入以上數學式1中的q等係以如前述XRD分析法描述之相同方式得到的數值。
數學式1的q等可為,例如,在0.5nm-1至10nm-1範圍內的散射向量。另一例子中,數學式1的q可為0.7nm-1或更高,0.9nm-1或更高,1.1nm-1或更高,1.3nm-1或更高,或1.5nm-1或更高。另一例子中,數學式1中的q亦可為9nm-1或更低,8nm-1或更低,7nm-1或更低,6nm-1或更低,5nm-1或更低,4nm-1或更低,3.5nm-1或更低,或3nm-1或更低。
數學式1描述當嵌段共聚物自組形成相分離結構時,各含有前述鏈的嵌段之間的距離D和成鏈原子數之間的關係。當含有前述鏈的嵌段共聚物中之成鏈原子數滿足數學式1時,鏈的晶度提高,並藉此可明顯改良相分離或垂直定向性質。另一例子中,數學式1中的nq/(2×π)可為4.5nm-1或更低。以上描述中,藉由使用數學式,D=2×π/q,可計算出含有以上鏈之嵌段中的距離(D,單位:nm),其中D代表嵌段間的上述距離(D,單位:nm),且π和q如數學式1中之定義。
本申請案的一個方面,介於嵌段共聚物中之嵌段1的表面能量和嵌段2的表面能量之間的差的絕對值可為10mN/m或更低,9mN/m或更低,8mN/m或更低,7.5mN/m或更低,或7mN/m或更低。且,介於以上表面能量之間的差的絕對值亦可為1.5mN/m,2mN/m,或2.5mN/m或更高。表面能量之間的差的絕對值在以上範圍內之嵌段1和嵌段2彼此藉共價鍵連接的結構能夠誘發相分離,此因不互溶程度足夠之故。以上描述中,嵌段 1可為,例如,含有前述鏈的前述嵌段。
表面能量可藉由使用Drop Shape Analyzer DSA100(KRUSS GmbH生產)測定。特定言之,在藉由將塗覆液(待測標的試樣(即,嵌段共聚物或均聚物)溶於氟苯中至固體濃度約2重量%而製得)以厚度約50nm且塗覆面積為4cm2(寬:2cm,長:2cm)施用在基板上,於室溫乾燥約1小時,及之後於160℃熱退火約1小時而製得的膜上可測得表面能量。重複5次藉由將本領域已知其表面張力的去離子水滴在以上經熱退火的膜上以測定接觸角度的程序,並將這5個測得的接觸角度值加以平均。類似地,重複5次藉由將本領域已知其表面張力的二碘甲烷滴在以上經熱退火的膜上以測定接觸角度的程序,並將這5個測得的接觸角度值加以平均。然後,使用分別以去離子水和二碘甲烷測得之接觸角度的平均值,將對應於溶劑之表面張力的數值(Strom值)代入根據Owens-Wendt-Rabel-Kaelble方法的數學式中,能夠得到表面能量。藉由將上述方法用於僅由構成以上嵌段之單體所構成的均聚物上,可得到對應於嵌段共聚物的各嵌段之表面能量的數值。
嵌段共聚物含有前述鏈時,含有該鏈的嵌段所具有的表面能量高於其他嵌段所具有的表面能量。例如,當嵌段共聚物的嵌段1中含有以上鏈時,嵌段1的表面能量高於嵌段2。此處,嵌段1的表面能量可在約20mN/m至40mN/m範圍內。以上嵌段1的表面能量可為 22mN/m或更高,24mN/m或更高,26mN/m或更高,或28mN/m或更高。以上嵌段1的表面能量亦可為38mN/m或更低,36mN/m或更低,34mN/m或更低,或32mN/m或更低。前述之含有嵌段1且嵌段1的表面能量不同於嵌段2之嵌段共聚物可展現極佳的自組性質。
嵌段共聚物中,介於嵌段1和嵌段2之間之密度差的絕對值可為0.25g/cm3或更高,0.3g/cm3或更高,0.35g/cm3或更高,0.4g/cm3或更高,或0.45g/cm3或更高。前述密度差的絕對值可為0.9g/cm3或更高,0.8g/cm3或更低,0.7g/cm3或更低,0.65g/cm3或更低,或0.6g/cm3或更低。嵌段1和嵌段2之密度差的絕對值在以上範圍內且彼此藉共價鍵連接之結構因為足夠的不互溶程度造成的相分離而可誘發有效的微相分離。
以上嵌段共聚物中之各嵌段的密度可藉由使用本領域中習知的浮力法測定;例如,可藉由分析嵌段共聚物在溶劑(如乙醇,已知其於空氣中質量和密度)中的質量而測得密度。
嵌段共聚物含有前述鏈時,含有此鏈的嵌段所具有的密度低於其他嵌段。例如,嵌段共聚物的嵌段1中含有前述鏈時,嵌段1的密度低於嵌段2。此處,嵌段1的密度可在約0.9g/cm3至1.5g/cm3範圍內。以上嵌段1的密度可為0.95g/cm3或更高。以上嵌段1的密度可為1.4g/cm3或更低,1.3g/cm3或更低,1.2g/cm3或更低,1.1g/cm3或更低,或1.05g/cm3或更低。含有以上嵌段1 (其密度不同於上述嵌段2)之嵌段共聚物可展現極佳的自組性質。上述表面能量和密度可為於室溫測得的數值。
嵌段共聚物可含有體積分率在0.4至0.8範圍內的嵌段和體積分率在0.2至0.6範圍內的嵌段。嵌段共聚物含有上述鏈時,含有鏈之嵌段的體積分率可在0.4至0.8範圍內。例如,此鏈含於嵌段1中時,嵌段1的體積分率可在0.4至0.8範圍內,而嵌段2的體積分率可在0.2至0.6範圍內。嵌段1和嵌段2的體積分率的和等於1。含有上述體積分率之各嵌段之嵌段共聚物展現極佳的自組性質。基於嵌段的密度和分子量(其藉凝膠穿透層析法(GPC)測得)得到嵌段共聚物中之各嵌段的體積分率。
嵌段共聚物的數量平均分子量(Mn)可為,例如,在3,000至300,000範圍內。本說明書中,“數量平均分子量”是指以GPC測得並基於聚苯乙烯標準品校正的值,且在本說明書中,除非特定指明,否則“分子量”是指數量平均分子量。另一例子中,Mn可為,例如,3000或更高,5000或更高,7000或更高,9000或更高,11000或更高,13000或更高,或15000或更高。又另一例子中,Mn可為約250000或更低,200000或更低,180000或更低,160000或更低,140000或更低,120000或更低,100000或更低,90000或更低,80000或更低,70000或更低,60000或更低,50000或更低,40000或更低,30000或更低,或25000或更低。嵌段共聚物的多分散性(Mw/Mn)可以在1.01至1.60的範圍內。另一例子 中,Mw/Mn可為約1.1或更高,約1.2或更高,約1.3或更高,或約1.4或更高。
在此範圍內,嵌段共聚物可展現足夠的自組性。可以考慮感興趣的自組結構等,調整嵌段共聚物的Mn等。
嵌段共聚物至少含有前述嵌段1和嵌段2時,嵌段1(如,含有前述鏈的嵌段之比例)在以上嵌段共聚物中之比例可在10mol%至90mol%範圍內。
本申請案中,對於製備以上嵌段共聚物的詳細方法沒有特別的限制,只要該方法包括藉由使用可形成前述結構單元各者之單體而形成嵌段共聚物的至少一個嵌段即可。
例如,使用以上單體,在活性自由基聚合(LRP)方法中製得嵌段共聚物。該方法的例子包括藉陰離子聚合反應合成,其中有機稀土金屬錯合物或有機鹼金屬化合物作為聚合反應引發劑,此在鹼金屬和無機酸鹽(如鹼土金屬)存在下進行;藉陰離子聚合法合成,其中有機鹼金屬化合物作為聚合反應引發劑,此在有機鋁化合物存在下進行;原子轉移自由基聚合反應(ATRP)方法,其中ATRP劑作為聚合反應控制劑;藉電子轉移再生活化劑(ARGET)ATRP方法,其中ATRP劑作為聚合反應控制劑,但聚合反應發生於有機或無機還原劑(其產生電子)存在時;用於連續活化劑再生之引發劑(ICAR)ATRP方法;藉可逆性加成-裂鏈轉移(RAFT)方法之聚 合反應,其中,使用無機還原劑和RAFT劑;及使用有機碲化合物作為引發劑之方法,可自其中選用適當的方法。
例如,前述嵌段共聚物可經由反應物(其包括能夠形成前述嵌段的單體)之聚合反應,藉由活性自由基聚合法,在自由基引發劑和活性自由基聚合反應劑存在下進行。
對於形成在製備嵌段共聚物的期間內與前述單體形成的嵌段一併含於嵌段共聚物中之的另一嵌段之方法沒有特別的限制;可以考慮用於形成其他嵌段之感興趣的嵌段類型,適當地選擇單體。
製備嵌段共聚物之程序可進一步包括,例如,使經由以上程序製得的聚合反應產物沉澱於非溶劑中。
對於自由基引發劑的類型沒有特別的限制,且可以考慮聚合效能,適當地選擇自由基引發劑;例如,可以使用偶氮化合物(如偶氮基雙異丁腈(AIBN)和2,2’-偶氮基雙-(2,4-二甲基戊腈)或過氧化物系列(如苄醯過氧化物(BPO)和二-三級丁基過氧化物(DTBP))。
活性自由基聚合程序可以,例如,在溶劑(如二氯甲烷、1,2-二氯乙烷、氯苯、二氯苯、苯、甲苯、丙酮、氯仿、四氫呋喃、二噁烷、單甘二甲醚(monoglyme)、二甘二甲醚(diglyme)、二甲基甲醯胺、二甲亞碸、和二甲基乙醯胺)中進行。
非溶劑的例子包括,但不限於,醇(如甲醇、乙醇、正丙醇、和異丙醇)、二醇(如乙二醇)、正己烷、環己烷、正庚烷、和醚(如石油醚)。
本申請案亦係關於含有前述嵌段共聚物之聚合物膜。該聚合物膜可用於各種應用(例如,各種電子或電力設備)、用於形成前述圖案之程序、用於磁性儲存記錄介質(如快閃記憶體)或用於生物感知器。
一個例子中,前述嵌段共聚物可經由在前述聚合物膜中之自組而實現規則結構,如球、圓柱、螺旋二十四面體或層狀物。
例如,嵌段1、嵌段2或(在共價鍵結至嵌段1和嵌段2中之任一者之其他嵌段的鏈段中)鏈段在嵌段共聚物中形成規則結構,如層狀物形式或圓柱形式。
本申請案中之以上聚合物膜可具有平面內繞射圖,其係在GISAXS分析期間內垂直於GISAXS繞射圖的x-分量的峰。另一例子中,在以上GISAXS繞射圖的x-分量上觀察到的峰數可為至少2,且,當有數個峰存在時,可觀察到的峰之散射向量q值為整數比。
本申請案亦係關於藉由使用前述嵌段共聚物形成聚合物膜之方法。該方法可包括以自組狀態在基板上形成含有以上嵌段共聚物之聚合物膜。例如,以上方法包括藉澱積之類,在基板上形成以上嵌段共聚物的層或塗覆溶液(其中嵌段共聚物溶於適當溶劑中)的層,且,必要時,亦可包括對以上層進行退火或熱處理的程序。
以上退火或熱處理可以,例如,基於嵌段共聚物的相轉變溫度或玻璃轉變溫度而進行;例如,可以在等於或大於以上玻璃轉變溫度或相轉變溫度的溫度進行。未特別限制此熱處理的期間且可為,例如,在約1分鐘至72小時的範圍內,雖可視須要地加以改變。聚合物薄膜的熱處理溫度亦可為,例如,約100℃至250℃,其可取決於所用嵌段共聚物而改變。
另一例子中,以上方式形成的層可以在室溫非極性溶劑和/或極性溶劑中進行約1分鐘至72小時的溶劑退火。
本申請案亦係關於形成圖案之方法。以上方法可包括,例如,從由基板和形成於該基板上並含有以上自組的嵌段共聚物之聚合物膜所製成的積層物選擇性地移除該嵌段共聚物的嵌段1或嵌段2之方法。以上方法可為在以上基板上形成圖案之方法。例如,以上方法可包括在基板上形成含有以上嵌段共聚物的聚合物膜,選擇性地移除存在於以上膜中之嵌段共聚物的任一或更多個嵌段,及之後蝕刻此基板。以上方法有助於形成微細圖案,例如,奈米尺寸。此外,藉以上方法亦可形成多種圖案(如奈米條和奈米孔),此取決於聚合物膜中的嵌段共聚物結構。必要時,以上嵌段共聚物可以與另一共聚物、均聚物之類混合以形成圖案。未特別限制以上方法所施用之基板的類型且可經選擇以適合該施用;例如,可使用氧化矽。
例如,以上方法可形成展現高深寬比的氧化 矽奈米尺寸圖案。可實現各種形式(如奈米條和奈米孔),例如,藉由在氧化矽上形成以上的聚合物膜,選擇性地移除以上聚合物膜(其中,嵌段共聚物構成預定結構)中之嵌段共聚物的任一嵌段,及之後藉各種技巧(例如,藉反應性離子蝕刻)中之任一者蝕刻氧化矽。以上方法亦有助於實現具有高深寬比的奈米圖案。
例如,可以數十奈米尺寸實現以上圖案,且此圖案可用於各種應用包括,例如,用於下一代資訊和電子產品的磁性記錄介質。
例如,可藉以上方法形成其寬度約3nm至40nm的奈米結構(如奈米線)間隔配置(如,間隔6nm至80nm)的圖案。另一例子中,亦可實現其寬度(如直徑)為約3nm至40nm之奈米孔以約6nm至80nm間隔配置的結構。
此外,以上結構中的奈米線或奈米孔可製成具有高深寬比。
以上方法中,對於選擇性地移除嵌段共聚物之任一嵌段的方法沒有特別的限制;例如,可以使用使得聚合膜以適當電磁波(如紫外射線)照射以移除相對軟嵌段之方法。此處,紫外射線照射條件由嵌段共聚物中的嵌段類型決定;例如,其可包括照射波長約254nm的紫外射線經1分鐘至60分鐘。
此外,紫外射線照射之後,可藉由以酸之類處理聚合物膜的方式,進行進一步移除已事先藉紫外射線 瓦解之鏈段的程序。
此外,對於使用經選擇性地移除某些嵌段的聚合物膜作為遮罩,蝕刻基板之程序沒有特別的限制;例如,以上蝕刻可以經由以CF4/Ar離子之類的反應性離子蝕刻進行。以上蝕刻之後可經由氧電漿處理之類進行自基板移除聚合物膜的程序。
本申請案提出嵌段共聚物及其用途。本申請案之嵌段共聚物展現極佳的自組性質或相分離性質,並因此而可以無限制地被賦予各種所要求的功能。
圖1出示實例1之聚合物膜的AFM結果。
下文將藉由根據本申請案之實例更詳細地描述本申請案,但本申請案之範圍不限於下文提出的實例。
實例1. 單體之合成
藉以下方法合成以下結構式A所示化合物(1,2,4,5-四氟苯乙烯-3-三級戊酸酯):將五氟苯乙烯 (25g,129mmol)加至三級丁醇和氫氧化鉀(37.5g,161mmol)的400mL混合溶液中,使所得者全數迴流2小時;此反應物冷卻至室溫並於之後添加1200mL水;此加合物以二乙醚(300mL)萃取3次,使得先前反應中使用之殘留的丁醇揮發;含水溶液層以10重量%氫氯酸溶液酸化至pH約3以使得標的物沉澱;再度以二乙醚(300mL)萃取3次,收集有機層,以MgSO4脫水,並移除溶劑以得到粗產物(3-羥基-1,2,4,5-四氟苯乙烯);此粗產物以管柱層析法,使用己烷和二氯甲烷(DCM)作為流動相加以純化,以得到無色液體3-羥基-1,2,4,5-四氟苯乙烯(11.4g)。以上物質的NMR分析結果如下。
<NMR分析結果>
1H-NMR(DMSO-d):δ11.7(s,1H);δ6.60(dd,1H);δ5.89(d,1H);δ5.62(d,1H)
將3-羥基-1,2,4,5-四氟苯乙烯(4.0g,21mmol)溶於DCM(200mL)中,於其中依序添加甲基丙烯酸(2.0g,23mmol)、N,N'-二環己基碳化二醯亞胺(DCC)(4.7g,23mmol)和對-二甲基胺基吡啶(DMAP)(1.g,8.4mmol);使此物質反應24小時,過濾移除脲副產物,移除溶劑,之後藉管柱層析法,使用DCM/己烷溶液純化,以得到透明的液態標的化合物1,2,4,5-四氟苯乙烯-3-三級戊酸酯(5.1g,19mmol,88%),其為以下結構式A所示者。以上化合物的NMR 分析結果如下。
<NMR分析結果>
1H-NMR(CDCl3):δ6.64(dd,1H);δ6.07(d,1H);δ5.68(d,1H);δ1.38(s,9H).
嵌段共聚物之合成
為使用合成的單體聚合嵌段共聚物,使用偶氮基雙異丁腈(AIBN)作為聚合反應引發劑,其與可逆性加成-裂鏈轉移(RAFT)劑(2-氰基-2-丙基十二烷基三硫代碳酸酯)和以上化合物(結構式A所示者)以30:2:0.2(結構式A所示化合物:RAFT劑:AIBN)的重量比溶於苯甲醚中(固體濃度:30重量%)。使以上溶液在氮氣氛下於70℃反應4小時以合成巨引發劑(數量平均分子量:6800,分子量分佈:1.16),其與五氟苯乙烯和AIBN以1:490:10:0.5(巨引發劑:五氟苯乙烯:結構 式A所示化合物:AIBN)的重量比溶於苯甲醚中(固體濃度:70重量%)。使所製得的溶液在氮氣氛下於70℃反應5小時以製備嵌段共聚物。所製得的嵌段共聚物的數量平均分子量和分子量分佈分別是13800和1.15。
試驗例1.
使用實例1中合成的嵌段共聚物形成自組聚合物膜,並觀察其結果。此嵌段共聚物以0.7重量%的濃度溶於溶劑中,之後以3000rpm的速率旋轉塗覆於矽晶圓上約60秒以形成聚合物薄膜。此膜於160℃熱退火1小時以誘發微相分離,其結果示於以下圖1。

Claims (18)

  1. 一種嵌段共聚物,其包含藉以下結構式1所示的結構單元之第一嵌段和藉以下結構式5所示的結構單元之第二嵌段: 其中在結構式1中,R代表氫原子或烷基;X代表單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;Y代表單羥基取代基,其包括含括8或更多個成鏈原 子的直鏈連接至彼的環結構;且其中在結構式5,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X2-或-X2-C(=O)-,其中X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;且R1至R5各者獨立地代表氫原子、烷基、鹵烷基、鹵原子或藉以下結構式6所示的取代基,其中一或多個取代基(其為藉以下結構式6所示者)含括於標示為R1至R5的位置: 其中在結構式6中,Y代表烷基,X3代表氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
  2. 如申請專利範圍第1項之嵌段共聚物,其中結構式1的X代表單鍵、氧原子、羰基、-C(=O)-O-、或-O-C(=O)-。
  3. 如申請專利範圍第1項之嵌段共聚物,其中該直鏈包括8至20個成鏈原子。
  4. 如申請專利範圍第1項之嵌段共聚物,其中該成鏈原子係碳、氧、氮、或硫。
  5. 如申請專利範圍第1項之嵌段共聚物,其中該成鏈原子係碳或氧。
  6. 如申請專利範圍第1項之嵌段共聚物,其中Y的環結構係芳環結構或脂環狀環結構。
  7. 如申請專利範圍第1項之嵌段共聚物,其中結構式1的Y係藉以下的結構式2所示:[結構式2]-P-Q-Z其中在結構式2中,P代表伸芳基;Q代表單鍵、氧原子或-NR3-,其中R3代表氫原子、烷基、烯基、炔基、烷氧基或芳基;且Z代表具8或更多個成鏈原子的直鏈。
  8. 如申請專利範圍第1項之嵌段共聚物,其中一或多個鹵原子含括於結構式5之標示為R1至R5的位置。
  9. 如申請專利範圍第1項之嵌段共聚物,其中結構式6的Y代表具1至20個碳的支鏈型烷基。
  10. 如申請專利範圍第1項之嵌段共聚物,其包含:第二嵌段,其包括比例由0.1mol%至5mol%之結構式5的結構單元。
  11. 如申請專利範圍第1項之嵌段共聚物,其中該第二嵌段進一步包括藉以下結構式8所示的結構單元: 其中在結構式8中,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或 -X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;且W代表包括至少一個鹵原子的芳基。
  12. 如申請專利範圍第1項之嵌段共聚物,其中該第二嵌段進一步包括藉以下結構式9所示的結構單元: 其中在結構式9中,X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-,其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基;且R1至R5各者獨立地代表氫原子、烷基、鹵烷基或鹵原子,其中一或多個鹵原子含括於標示為R1至R5的位置。
  13. 如申請專利範圍第12項之嵌段共聚物,其中3或更多個鹵原子含括於結構式9中標示為R1至R5的位置。
  14. 如申請專利範圍第12項之嵌段共聚物,其中 或更多個鹵原子含括於結構式9中標示為R1至R5的位置。
  15. 如申請專利範圍第12項之嵌段共聚物,其中該鹵原子係氟原子。
  16. 一種包含如申請專利範圍第1項之嵌段共聚物之聚合物膜,其中該嵌段共聚物經自組。
  17. 一種形成聚合物膜之方法,該方法包含:在基板上形成包括如申請專利範圍第1項之嵌段共聚物之聚合物膜,其中該嵌段共聚物經自組。
  18. 一種形成圖案之方法,該方法包含:自基板和聚合物膜(其形成於基板上並包括嵌段共聚物)構成的積層物選擇性地移除如申請專利範圍第1項之嵌段共聚物的任一嵌段,其中該嵌段共聚物經自組。
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