TW201425355A - 奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法 - Google Patents
奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法 Download PDFInfo
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- TW201425355A TW201425355A TW102142162A TW102142162A TW201425355A TW 201425355 A TW201425355 A TW 201425355A TW 102142162 A TW102142162 A TW 102142162A TW 102142162 A TW102142162 A TW 102142162A TW 201425355 A TW201425355 A TW 201425355A
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- Prior art keywords
- resin
- nanoimprinting
- substrate
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- phenyl
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- 239000011347 resin Substances 0.000 title claims abstract description 161
- 239000000758 substrate Substances 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 20
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 238000012546 transfer Methods 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 20
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
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- 125000006165 cyclic alkyl group Chemical group 0.000 abstract description 7
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- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 17
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
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- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 150000003232 pyrogallols Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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Abstract
本發明之課題係提供一種奈米壓印用樹脂,其係在進行奈米壓印之際,在將模版剝離時防止被轉印樹脂由基板剝離,又,進行熱奈米壓印之際,可提升產量,且可精確地將模板上之圖案轉印於被轉印樹脂。本發明之解決手段係下述式(1)所示之奈米壓印用樹脂:□(式中,R1~R5各自獨立,表示-H或-OH,R1~R5之至少1者為-OH;R6表示碳數1~20之直鏈狀、分枝狀或環狀烷基、碳數6~20之芳基、或碳數7~20之芳烷基;X表示醯胺或酯;Y雖然表示醯胺或酯,不過亦可不包含Y;p表示1~10之整數;m及n為1以上之整數)。
Description
本發明係關於奈米壓印(nanoimprint)用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法,特別係關於藉由設置在奈米壓印用基板與供轉印模板(鑄型)用之被轉印樹脂層之間,使模板轉印而剝離時,被轉印樹脂層不會從基板剝離而使用之奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法。
伴隨近年IT技術之進步,正尋求藉由半導體裝置之更微細化而達成高速動作、低耗電動作、被稱為「系統LSI」之功能之統合化等高級技術。該半導體裝置製程之核心技術的微影術技術,隨著微細化進展,除曝光裝置本身的初期成本呈指數增加外,尚有所謂「用以得到與所用光波長同等程度之解析度的光罩價格亦上升」的問題。
與此相對地,1995年由普林斯頓大學之Chou氏等所提出之奈米壓印微影術,作為廉價且同時具有10nm左右之解析度的加工技術而受到關注。奈米壓印係將模板壓附在設置於基板上之被轉印樹脂層,並將以奈
米等級在模板上所形成的圖案轉印於被轉印樹脂層的技術,與現有之微影術技術相比,由於成本較低且可形成微細之圖案,所以在半導體等電子裝置、光裝置、記錄媒體、化學‧生物裝置、MEMS等產業機械方面的應用有所進展。
就奈米壓印之代表性方法而言,已知有熱奈米壓印、光奈米壓印,此等方法依據被轉印樹脂之特性而區分。在前述方法中,熱奈米壓印係藉由將聚甲基丙烯酸甲酯(PMMA)等熱塑性樹脂作為被轉印樹脂塗布於基板上,升溫至樹脂之玻璃轉移溫度(PMMA為105℃)以上並壓合模板,冷卻後將模板及基板分離,而將模板之圖案轉印至被轉印樹脂的方法。
然而,如第1圖所示,除「(1)在塗布於基板1上之被轉印樹脂2上,(2)將模板3壓合後,(3)將模板3剝離時,被轉印樹脂2亦一起剝離」之奈米壓印共通的問題外,熱奈米壓印方法亦有「被轉印樹脂之升溫、冷卻費時,產量降低」的問題。
為了解決上述問題,已知:將玻璃基板以矽烷偶合劑處理後,塗布被轉印樹脂(參照非專利文獻1);以及在基板上之金屬塗層上,使含硫醇之二苯甲酮衍生物反應後,形成聚苯乙烯樹脂層作為被轉印樹脂(參照非專利文獻2)。然而,在前述非專利文獻1所記載之方法中,由於以矽烷偶合劑處理,基板限定於玻璃,又,在非專利文獻2所記載之方法中,必須為金屬塗層,有「基板與被轉印樹脂之組合受限定」的問題。
[非專利文獻1]Dae-Geun Choi et al,. “Measurement of Surface Adhesion Force of Adhesion Promoter and Release Layer for UV-Nanoimprint Lithography”, Journal of Nanoscience and Nanotechnology, Vol.9, p769-773, 2009
[非專利文獻2]Hirokazu Oda et al. “Photoreactive Chemisorbed Monolayer Suppressing Polymer Dewetting in Thermal Nanoimprint Lithography”, Langmuir, 2009, 25(12), p6604-6606
本發明係用於解決上述問題點所完成之發明,在進行專心研究時,新發現藉由將下述式(1)所示之奈米壓印用樹脂積層於基板上,並在其上積層轉印模板之被轉印樹脂,可使基板與被轉印樹脂之接著性提高,無論基板及被轉印樹脂之種類為何,將模板剝離時皆不會使被轉印樹脂從基板剝離,再者,在使用熱塑性樹脂作為被轉印樹脂進行熱奈米壓印之情況,由於被轉印樹脂密著於基板,即使將模板剝離時之溫度高,被轉印樹脂亦不會從基板剝離,因此可提高產量,同時可精確地將模板上之圖案轉印於被轉印樹脂。
(式中,R1~R5各自獨立,表示-H或-OH,R1~R5之至少1者為-OH;R6表示碳數1~20之直鏈狀、分枝狀或環狀烷基、碳數6~20之芳基、或碳數7~20之芳烷基;X表示醯胺或酯;Y雖然表示醯胺或酯,不過亦可不包含Y;p表示1~10之整數;m及n為1以上之整數)。
亦即,本發明之目的在於提供奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法。
本發明如以下所示,為奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法。
(1)一種下述式(1)所示之奈米壓印用樹脂:
(式中,R1~R5各自獨立,表示-H或-OH,R1~R5之至少1者為-OH;R6表示碳數1~20之直鏈狀、分枝狀或環狀烷基、碳數6~20之芳基、或碳數7~20之芳烷基;X表示醯胺或酯;Y雖然表示醯胺或酯,不過亦可不包含Y;p表示1~10之整數;m及n為1以上之整數)。
(2)如上述(1)記載之奈米壓印用樹脂,其中m及n為m:n=1:99~90:10。
(3)如上述(1)或(2)記載之奈米壓印用樹脂,其中R1~R5之中,2個為-OH。
(4)如上述(1)至(3)中任一項記載之奈米壓印用樹脂,其中該奈米壓印用樹脂係被用在基板與模板所轉印之被轉印樹脂之間。
(5)一種積層體,其包含如上述(1)至(4)記載之奈米壓印用樹脂。
(6)一種基板,其包含如上述(1)至(4)記載之奈米壓
印用樹脂。
(7)一種奈米壓印基板之製造方法,其包含:將如上述(1)至(3)記載之奈米壓印用樹脂積層在基板上的步驟;將轉印模板圖案之層積層在該奈米壓印用樹脂之層上的步驟;將模板之圖案轉印的步驟。
(8)如上述(7)記載之奈米壓印基板之製造方法,其中該轉印模板圖案之層為熱塑性樹脂,該轉印模板圖案之步驟包含:將積層有該熱塑性樹脂之基板加熱至高於該熱塑性樹脂之玻璃轉移溫度的溫度的步驟;將模板壓合之步驟;將該基板冷卻至低於該熱塑性樹脂之玻璃轉移溫度之溫度的步驟;及將模板剝離之步驟。
(9)如上述(7)記載之奈米壓印基板之製造方法,其中該轉印模板圖案之層為熱硬化性樹脂,該轉印模板圖案之步驟包含:於低於該熱硬化性樹脂之玻璃轉移溫度的溫度將模板壓合的步驟;將積層有該熱硬化性樹脂之基板加熱至高於該熱硬化性樹脂之玻璃轉移溫度之溫度的步驟;及將模板剝離的步驟。
(10)如上述(7)記載之奈米壓印基板之製造方法,其
中該轉印模板圖案之層係由包含聚合性單體與光聚合起始劑之溶液所形成者;該轉印模板圖案之步驟包含:將模板壓合之步驟;將聚合性單體交聯‧硬化之步驟;及將模板剝離之步驟。
藉由將本發明之奈米壓印用樹脂之層設置於基板與轉印模板圖案之被轉印樹脂之間並進行奈米壓印,無論基板及被轉印樹脂之種類為何,在將模板剝離時,皆可防止被轉印樹脂從基板剝離。
又,藉由使用本發明之奈米壓印用樹脂,即使將模板剝離時之溫度高,亦可精確地將模板圖案轉印至被轉印樹脂,因此可使熱奈米壓印之產量提高。
1‧‧‧基板
2‧‧‧被轉印樹脂
3‧‧‧模板
11‧‧‧基板
12‧‧‧奈米壓印用樹脂
13‧‧‧被轉印樹脂
14‧‧‧模板
第1圖係表示先前之奈米壓印之順序的概略圖。
第2圖係表示本發明之奈米壓印之順序的概略圖。
第3圖係代替圖式用之照片,為本發明之實施例中所用之模板的AMF照片。
第4圖係代替圖式用之照片,為實施例2、比較例1及比較例2中所得到之奈米壓印基板表面的AFM照片。
第5圖係代替圖式用之照片,為實施例3及比較例3所得到之奈米壓印基板表面的AFM照片。
第6圖係代替圖式用之照片,為實施例4及比較例4中所得到之奈米壓印基板表面的AFM照片。
第7圖係代替圖式用之照片,為實施例5及實施例6中所得到之奈米壓印基板表面的AFM照片。
以下,針對本發明之奈米壓印用樹脂、含該樹脂之積層體、含該樹脂之印刷基板、及奈米壓印基板之製造方法進一步具體地說明。
第2圖係表示本發明之奈米壓印基板之製造方法的概略,藉由:(1)將本發明之奈米壓印用樹脂12積層在基板11上,(2)將被轉印樹脂或含有聚合性單體及光聚合起始劑之溶液13(以下,有時簡記為「被轉印樹脂13」)積層在該奈米壓印用樹脂12上,(3)將模板14壓合在前述(2)所製作之積層體上,(4)將模板14分離,將模板14之圖案轉印於被轉印樹脂13上,而可製成奈米壓印基板。
就上述第2圖所示之奈米壓印方法而言,在被轉印樹脂13係使用熱塑性樹脂進行熱奈米壓印之情況,於第2圖(3)之步驟中,將步驟(2)所製作之積層體加熱至被轉印樹脂13之玻璃轉移溫度以上後,將模板14壓合,繼而,冷卻至被轉印樹脂13之玻璃轉移溫度以下後,於步驟(4)中將模板14分離即可。又,在被轉印樹脂13係使用熱硬化性樹脂進行熱奈米壓印之情況,於步驟(3)中,在低於被轉印樹脂13硬化之溫度的溫度,將模板14壓合,繼而,加熱至高於被轉印樹脂13之硬化溫度的溫度,將被轉印樹脂13硬化後,於步驟(4)中將模板14分離即可。
另一方面,在進行光奈米壓印之情況,於步驟(2)中塗布含有聚合性單體及光聚合起始劑之溶液,於步驟(3)中將以透明材質製作之模板14壓合後,從模板14側,或在使用透明基材之情況,從基材側照射紫外線等,使聚合性單體交聯‧硬化,並於步驟(4)中將模板14分離即可。
基板11之材質,只要可進行奈米壓印者即可,無特別限制,只需由矽、玻璃、藍寶石、金等無機物,聚對苯二甲酸乙二酯(PET)、聚四氟乙烯(PTFE)、聚對苯二甲酸萘二酯(polynaphthalene terephthalate,PEN)、聚碳酸酯(PC)、三乙醯基纖維素(TAC)、聚甲基丙烯酸甲酯(PMMA)、甲基丙烯酸甲酯與苯乙烯之共聚物(MS)等樹脂適當選擇即可。
本發明之奈米壓印用樹脂12係以下述式(1)所示之樹脂構成。
(式中,R1~R5各自獨立,表示-H或-OH,R1~R5之至少1者為-OH;R6表示碳數1~20之直鏈狀、分枝狀或環狀烷基、碳數6~20之芳基、或碳數7~20之芳烷基;X表示醯胺或酯;Y雖然表示醯胺或酯,不過亦可不包含Y;p表示1~10之整數;m及n為1以上之整數)。
上述之樹脂,為由苯環上至少經1個-OH基取代之親水性部分及疏水性之R6部分所構成之兩親媒性樹脂。R1~R5之至少1者為-OH基,在-OH基為複數個之情況,可取代於任何位置。具體而言,可列舉:-OH基為一個之苯酚,-OH基為2個之鄰苯二酚、間苯二酚、氫醌,-OH基為3個之五倍子酚(pyrogallol)、間苯三酚,-OH基為4個之四羥基苯,-OH基為5個之五羥基苯等。前述之苯環中,由將親水-疏水平衡最佳化而言,以-OH基係2~3個為較佳,以2個為特佳。再者,為使-OH基持有對基板之配向性,以鄰接為更佳。
式(1)之p,只要為1~10之整數即可。X可選自醯胺或酯。又,Y亦可選自醯胺或酯,不過亦可不包含Y。
R6為疏水性,只要具有與被轉印樹脂之親和性即可,無特別限制,可列舉如:碳數1~20之直鏈狀、分枝狀或環狀烷基,碳數6~20之芳基,碳數7~20之芳烷基等。
就碳數1~20之直鏈狀、分枝狀或環狀烷基之具體例而言,可列舉如:甲基、乙基、正丙基、2-丙基、正丁基、1-甲基丙基、2-甲基丙基、三級丁基、正戊
基、1-甲基丁基、1-乙基丙基、三級戊基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、正己基、1-甲基戊基、1-乙基丁基、2-甲基戊基、3-甲基戊基、4-甲基戊基、2-甲基戊-3-基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、1-乙基丁基、2-乙基丁基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、十九基、二十基、環丙基、環丁基、環戊基或環己基等。前述之烷基中,以碳數1~12之烷基為較佳。
就碳數6~20之芳基之具體例而言,可列舉:苯基、茚基、并環戊二烯基(pentalenyl)、萘基、薁基、茀基(fluorenyl)、菲基(phenanthrenyl)、蒽基、苊基(acenaphtylenyl)、伸聯苯基(biphenylenyl)、稠四苯基(naphthacenyl)或芘基等。
就碳數7~20之芳烷基之具體例而言,可列舉:苯甲基、苯乙基、1-苯基丙基、2-苯基丙基、3-苯基丙基、1-苯基丁基、2-苯基丁基、3-苯基丁基、4-苯基丁基、1-苯基戊基丁基、2-苯基戊基丁基、3-苯基戊基丁基、4-苯基戊基丁基、5-苯基戊基丁基、1-苯基己基丁基、2-苯基己基丁基、3-苯基己基丁基、4-苯基己基丁基、5-苯基己基丁基、6-苯基己基丁基、1-苯基庚基、1-苯基辛基、1-苯基壬基、1-苯基癸基、1-苯基十一基、1-苯基十二基、1-苯基十三基或1-苯基十四基等。
m及n為1以上之整數,前述m及n之比,以m
:n=1:99~90:10為較佳,以2:98~80:20為更佳,以5:95~20:80為特佳。
式(1)所示之樹脂,可藉由例如將下述式(2)所示之化合物及式(3)所示之化合物聚合而得到。
(式中,R1~R5各自獨立,表示-H或-OH,R1~R5之至少1者為-OH;X表示醯胺或酯;p表示1~10之整數)。
(式中,R6表示碳數1~20之直鏈狀、分枝狀或環狀烷基、碳數6~20之芳基、或碳數7~20之芳烷基;Y雖然表示醯胺或酯,不過亦可不包含Y)。
就上述式(2)所示之化合物而言,可列舉:多巴胺丙烯醯胺、間苯二酚丙烯醯胺、五倍子酚丙烯醯胺、間苯三酚丙烯醯胺、四羥基苯丙烯醯胺等。又,可列舉:與苯酚、鄰苯二酚、間苯二酚、氫醌、五倍子酚、間苯三酚、四羥基苯以烷基鍵結之丙烯醯胺及丙烯酸衍生物等。
上述式(2)所示之化合物,例如,就起始原料而言,可使用多巴胺鹽酸鹽、間苯二酚烷基胺鹽酸鹽、五倍子酚烷基胺鹽酸鹽、間苯三酚烷基胺鹽酸鹽、四氫苯烷基胺鹽酸鹽、酚烷基羧酸、間苯二酚烷基羧酸、五倍子酚烷基羧酸、間苯三酚烷基羧酸、四氫苯烷基羧酸等化合物,依照以下記載之順序而合成。
在水中溶解有碳酸氫鈉(NaHCO3)、硼酸鈉(Sodium Borate)之緩衝液中添加前述起始原料,將此溶液攪拌的同時,滴入甲基丙烯酸酐(Methacrylate anhydride)之四氫呋喃(THF)溶液。此時,以使用NaOH水溶液將溶液保持於pH8以上為較佳。將此溶液攪拌一晚後,使用HCl將溶液調整至pH2以下後,添加乙酸乙酯(Ethyl acetate),並萃取生成物。將此溶液以硫酸鈉(Na2SO4)乾燥後,用蒸發器濃縮,進行再結晶。繼而,藉由減壓過濾將所得到之化合物回收,藉由進行真空乾燥,可得到在起始原料上連結有雙鍵的式(2)之化合物。
就上述式(3)所示之化合物而言,在Y為醯胺或酯,R6為碳數1~20之直鏈狀、分枝狀或環狀烷基的情況,可列舉:甲基丙烯醯胺、乙基丙烯醯胺、正丙基丙烯醯胺、2-丙基丙烯醯胺、正丁基丙烯醯胺、1-甲基丙基丙烯醯胺、2-甲基丙基丙烯醯胺、三級丁基丙烯醯胺、正戊基丙烯醯胺、1-甲基丁基丙烯醯胺、1-乙基丙基丙烯醯胺、三級戊基丙烯醯胺、2-甲基丁基丙烯醯胺、3-甲基丁基丙烯醯胺、2,2-二甲基丙基丙烯醯胺、正己基丙烯醯胺、1-甲基戊基丙烯醯胺、1-乙基丁基丙烯醯胺、2-甲基戊基丙烯醯胺、3-甲基戊基丙烯醯胺、4-甲基戊基丙烯醯胺、2-甲基戊-3-基丙烯醯胺、3,3-二甲基丁基丙烯醯胺、2,2-二甲基丁基丙烯醯胺、1,1-二甲基丁基丙烯醯胺、1,2-二甲基丁基丙烯醯胺、1,3-二甲基丁基丙烯醯胺、2,3-二甲基丁基丙烯醯胺、1-乙基丁基丙烯醯胺、2-乙基丁基丙烯醯胺、庚基丙烯醯胺、辛基丙烯醯胺、壬基丙烯醯胺、癸基丙烯醯胺、十一基丙烯醯胺、十二基丙烯醯胺、十三基丙烯醯胺、十四基丙烯醯胺、十五基丙烯醯胺、十六基丙烯醯胺、十七基丙烯醯胺、十八基丙烯醯胺、十九基丙烯醯胺、二十基丙烯醯胺、環丙基丙烯醯胺、環丁基丙烯醯胺、環戊基丙烯醯胺、環己基丙烯醯胺等烷基丙烯醯胺類;及甲酯、乙酯、正丙酯、2-丙酯、正丁酯、1-甲基丙酯、2-甲基丙酯、三級丁酯、正戊酯、1-甲基丁酯、1-乙基丙酯、三級戊酯、2-甲基丁酯、3-甲基丁酯、2,2-二甲基丙酯、正己酯、1-甲基戊酯、1-乙基丁酯、2-甲基戊酯、3-甲基戊酯、4-甲基戊酯
、2-甲基戊-3-酯、3,3-二甲基丁酯、2,2-二甲基丁酯、1,1-二甲基丁酯、1,2-二甲基丁酯、1,3-二甲基丁酯、2,3-二甲基丁酯、1-乙基丁酯、2-乙基丁酯、庚酯、辛酯、壬酯、癸酯、十一酯、十二酯、十三酯、十四酯、十五酯、十六酯、十七酯、十八酯、十九酯、二十酯、環丙酯、環丁酯、環戊酯、環己酯等烷酯類。
在Y為醯胺或酯,R6為碳數6~20之芳基的情況,可列舉:苯基丙烯醯胺、茚基丙烯醯胺、并環戊二烯基丙烯醯胺、萘基丙烯醯胺、薁基丙烯醯胺、茀基丙烯醯胺、菲基丙烯醯胺、蒽基丙烯醯胺、苊基丙烯醯胺、伸聯苯基丙烯醯胺、稠四苯基丙烯醯胺或芘基丙烯醯胺等芳基丙烯醯胺類;及苯酯、茚酯、并環戊二烯酯、萘酯、薁酯、茀酯、菲酯、蒽酯、苊酯、伸聯苯酯、稠四苯酯或芘酯等芳酯類。
又,在Y為醯胺或酯,R6為碳數7~20之芳烷基的情況,可列舉:苯甲基丙烯醯胺、苯乙基丙烯醯胺、1-苯基丙基丙烯醯胺、2-苯基丙基丙烯醯胺、3-苯基丙基丙烯醯胺、1-苯基丁基丙烯醯胺、2-苯基丁基丙烯醯胺、3-苯基丁基丙烯醯胺、4-苯基丁基丙烯醯胺、1-苯基戊基丁基丙烯醯胺、2-苯基戊基丁基丙烯醯胺、3-苯基戊基丁基丙烯醯胺、4-苯基戊基丁基丙烯醯胺、5-苯基戊基丁基丙烯醯胺、1-苯基己基丁基丙烯醯胺、2-苯基己基丁基丙烯醯胺、3-苯基己基丁基丙烯醯胺、4-苯基己基丁基丙烯醯胺、5-苯基己基丁基丙烯醯胺、6-苯基己基丁基丙烯醯胺、1-苯基庚基丙烯醯胺、1-苯基辛基
丙烯醯胺、1-苯基壬基丙烯醯胺、1-苯基癸基丙烯醯胺、1-苯基十一基丙烯醯胺、1-苯基十二基丙烯醯胺、1-苯基十三基丙烯醯胺或1-苯基十四基丙烯醯胺等芳烷基丙烯醯胺類;及苯甲酯、苯乙酯、1-苯基丙酯、2-苯基丙酯、3-苯基丙酯、1-苯基丁酯、2-苯基丁酯、3-苯基丁酯、4-苯基丁酯、1-苯基戊基丁酯、2-苯基戊基丁酯、3-苯基戊基丁酯、4-苯基戊基丁酯、5-苯基戊基丁酯、1-苯基己基丁酯、2-苯基己基丁酯、3-苯基己基丁酯、4-苯基己基丁酯、5-苯基己基丁酯、6-苯基己基丁酯、1-苯基庚酯、1-苯基辛酯、1-苯基壬酯、1-苯基癸酯、1-苯基十一酯、1-苯基十二酯、1-苯基十三酯或1-苯基十四酯等芳烷酯類。
另一方面,就上述式(3)中不包含Y之化合物而言,在R6為碳數1~20之直鏈狀、分枝狀或環狀烷基的情況,可列舉:丙烯、2-甲基-1-丙烯、1-丁烯、2-甲基-1-丁烯、3-甲基-1-丁烯、3,3-二甲基-1-丁烯、3-甲基-2-乙基-1-丁烯、2,3-二甲基-1-丁烯、2-三級丁基-3,3-二甲基-1-丁烯、1-戊烯、2-甲基-1-戊烯、3-甲基-1-戊烯、4-甲基-1-戊烯、2-甲基-3-乙基-1-戊烯、2,4,4-三甲基-1-戊烯、1-己烯、2-乙基-1-己烯、2-丁基-1-己烯、3,3-二甲基-1-己烯、5-甲基-1-己烯、4-甲基-1-己烯、3-甲基-1-己烯、2,3-甲基-1-己烯、4,5-二甲基-1-己烯、3,4,5-三甲基-1-己烯、3,3,5-三甲基-1-己烯、2,4-二甲基-1-己烯、2,4,4-三甲基-1-己烯、4,4-二甲基-1-己烯、3-乙基-1-己烯、2,3-二甲基-1-己烯、1-庚烯、1-辛烯、1-壬烯、1-
癸烯、1-十一烯、1-十二烯、1-十三烯、1-十四烯、1-十五烯、1-十六烯、1-十七烯、1-十八烯、1-十九烯、1-二十烯、環丙烯、環丁烯、環戊烯或環己烯等。
就上述式(3)中不包含Y之化合物而言,在R6為碳數6~20之芳基的情況,可列舉:乙烯基苯(苯乙烯)、1-乙烯基茚、5-乙烯基茚、1-乙烯基并環戊二烯、1-乙烯基萘、2-乙烯基萘、2-乙烯基薁、9-乙烯基-9H-茀、2-乙烯基-9H-茀、1-乙烯基菲、2-乙烯基菲、3-乙烯基菲、6-乙烯基菲、8-乙烯基菲、1-乙烯基蒽、2-乙烯基蒽、9-乙烯基蒽、1-乙烯基苊、2-乙烯基伸聯苯、1-乙烯基稠四苯、2-乙烯基稠四苯、1-乙烯基芘、4-乙烯基芘等乙烯基芳香族類。
就上述式(3)中不包含Y之化合物而言,在R6為碳數7~20之芳烷基的情況,可列舉:3-苯基-1-丙烯、2-苯基-1-丙烯、4-苯基-1-丁烯、3-苯基-1-丁烯、2-苯基-1-丁烯、5-苯基-1-戊烯、4-苯基-1-戊烯、3-苯基-1-戊烯、2-苯基-1-戊烯、6-苯基-1-己烯、5-苯基-1-己烯、4-苯基-1-己烯、3-苯基-1-己烯、2-苯基-1-己烯、7-苯基-1-庚烯、6-苯基-1-庚烯、5-苯基-1-庚烯、4-苯基-1-庚烯、3-苯基-1-庚烯、2-苯基-1-庚烯、8-苯基-1-辛烯、7-苯基-1-辛烯、6-苯基-1-辛烯、5-苯基-1-辛烯、4-苯基-1-辛烯、3-苯基-1-辛烯、2-苯基-1-辛烯、9-苯基-1-壬烯、8-苯基-1-壬烯、7-苯基-1-壬烯、6-苯基-1-壬烯、5-苯基-1-壬烯、4-苯基-1-壬烯、3-苯基-1-壬烯、2-苯基-1-壬烯、10-苯基-1-癸烯、9-苯基-1-癸烯、8-苯基-1-癸烯、7-苯
基-1-癸烯、6-苯基-1-癸烯、5-苯基-1-癸烯、4-苯基-1-癸烯、3-苯基-1-癸烯、2-苯基-1-癸烯、11-苯基-1-十一烯、10-苯基-1-十一烯、9-苯基-1-十一烯、8-苯基-1-十一烯、7-苯基-1-十一烯、6-苯基-1-十一烯、5-苯基-1-十一烯、4-苯基-1-十一烯、3-苯基-1-十一烯、2-苯基-1-十一烯、12-苯基-1-十二烯、11-苯基-1-十二烯、10-苯基-1-十二烯、9-苯基-1-十二烯、8-苯基-1-十二烯、7-苯基-1-十二烯、6-苯基-1-十二烯、5-苯基-1-十二烯、4-苯基-1-十二烯、3-苯基-1-十二烯、2-苯基-1-十二烯、13-苯基-1-十三烯、12-苯基-1-十三烯、11-苯基-1-十三烯、10-苯基-1-十三烯、9-苯基-1-十三烯、8-苯基-1-十三烯、7-苯基-1-十三烯、6-苯基-1-十三烯、5-苯基-1-十三烯、4-苯基-1-十三烯、3-苯基-1-十三烯、2-苯基-1-十三烯、14-苯基-1-十四烯、13-苯基-1-十四烯、12-苯基-1-十四烯、11-苯基-1-十四烯、10-苯基-1-十四烯、9-苯基-1-十四烯、8-苯基-1-十四烯、7-苯基-1-十四烯、6-苯基-1-十四烯、5-苯基-1-十四烯、4-苯基-1-十四烯、3-苯基-1-十四烯、2-苯基-1-十四烯等。
本發明之兩親媒性高分子,可使用上述式(2)及式(3)之化合物,依照以下記載之順序合成。
在二甲亞碸(DMSO)與苯之混合溶劑中,使上述式(2)及式(3)之化合物、及偶氮雙異丁腈(Azobisisobutyronitrile)等自由基聚合起始劑溶解,進行3次冷凍脫氣。將此溶液於氮氣環境下加熱至60℃,進行自由基聚合。聚合後,將反應溶液滴入乙腈中,離心後
,將合成之高分子減壓乾燥,而可製作本發明之奈米壓印用樹脂。所得到之樹脂的重量平均分子量,若分子量過大,則因黏度及氫鍵而使溶解性降低,又,若分子量過小,則有無法形成膜之虞,故以5,000~500,000為較佳,以10,000~100,000為更佳。重量平均分子量可藉由調整起始劑與單體之比率而調整。又,m:n之比,只要調整式(2)及式(3)所示之化合物的添加量即可。再者,本發明中之「重量平均分子量」,意指使用TOSOH製HLC-8320GPC測定,以聚苯乙烯換算時之重量平均分子量。
就依照上述之方法所得到的本發明之奈米壓印用樹脂而言,可列舉如以下所示之樹脂。
本發明之奈米壓印用樹脂,係設置於基板11與被轉印樹脂13之間,提高基板11與被轉印樹脂13之接著性,可防止將模板分離時被轉印樹脂13由基板11剝離,因此亦可使用於熱奈米壓印、光奈米壓印之任一種轉印方法。
在熱奈米壓印之情況,被轉印樹脂13只要為熱奈米壓印中一般所用之熱塑性樹脂或熱硬化性樹脂即可,無特別限制。在使用熱塑性樹脂之情況,係將被轉印樹脂之熱塑性樹脂加熱至玻璃轉移溫度(Tg)以上,使其軟化後,藉由壓合形成有微細圖案之模板,冷卻至低於玻璃轉移溫度之溫度,而轉印微細圖案,因此以具有低於轉印時加熱溫度之玻璃轉移溫度的熱塑性樹脂為較
佳。又,在使用熱硬化性樹脂之情況,由對熱於奈米壓印法適合性之觀點而言,以具有比將形成有微細圖案之模板壓合時之加熱溫度高之玻璃轉移溫度的熱硬化性樹脂為較佳。
就前述熱塑性樹脂而言,可列舉:聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚乙酸乙烯酯(PVAc)、聚四氟乙烯(PTFE)、丙烯腈丁二烯苯乙烯樹脂(ABS樹脂)、AS樹脂、丙烯酸樹脂(PMMA)、聚胺基甲酸酯樹脂(TPU)、聚乙烯醇(PVA)、聚碳酸酯(PC)、聚碸(PSF)、聚乳酸(PLA)、聚己內酯(PCL)、聚丁二烯(BR)、聚異戊二烯(IR)等。
就前述熱硬化性樹脂而言,可列舉:酚樹脂(PF)、環氧樹脂(EP)、三聚氰胺樹脂(MF)、尿素樹脂(UF)、不飽和聚酯樹脂(UP)、醇酸樹脂、聚胺基甲酸酯(PUR)、熱硬化性聚醯亞胺(PI)等。只要考慮壓合模板時之溫度,選擇適宜樹脂即可。
就使用於光奈米壓印之光硬化性樹脂而言,只要為該領域中先前即使用之光硬化性樹脂即可,無特別限制,可列舉如:對紫外線、可視光具有硬化性之聚酯丙烯酸酯系、丙烯酸系、環氧丙烯酸酯系、胺基甲酸酯丙烯酸酯系等具有不飽和雙鍵之光硬化性樹脂。前述之光硬化性樹脂包含聚合性單體、或聚合性聚體及該單體交聯而成之寡聚物,且可藉由使用光聚合起始劑進行交聯而硬化。
就單體而言,可使用包含具有至少1個以上官
能基,且藉由對光聚合起始劑照射硬化能量射線所產生之離子或自由基而進行離子聚合、自由基聚合而增加分子量或形成交聯構造的單體或寡聚物等者。此處所謂官能基,為乙烯基、羧基、羥基等成為反應原因之原子團或鍵結樣式。就此種單體、寡聚物而言,可列舉:環氧基丙烯酸酯、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、聚矽氧丙烯酸酯等丙烯酸型、及不飽和聚酯/苯乙烯系、聚烯/苯乙烯系等非丙烯酸系,不過其中由硬化速度、物性選擇之寬廣度而言,以丙烯酸型為較佳。此種丙烯酸型之代表例如以下所示。
首先,就單官能基者而言,可列舉:丙烯酸2-乙基己酯、丙烯酸2-乙基己酯EO加成物、乙氧基二乙二醇丙烯酸酯、丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、丙烯酸2-羥乙酯之己內酯加成物、丙烯酸2-苯氧基乙酯、苯氧基二乙二醇丙烯酸酯、壬基酚EO加成物丙烯酸酯、於壬基酚EO加成物上加成有己內酯之丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸四氫糠基酯、糠醇之己內酯加成物丙烯酸酯、丙烯醯基啉、丙烯酸二環戊烯酯、丙烯酸二環戊酯、丙烯酸二環戊烯基氧乙酯、丙烯酸異莰酯、4,4-二甲基-1,3-二氧雜環戊烷(dioxolane)之己內酯加成物之丙烯酸酯、3-甲基-5,5-二甲基-1,3-二氧雜環戊烷之己內酯加成物之丙烯酸酯等。
又,就多官能基者而言,可列舉:己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、羥基三甲基乙酸新戊二醇酯二
丙烯酸酯、羥基三甲基乙酸新戊二醇酯之己內酯加成物之二丙烯酸酯、1,6-己二醇之二甘油基醚之丙烯酸加成物、羥基三甲基乙醛與三羥甲基丙烷之縮醛化合物之二丙烯酸酯、2,2-雙[4-(丙烯醯氧基二乙氧基)苯基]丙烷、2,2-雙[4-(丙烯醯氧基二乙氧基)苯基]甲烷、氫化雙酚環氧乙烷加成物之二丙烯酸酯、三環癸烷二甲醇之二丙烯酸酯、三羥甲基丙烷之三丙烯酸酯、新戊四醇之三丙烯酸酯、三羥甲基丙烷環氧丙烷加成物之三丙烯酸酯、甘油環氧丙烷加成物之三丙烯酸酯、二新戊四醇之六丙烯酸酯五丙烯酸酯混合物、二新戊四醇之己內酯加成物之丙烯酸酯、參(丙烯醯氧基乙基)異氰酸酯、磷酸2-丙烯醯氧基乙酯等。
就所使用之光聚合起始劑而言,無特別限定,可選擇周知者而使用。具體而言,可列舉:苯乙酮系、二苯甲酮系、米其勒酮(Michler’s ketone)系、苯甲基系、苯偶姻系、苯偶姻醚系、苯甲基二甲酮(benzyldimethyl ketal)、苯偶姻苯甲酸酯系、α-醯基肟酯(acyloxime ester)等羰基化合物、四甲基秋蘭姆單硫化物(tetramethylthiuram monosulfide)、噻噸酮類(thioxanthone)等硫化合物、2,4,6-三甲基苯甲基二苯基膦氧化物等磷化合物等。
再者,本發明之奈米壓印用樹脂,即使為原有狀樣,亦可提高光硬化性樹脂等被轉印樹脂13與基板之接著性,然而為了更提高接著性,藉由在式(1)之R6之直鏈狀、分枝狀或環狀烷基、芳基、或芳烷基的末端,
導入環氧基、疊氮基、或乙烯基等,於聚合性單體硬化時一體地硬化,而可進一步提高接著性。
就在上述之末端導入有環氧基、疊氮基、或乙烯基等之化合物之例而言,可列舉:縮水甘油基丙烯酸酯、疊氮基丙烯酸酯、1,2-丁二烯。
模板14上之微細圖案,只要因應期望之模板材料或精度,藉由周知之加工法形成即可。例如,可採取光微影術、集束離子束微影術、電子束描畫法、切削加工等機械加工;或可採取藉由由模板原盤之成形法、電鍍法等之複製品製作等手法。
只要將本發明之奈米壓印樹脂12及被轉印樹脂13溶解:對於疏水性聚合物,溶解於氯仿等有機溶劑,對於水溶性聚合物,溶解於水;且藉由旋塗、澆鑄(cast)等,依奈米壓印樹脂12,繼而被轉印樹脂13之順序積層在基板上即可。奈米壓印樹脂12及被轉印樹脂13之厚度,以0.1~100μm為較佳。又,在使用含聚合性單體及光聚合起始劑之溶液作為被轉印樹脂13的情況,只要以旋塗等方法使溶液層成為0.1~100μm之厚度即可。
以下揭示實施例,具體地說明本發明,不過該實施例係僅為了本發明之說明,為了具體型態之參考而提供者。此等例示雖用於說明本發明之特定具體型態,然而並非表示限定或限制本申請案所揭示之發明範圍者。
[奈米壓印用模板之製作]
藉由在直徑1μm之孔洞以1μm之間隔形成四角格子狀之矽基板上,澆鑄聚苯乙烯(Aldrich公司製182427,重量平均分子量=約28萬)之氯仿溶液(10mg/mL),於常溫使其乾燥,而製作聚苯乙烯膜。然後,浸漬於乙醇中,使用鑷子,由矽基板將具有突起狀構造的聚苯乙烯膜剝離。將所製作之聚苯乙烯膜以突起構造向上之方式放置於平皿,並澆鑄聚二甲基矽氧烷彈性體(PDMS)之前驅體與白金觸媒以10:1混合者(Dow Corning Toray公司製,SylPot184(註冊商標)),藉由減壓脫泡後,使其於70℃硬化5小時。硬化後,藉由氯仿(或苯)將聚苯乙烯膜溶解,而製作聚二甲基矽氧烷彈性體模板(以下有時記載為「PDMS模板」)。將所得到之PDMS模板的原子力顯微鏡(AFM,Seiko Instrument製,SPI-400)照片示於第3圖中。
<實施例1>
[奈米壓印用樹脂之製作]
在以Milipore公司之超純水製造裝置製作之100ml超純水(Milli-Q)中,添加4.0g之碳酸氫鈉(和光純藥工業股份有限公司製198-01315)、10.0g之硼酸鈉(和光純藥工業股份有限公司製192-01455)、及5.0g之多巴胺氯化物(DOPA:Dopamine chloride,Aldrich公司製H8502)。將此溶液攪拌的同時,將4.7ml之甲基丙烯酸酐(Aldrich公司製276685)溶解於25ml之四氫呋喃(THF:和光純藥工業股份有限公司製200-00486)的溶液滴入。此時,使用1mol/L之NaOH水溶液,將溶液保持pH8以上。將此溶液
攪拌一晚後,使用6mol/L之HCl,將溶液調整為pH2以下後,添加乙酸乙酯萃取生成物。將此溶液以硫酸鈉乾燥後,以蒸發器濃縮,進行再結晶。藉由減壓過濾回收多巴胺甲基丙烯醯胺(DMA:Dopamine methacrylamide),並進行真空乾燥。本發明之兩親媒性高分子,係在二甲亞碸(DMSO):苯=3:50之混合溶劑中,以DMA 0.673mmol、N-十二基丙烯醯胺(NDA:N-dodecylacrylamide)5.43mmol、偶氮雙異丁腈(Azobisisobutyronitrile)0.125mmol的比率溶解,並進行3次冷凍脫氣。將此溶液在氮氣環境下加熱至60℃,進行自由基聚合。聚合後,將反應溶液滴入乙腈中,離心後,將所合成之高分子減壓乾燥,製作本發明之奈米壓印用樹脂(以下,有時記載為「PDOPA樹脂」)。
[奈米壓印試驗(奈米壓印溫度之影響)]
<實施例2>
藉由在玻璃基板(松浪硝子公司製蓋玻璃)上,將在實施例1中所製作之PDOPA樹脂的氯仿溶液(2mg/mL),以3,000rpm旋塗,繼而,將聚苯乙烯(PS:Aldrich公司製182427,玻璃轉移點約100℃)之氯仿溶液(2mg/mL),以3,000rpm旋塗,而於玻璃基板上製作薄膜之積層體。繼而,藉由在設置於減壓室內的上下之加熱台(hot stage)的下部加熱台上,設置前述基板,並於前述基板上配置PDMS模板,將上部加熱台以約100kPa之壓力壓合後,於減壓下(壓力10-1Pa)、100℃退火(annealing)1小時,然後導入空氣,使減壓室內部回復至常壓,將加熱台溫度冷
卻至50℃後,釋放對加熱台所施之壓力,而進行奈米壓印。所得到之奈米壓印基板表面之表面構造,係藉由原子力顯微鏡(AFM、Seiko Instrument製、SPI-400)進行觀察。第4圖(1)表示在實施例2中所得到之奈米壓印基板表面的AFM照片。
<比較例1>
除了未進行PDOPA樹脂之氯仿溶液的旋塗以外,以與實施例1同樣之順序進行奈米壓印。第4圖(2)表示在比較例1中所得到之奈米壓印基板表面的AFM照片。
<比較例2>
除了未進行PDOPA樹脂之氯仿溶液的旋塗,並將退火後加熱台之溫度冷卻至30℃以外,以與實施例1同樣之順序進行奈米壓印。第4圖(3)表示在比較例2中所得到之奈米壓印基板表面的AFM照片。
如第4圖(3)所示,在未設置PDOPA樹脂層的情況、奈米壓印後,藉由將玻璃基板充分冷卻至30℃為止,可在解析度低之聚苯乙烯層上轉印PDMS模板之圖案。然而,在設定成提高玻璃基板之冷卻溫度(50℃)的情況,將PDMS模板剝下時,設置於玻璃基板上之聚苯乙烯層亦剝離,無法轉印PDMS模板之圖案。另一方面,在玻璃基板與聚苯乙烯層之間設置有PDOPA樹脂層之實施例1,即使玻璃基板之冷卻溫度為50℃,將PDMS模板剝下時,聚苯乙烯層未被剝離,可精確地轉印PDMS模板之圖案。
[奈米壓印試驗(基板之影響)]
<實施例3>
除作為基板使用聚對苯二甲酸乙二酯(PET,Sanplatec公司製)代替玻璃以外,以與實施例2同樣順序進行奈米壓印。第5圖(1)表示實施例2中所得到之奈米壓印基板表面的AFM照片。
<比較例3>
除未進行PDOPA樹脂之氯仿溶液的旋塗以外,以與實施例3同樣順序進行奈米壓印。第5圖(2)表示在比較例3中所得到之奈米壓印基板表面的AFM照片。
<實施例4>
除了使用聚四氟乙烯(PTFE,Sanplatec公司製)代替玻璃作為基板以外,以與實施例2同樣順序進行奈米壓印。第6圖(1)表示在實施例4中所得到之奈米壓印基板表面的AFM照片。
<比較例4>
除未進行PDOPA樹脂之氯仿溶液的旋塗,並將聚四氟乙烯以澆鑄法代替旋塗而進行積層以外,以與實施例4同樣順序進行奈米壓印。第6圖(2)表示在比較例3中所得到之奈米壓印基板表面的AFM照片。
如比較例1、3、4所明示,在未設置PDOPA樹脂層而進行奈米壓印的情況,將疏水性高之PET作為基板的比較例3,係如第5圖(2)所示,雖可於聚苯乙烯層轉印PDMS模板圖案,然而將疏水性小之比較例1之玻璃,比較例4之PTFE用於基板的情況,如第4圖(2)及第6圖(2)所示,無法將PDMS模板之圖案轉印於聚苯乙烯層。
另一方面,在基板與聚苯乙烯層之間設置PDOPA樹脂層的實施例2~4,如第4圖(1)、第5圖(1)及第6圖(1)所示,無論基板之種類為何,均可將PDMS模板之圖案精確地轉印於聚苯乙烯層。
[奈米壓印試驗(積層樹脂之影響)]
<實施例5>
除了使用聚乙烯醇(PVA,和光純藥製,玻璃轉移溫度約85℃)之水溶液(10mg/mL)代替聚苯乙烯以外,以與實施例2同樣順序進行奈米壓印。第7圖(1)表示在實施例5中所得到之奈米壓印基板表面的AFM照片。
<實施例6>
除了使用聚乙烯醇縮丁醛(PVB,和光純藥製,玻璃轉移溫度約70℃)之氯仿溶液(5mg/mL)代替聚苯乙烯以外,以與實施例2同樣順序進行奈米壓印。第7圖(2)表示在實施例6中所得到之奈米壓印基板表面的AFM照片。
如實施例2、5、6所明示,若在基板與轉印PDMS模板之樹脂層之間設置PDOPA樹脂層,無論轉印PDMS模板的樹脂層為疏水性(實施例2、6)或親水性(實施例5),皆可精確地轉印PDMS模板之圖案。
由上述之實施例1~6及比較例1~4所明示,藉由將本發明之PDOPA樹脂層設置於基板及轉印PDMS模板之樹脂層之間,無關於基板之種類、轉印PDMS模板之樹脂層之種類,再者,即使奈米壓印後未充分冷卻,均可將PDMS模板之圖案轉印於被轉印樹脂層。
藉由使用本發明之奈米壓印用樹脂,無關於基板之種類、轉印模板之被轉印樹脂層之種類,均可進行奈米壓印,更且,將模板剝離時,無需將基板充分冷卻。因此,可使用多種基板、樹脂進行奈米壓印,而可使用先前奈米壓印無法賦形之材質作為基板,例如,在用於醫療材料之Teflon(註冊商標)基板上賦予適於細胞支架的形狀,或亦可在玻璃上將聚合物性抗反射膜賦形。再者,由於剝離模板時無需充分冷卻,而可縮短製造時間,並可提高製造效率,因此對奈米壓印之更為普及頗為有用。
因此,本發明可用於半導體積體電路或液晶顯示裝置用構件、光學零件、記錄媒體、光波導、保護薄膜、微反應器、奈米裝置、醫療領域分離分析用晶片等製品。
11‧‧‧基板
12‧‧‧奈米壓印用樹脂
13‧‧‧被轉印樹脂
14‧‧‧模板
Claims (13)
- 一種下述式(1)所示之奈米壓印用樹脂:
- 如請求項1之奈米壓印用樹脂,其中該m及n係m:n=1:99~90:10。
- 如請求項1之奈米壓印用樹脂,其中該R1~R5之中,2個為-OH。
- 如請求項2之奈米壓印用樹脂,其中該R1~R5之中,2個為-OH。
- 如請求項1至4中任一項之奈米壓印用樹脂,其中該奈米壓印用樹脂係被用在基板與模板所轉印之被轉印樹脂之間。
- 一種積層體,其包含如請求項1至4中任一項之奈米壓印用樹脂。
- 一種積層體,其包含如請求項5之奈米壓印用樹脂。
- 一種基板,其包含如請求項1至4中任一項之奈米壓印用樹脂。
- 一種基板,其包含如請求項5之奈米壓印用樹脂。
- 一種奈米壓印基板之製造方法,其包含:將如請求項1至4中任一項之奈米壓印用樹脂積層在基板上的步驟;將轉印模板圖案之層積層在該奈米壓印用樹脂之層上的步驟;轉印模板圖案的步驟。
- 如請求項10之奈米壓印基板之製造方法,其中該轉印模板圖案之層為熱塑性樹脂,該轉印模板圖案之步驟包含:將積層有該熱塑性樹脂之基板加熱至高於該熱塑性樹脂之玻璃轉移溫度的溫度的步驟;將模板壓合的步驟;將該基板冷卻至低於該熱塑性樹脂之玻璃轉移溫度之溫度的步驟;及將模板剝離的步驟。
- 如請求項10之奈米壓印基板之製造方法,其中該轉印模板圖案之層為熱硬化性樹脂,該轉印模板圖案之步驟包含:在低於該熱硬化性樹脂之玻璃轉移溫度的溫度壓 合模板的步驟;將積層有該熱硬化性樹脂之基板加熱至高於該熱硬化性樹脂之玻璃轉移溫度之溫度的步驟;及將模板剝離的步驟。
- 如請求項10之奈米壓印基板之製造方法,其中該轉印模板圖案之層係由包含聚合性單體及光聚合起始劑之溶液所形成者,該轉印模板圖案之步驟包含:將模板壓合之步驟;將聚合性單體交聯‧硬化之步驟;及將模板剝離之步驟。
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JP6624808B2 (ja) * | 2014-07-25 | 2019-12-25 | キヤノン株式会社 | 光硬化性組成物、これを用いた硬化物パターンの製造方法、光学部品の製造方法、回路基板の製造方法 |
JP6740615B2 (ja) * | 2016-01-14 | 2020-08-19 | Jsr株式会社 | 樹脂組成物および感光性樹脂組成物、レジストパターンの製造方法、ならびにタッチパネル部材 |
KR102369383B1 (ko) * | 2017-12-07 | 2022-02-28 | 주식회사 엘지화학 | 카르본산 변성 니트릴계 공중합체 라텍스, 이의 제조방법, 이를 포함하는 딥 성형용 라텍스 조성물 및 이로부터 성형된 성형품 |
CN109971163B (zh) * | 2019-04-04 | 2021-02-02 | 陕西科技大学 | 一种水性聚氨酯/Fe3+凝胶材料的制备方法 |
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JP5033615B2 (ja) * | 2007-12-27 | 2012-09-26 | 株式会社日立製作所 | インプリント用基板 |
CN102372817A (zh) * | 2010-08-11 | 2012-03-14 | 郁锋 | 一种酰胺衍生物共聚物的制备方法及应用 |
JP2012183753A (ja) * | 2011-03-07 | 2012-09-27 | Fujifilm Corp | ナノインプリント方法 |
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