Source: http://patents.com/us-10005308.html
Timestamp: 2019-05-23 11:35:14
Document Index: 225226547

Matched Legal Cases: ['Application No. 098103713', 'Application No. 200980104066', 'Application No. 200980104066', 'Application No. 200980104066', 'Application No. 200980104066', 'Application No. 200980104066', 'Application No. 09707891', 'Application No. 10', 'Application No. 10', 'Application No. 10', 'Application No. 10', 'Application No. 10', 'Application No. 10', 'Application No. 10']

US Patent # 1,000,5308. Stamps and methods of forming a pattern on a substrate - Patents.com
United States Patent 10,005,308
Millward , et al. June 26, 2018
Stamps and methods of forming a pattern on a substrate
Methods for fabricating stamps and systems for patterning a substrate, and devices resulting from those methods are provided.
Millward; Dan B. (Boise, ID), Sandhu; Gurtej S. (Boise, ID)
Family ID: 43306691
14/669,612
US 20150191034 A1 Jul 9, 2015
12026214 Feb 5, 2008 8999492
Current CPC Class: B81C 99/009 (20130101); B82Y 10/00 (20130101); B82Y 30/00 (20130101); G03F 7/0002 (20130101); G03F 7/0017 (20130101); B41N 1/08 (20130101); B41N 3/036 (20130101); B82Y 40/00 (20130101); B05D 1/283 (20130101); B81C 2201/0149 (20130101); Y10T 428/24802 (20150115); Y02C 20/30 (20130101)
Current International Class: B32B 3/10 (20060101); B82Y 40/00 (20110101); B82Y 30/00 (20110101); B81C 99/00 (20100101); B41N 1/08 (20060101); B82Y 10/00 (20110101); B41N 3/03 (20060101); G03F 7/00 (20060101); B05D 1/28 (20060101)
4623674 November 1986 Bailey, Jr.
4797357 January 1989 Mura et al.
4818713 April 1989 Feygenson
4877647 October 1989 Klabunde
5374367 December 1994 Edamura et al.
5382373 January 1995 Carlson
5482656 January 1996 Hiraoka et al.
5538655 July 1996 Fauteux et al.
5580700 December 1996 Rahman et al.
5620850 April 1997 Bamdad et al.
5622668 April 1997 Thomas et al.
5834583 November 1998 Hancock et al.
5849810 December 1998 Mueller
5866297 February 1999 Barjesteh
5879582 March 1999 Havelka et al.
5879853 March 1999 Azuma
5891356 April 1999 Inoue et al.
5904824 May 1999 Oh et al.
5925259 July 1999 Biebuyck et al.
5948470 September 1999 Harrison et al.
5958704 September 1999 Starzl et al.
6051869 April 2000 Pan et al.
6111323 August 2000 Carter et al.
6143647 November 2000 Pan et al.
6207787 March 2001 Fahey et al.
6251791 June 2001 Tsai et al.
6270946 August 2001 Miller
6309580 October 2001 Chou
6310138 October 2001 Yonezawa et al.
6312971 November 2001 Amundson et al.
6368871 April 2002 Christel et al.
6403382 June 2002 Zhu et al.
6414164 July 2002 Afzali-Arclakani et al.
6423465 July 2002 Hawker et al.
6503841 January 2003 Criscuolo et al.
6506660 January 2003 Holmes et al.
6517933 February 2003 Soane et al.
6518194 February 2003 Winningham et al.
6537920 March 2003 Krivokapic
6548830 April 2003 Noguchi et al.
6565763 May 2003 Asakawa et al.
6565764 May 2003 Hiraoka et al.
6566248 May 2003 Wang et al.
6569528 May 2003 Nam et al.
6592764 July 2003 Stucky et al.
6630520 October 2003 Bruza et al.
6635912 October 2003 Ohkubo
6656308 December 2003 Hougham et al.
6679996 January 2004 Yao
6682660 January 2004 Sucholeiki et al.
6689473 February 2004 Guire et al.
6699797 March 2004 Morris et al.
6713238 March 2004 Chou et al.
6746825 June 2004 Nealey et al.
6767693 July 2004 Okoroanyanwu
6780492 August 2004 Hawker et al.
6781166 August 2004 Lieber et al.
6797202 September 2004 Endo et al.
6809210 October 2004 Chandross
6812132 November 2004 Ramachandrarao et al.
6825358 November 2004 Afzali-Ardakani et al.
6884842 April 2005 Soane et al.
6887332 May 2005 Kagan et al.
6890624 May 2005 Kambe et al.
6890703 May 2005 Hawker et al.
6908861 June 2005 Sreenivasan et al.
6911400 June 2005 Colburn et al.
6913697 July 2005 Lopez et al.
6924341 August 2005 Mays et al.
6926953 August 2005 Nealey et al.
6940485 September 2005 Noolandi
6946332 September 2005 Loo et al.
6949456 September 2005 Kumar
6952436 October 2005 Wirnsberger et al.
6957608 October 2005 Hubert et al.
6962823 November 2005 Empedocles et al.
6989426 January 2006 Hu et al.
6992115 January 2006 Hawker et al.
6995439 February 2006 Hill et al.
6998152 February 2006 Uhlenbrock
7001795 February 2006 Jiang et al.
7009227 March 2006 Patrick et al.
7030495 April 2006 Colburn et al.
7037738 May 2006 Sugiyama et al.
7037744 May 2006 Colburn et al.
7045851 May 2006 Black et al.
7056455 June 2006 Matyjaszewski et al.
7056849 June 2006 Wan et al.
7060774 June 2006 Sparrowe et al.
7066801 June 2006 Balijepalli et al.
7077992 July 2006 Sreenivasan et al.
7087267 August 2006 Breen et al.
7090784 August 2006 Asakawa et al.
7112617 September 2006 Kim et al.
7115305 October 2006 Bronikowski et al.
7115995 October 2006 Wong
7118784 October 2006 Xie
7119321 October 2006 Quinlan
7132370 November 2006 Paraschiv et al.
7135144 November 2006 Christel et al.
7135241 November 2006 Ferraris et al.
7135388 November 2006 Ryu et al.
7135523 November 2006 Ho et al.
7151209 December 2006 Empedocles et al.
7163712 January 2007 Chilkoti et al.
7166304 January 2007 Harris et al.
7172953 February 2007 Lieber et al.
7186613 March 2007 Kirner et al.
7189430 March 2007 Ajayan et al.
7189435 March 2007 Tuominen et al.
7190049 March 2007 Tuominen et al.
7202308 April 2007 Boussand et al.
7208836 April 2007 Manning
7252791 August 2007 Wasserscheid et al.
7259101 August 2007 Zurcher et al.
7279396 October 2007 Derderian et al.
7282240 October 2007 Jackman et al.
7291284 November 2007 Mirkin et al.
7311943 December 2007 Jacobson et al.
7326514 February 2008 Dai et al.
7332370 February 2008 Chang et al.
7332627 February 2008 Chandross et al.
7338275 March 2008 Choi et al.
7347953 March 2008 Black et al.
7368314 May 2008 Ufert
7407887 August 2008 Guo
7408186 August 2008 Merkulov et al.
7419772 September 2008 Watkins et al.
7470954 December 2008 Lee et al.
7514339 April 2009 Yang et al.
7521090 April 2009 Cheng et al.
7553760 June 2009 Yang et al.
7569855 August 2009 Lai
7585741 September 2009 Manning
7592247 September 2009 Yang et al.
7605081 October 2009 Yang et al.
7632544 December 2009 Ho et al.
7655383 February 2010 Mela et al.
7658773 February 2010 Pinnow
7700157 April 2010 Bronikowski et al.
7723009 May 2010 Sandhu et al.
7767099 August 2010 Li et al.
7799416 September 2010 Chan et al.
7888228 February 2011 Blanchard
7959975 June 2011 Millward
7964107 June 2011 Millward
8039196 October 2011 Kim et al.
8080615 December 2011 Millward
8083953 December 2011 Millward et al.
8083958 December 2011 Li et al.
8097175 January 2012 Millward et al.
8101261 January 2012 Millward et al.
8114300 February 2012 Millward
8114301 February 2012 Millward et al.
8114306 February 2012 Cheng et al.
8206601 June 2012 Bosworth et al.
8287749 October 2012 Hasegawa et al.
8294139 October 2012 Marsh et al.
8372295 February 2013 Millward
8394483 March 2013 Millward
8404124 March 2013 Millward et al.
8409449 April 2013 Millward et al.
8425982 April 2013 Regner
8426313 April 2013 Millward et al.
8445592 May 2013 Millward
8455082 June 2013 Millward
8512846 August 2013 Millward
8513359 August 2013 Millward
8518275 August 2013 Millward et al.
8551808 October 2013 Marsh et al.
8557128 October 2013 Millward
8609221 December 2013 Millward et al.
8633112 January 2014 Millward et al.
8641914 February 2014 Regner
8642157 February 2014 Millward et al.
8669645 March 2014 Millward et al.
8753738 June 2014 Millward et al.
8784974 July 2014 Millward
8785559 July 2014 Millward
8801894 August 2014 Millward
8808557 August 2014 Seino et al.
8900963 December 2014 Sills et al.
8956713 February 2015 Millward
2001/0024768 September 2001 Matsuo et al.
2001/0049195 December 2001 Chooi et al.
2002/0055239 May 2002 Tuominen et al.
2002/0084429 July 2002 Craighead et al.
2002/0158342 October 2002 Tuominen et al.
2002/0167117 November 2002 Chou
2003/0010241 January 2003 Fujihira et al.
2003/0034329 February 2003 Chou
2003/0068639 April 2003 Haneder et al.
2003/0077452 April 2003 Guire et al.
2003/0080471 May 2003 Chou
2003/0080472 May 2003 Chou
2003/0091752 May 2003 Nealey et al.
2003/0100822 May 2003 Lew et al.
2003/0108879 June 2003 Klaerner et al.
2003/0143375 July 2003 Noguchi et al.
2003/0157248 August 2003 Watkins et al.
2003/0178707 September 2003 Abbott
2003/0180522 September 2003 DeSimone et al.
2003/0180966 September 2003 Abbott et al.
2003/0185741 October 2003 Matyjaszweski et al.
2003/0196748 October 2003 Hougham et al.
2003/0218644 November 2003 Higuchi et al.
2003/0222048 December 2003 Asakawa et al.
2003/0235930 December 2003 Bao et al.
2004/0023287 February 2004 Harnack et al.
2004/0028875 February 2004 Van Rijn et al.
2004/0058059 March 2004 Linford et al.
2004/0076757 April 2004 Jacobson et al.
2004/0084298 May 2004 Yao et al.
2004/0109263 June 2004 Suda et al.
2004/0124092 July 2004 Black
2004/0125266 July 2004 Miyauchi et al.
2004/0127001 July 2004 Colburn et al.
2004/0142578 July 2004 Wiesner et al.
2004/0159633 August 2004 Whitesides et al.
2004/0163758 August 2004 Kagan et al.
2004/0175628 September 2004 Nealey et al.
2004/0192013 September 2004 Ryu et al.
2004/0222415 November 2004 Chou et al.
2004/0242688 December 2004 Chandross et al.
2004/0254317 December 2004 Hu
2004/0256615 December 2004 Sirringhaus et al.
2004/0256662 December 2004 Black et al.
2004/0265548 December 2004 Ho et al.
2005/0008828 January 2005 Libera et al.
2005/0062165 March 2005 Saenger et al.
2005/0074706 April 2005 Bristol et al.
2005/0079486 April 2005 Abbott
2005/0100830 May 2005 Xu et al.
2005/0120902 June 2005 Adams et al.
2005/0124135 June 2005 Ayazi et al.
2005/0133697 June 2005 Potyrailo et al.
2005/0147841 July 2005 Tavkhelidze
2005/0159293 July 2005 Wan et al.
2005/0167651 August 2005 Merkulov et al.
2005/0176256 August 2005 Kudelka
2005/0208752 September 2005 Colburn et al.
2005/0238889 October 2005 Iwamoto et al.
2005/0238967 October 2005 Rogers et al.
2005/0250053 November 2005 Marsh et al.
2005/0271805 December 2005 Kambe et al.
2005/0272341 December 2005 Colburn et al.
2006/0013956 January 2006 Angelescu et al.
2006/0014001 January 2006 Zhang et al.
2006/0014083 January 2006 Carlson
2006/0024590 February 2006 Sandhu
2006/0030495 February 2006 Gregg
2006/0035387 February 2006 Wagner et al.
2006/0038182 February 2006 Rogers et al.
2006/0046079 March 2006 Lee et al.
2006/0046480 March 2006 Guo
2006/0060863 March 2006 Lu et al.
2006/0062867 March 2006 Choi et al.
2006/0078681 April 2006 Hieda et al.
2006/0097134 May 2006 Rhodes
2006/0105562 May 2006 Yi
2006/0124467 June 2006 Ho et al.
2006/0128165 June 2006 Theiss et al.
2006/0134556 June 2006 Nealey et al.
2006/0137554 June 2006 Kron et al.
2006/0141222 June 2006 Fischer et al.
2006/0141245 June 2006 Stellacci et al.
2006/0154466 July 2006 Lee et al.
2006/0163646 July 2006 Black et al.
2006/0192283 August 2006 Benson
2006/0205875 September 2006 Cha et al.
2006/0211871 September 2006 Dai
2006/0217285 September 2006 Destarac
2006/0228635 October 2006 Suleski
2006/0231525 October 2006 Asakawa et al.
2006/0249784 November 2006 Black et al.
2006/0249796 November 2006 Tavkhelidze
2006/0254440 November 2006 Choi et al.
2006/0255505 November 2006 Sandhu et al.
2006/0257633 November 2006 Inoue et al.
2006/0258159 November 2006 Colburn et al.
2006/0278158 December 2006 Tolbert et al.
2006/0286305 December 2006 Thies et al.
2006/0286490 December 2006 Sandhu et al.
2007/0020749 January 2007 Nealey et al.
2007/0023247 February 2007 Ulicny et al.
2007/0023805 February 2007 Wells et al.
2007/0045562 March 2007 Parekh
2007/0045642 March 2007 Li
2007/0071881 March 2007 Chua et al.
2007/0072403 March 2007 Sakata
2007/0122749 May 2007 Fu et al.
2007/0122932 May 2007 Kodas et al.
2007/0138131 June 2007 Burdinski
2007/0161237 July 2007 Lieber et al.
2007/0175859 August 2007 Black et al.
2007/0181870 August 2007 Libertino et al.
2007/0183035 August 2007 Asakawa et al.
2007/0194403 August 2007 Cannon et al.
2007/0200477 August 2007 Tuominen et al.
2007/0208159 September 2007 McCloskey et al.
2007/0218202 September 2007 Ajayan et al.
2007/0222995 September 2007 Lu
2007/0224819 September 2007 Sandhu
2007/0224823 September 2007 Sandhu
2007/0227383 October 2007 Decre et al.
2007/0249117 October 2007 Kang et al.
2007/0272951 November 2007 Lieber et al.
2007/0281220 December 2007 Sandhu
2007/0289943 December 2007 Lu et al.
2007/0293041 December 2007 Yang
2008/0032238 February 2008 Lu et al.
2008/0038467 February 2008 Jagannathan et al.
2008/0038923 February 2008 Edelstein et al.
2008/0041818 February 2008 Kihara et al.
2008/0047930 February 2008 Blanchet et al.
2008/0064217 March 2008 Horii
2008/0073743 March 2008 Alizadeh et al.
2008/0078982 April 2008 Min et al.
2008/0078999 April 2008 Lai
2008/0083991 April 2008 Yang et al.
2008/0085601 April 2008 Park et al.
2008/0093743 April 2008 Yang et al.
2008/0102252 May 2008 Black et al.
2008/0103256 May 2008 Kim et al.
2008/0113169 May 2008 Cha et al.
2008/0164558 July 2008 Yang et al.
2008/0174726 July 2008 Kim
2008/0176767 July 2008 Millward
2008/0191200 August 2008 Frisbie et al.
2008/0193658 August 2008 Millward
2008/0217292 September 2008 Millward et al.
2008/0233297 September 2008 de Jong et al.
2008/0233323 September 2008 Cheng et al.
2008/0241218 October 2008 McMorrow
2008/0257187 October 2008 Millward
2008/0260941 October 2008 Jin
2008/0274413 November 2008 Millward
2008/0286659 November 2008 Millward
2008/0311347 December 2008 Millward et al.
2008/0315270 December 2008 Marsh et al.
2008/0318005 December 2008 Millward
2009/0062470 March 2009 Millward et al.
2009/0087664 April 2009 Nealey et al.
2009/0148795 June 2009 Li et al.
2009/0155579 June 2009 Greco et al.
2009/0196488 August 2009 Nealey et al.
2009/0200646 August 2009 Millward et al.
2009/0212016 August 2009 Cheng et al.
2009/0218567 September 2009 Mathew et al.
2009/0236309 September 2009 Millward et al.
2009/0240001 September 2009 Regner
2009/0263628 October 2009 Millward
2009/0267058 October 2009 Namdas et al.
2009/0274887 November 2009 Millward et al.
2010/0092873 April 2010 Sills et al.
2010/0102415 April 2010 Millward et al.
2010/0124826 May 2010 Millward et al.
2010/0137496 June 2010 Millward et al.
2010/0163180 July 2010 Millward
2010/0204402 August 2010 Millward et al.
2010/0279062 November 2010 Millward et al.
2010/0316849 December 2010 Millward et al.
2010/0323096 December 2010 Sills et al.
2011/0232515 September 2011 Millward
2012/0028471 February 2012 Oyama et al.
2012/0122292 May 2012 Sandhu et al.
2012/0133017 May 2012 Millward et al.
2012/0135146 May 2012 Cheng et al.
2012/0135159 May 2012 Xiao et al.
2012/0138570 June 2012 Millward et al.
2012/0164389 June 2012 Yang et al.
2012/0202017 August 2012 Nealey et al.
2012/0211871 August 2012 Russell et al.
2012/0223053 September 2012 Millward et al.
2012/0225243 September 2012 Millward
2013/0105755 May 2013 Sills et al.
2013/0285214 October 2013 Millward et al.
2013/0295323 November 2013 Millward
2013/0330668 December 2013 Wu et al.
2013/0330688 December 2013 Hedrick et al.
2014/0060736 March 2014 Millward et al.
2014/0127626 May 2014 Senzaki et al.
2014/0272723 September 2014 Somervell et al.
2015/0021293 January 2015 Morris et al.
1562730 Jan 2005 CN
1799131 Jul 2006 CN
101013662 Aug 2007 CN
784543 Apr 2000 EP
1416303 May 2004 EP
1906237 Apr 2008 EP
1593164 Jun 2010 EP
11080414 Mar 1999 JP
2003155365 May 2003 JP
2004335962 Nov 2004 JP
2005008882 Jan 2005 JP
2005029779 Feb 2005 JP
2006036923 Feb 2006 JP
2006055982 Mar 2006 JP
2006110434 Apr 2006 JP
2007194175 Aug 2007 JP
2008036491 Feb 2008 JP
2008043873 Feb 2008 JP
1020060128378 Dec 2006 KR
1020070029762 Mar 2007 KR
100771886 Nov 2007 KR
200400990 Mar 1992 TW
200633925 Oct 1994 TW
200740602 Jan 1996 TW
200802421 Feb 1996 TW
584670 Apr 2004 TW
200419017 Oct 2004 TW
200511364 Mar 2005 TW
I256110 Jun 2006 TW
I253456 Nov 2007 TW
90007575 Jul 1990 WO
9706013 Feb 1997 WO
9839645 Sep 1998 WO
9947570 Sep 1999 WO
0002090 Jan 2000 WO
0031183 Jun 2000 WO
0218080 Mar 2002 WO
02081372 Oct 2002 WO
03045840 Jun 2003 WO
2005122285 Dec 2005 WO
2006003592 Jan 2006 WO
2006003594 Jan 2006 WO
2006076016 Jul 2006 WO
2006078952 Jul 2006 WO
2006112887 Oct 2006 WO
2007001294 Jan 2007 WO
2007013889 Feb 2007 WO
2007024241 Mar 2007 WO
2007024323 Mar 2007 WO
2007019439 May 2007 WO
2007055041 May 2007 WO
2008055137 May 2008 WO
2008091741 Jul 2008 WO
2008096335 Aug 2008 WO
2008097736 Aug 2008 WO
2008118635 Oct 2008 WO
2008124219 Oct 2008 WO
2008130847 Oct 2008 WO
2008145268 Dec 2008 WO
2008156977 Dec 2008 WO
2009099924 Aug 2009 WO
2009102551 Aug 2009 WO
2009117238 Sep 2009 WO
2009117243 Sep 2009 WO
2009134635 Nov 2009 WO
Gates et al., Unconventional Nanofabrication, Annu. Rev. Mater. Res., vol. 34, (2004), pp. 339-372. cited by applicant .
Gates, Nanofabrication with Molds & Stamps, Materials Today, (Feb. 2005), pp. 44-49. cited by applicant .
Ge et al., Thermal Conductance of Hydrophilic and Hydrophobic Interfaces, Physical Review Letters, vol. 96, (May 8, 2006), pp. 186101-1-186101-4. cited by applicant .
Gelest, Inc., Silane Coupling Agents: Connecting Across Boundaries, v2.0, ( 2006), pp. 1-56. cited by applicant .
Genua et al., Functional Patterns Obtained by Nanoimprinting Lithography and Subsequent Growth of Polymer Brushes, Nanotechnology, vol. 18, (2007), pp. 1-7. cited by applicant .
Gillmor et al., Hydrophilic/Hydrophobic Patterned Surfaces as Templates for DNA Arrays, Langmuir, vol. 16, No. 18, (2000), pp. 7223-7228. cited by applicant .
Grubbs, Hybrid Metal-Polymer Composites from Functional Block Copolymers, J. Of Polymer Sci.: Part A: Polymer Chemistry, vol. 43, Issue 19, (Oct. 1, 2005), pp. 4323-4336. cited by applicant .
Guarini et al., Nanoscale Patterning Using Self-Assembled Polymers for Semiconductor Applications, J. Vac. Sci. Technol. B 19(6), (Nov./Dec. 2001), pp. 2784-2788. cited by applicant .
Gudipati et al., Hyperbranched Fluoropolymer and Linear Poly(ethylene glycol) Based Amphiphilic Crosslinked Networks as Efficient Antifouling Coatings: An Insight into the Surface Compositions, Topographies, and Morphologies, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 42, (2004), pp. 6193-6208. cited by applicant .
Guo et al., Synthesis and Characterization of Novel Biodegradable Unsaturated Poly(ester amide)/Poly(ethylene glycol) Diacrylate Hydrogels, Journal of Polymer Science Part A: Polymer Chemistry, vol. 43, Issue 17, (2005), pp. 3932-3944 (Abstract only). cited by applicant .
Hadziioannou, Semiconducting Block Copolymers for Self-Assembled Photovoltaic Devices, MRS Bulletin, (Jun. 2002), pp. 456-460. cited by applicant .
Hamers, Passivation and Activation: How Do Monovalent Atoms Modify the Reactivity of Silicon Surfaces? A Perspective on the Article, "The Mechanism of Amine Formation on Si(100) Activated with Chlorine Atoms", by C.C. Finstad, A.D. Thorsness, and A.J. Muscat, Surface Sci., vol. 600, (2006), pp. 3361-3362. cited by applicant .
Hamley, I. W., Introduction to Block Copolymers, Developments in Block Copolymers Science and Technology, John Wiley & Sons, Ltd., (2004), pp. 1-29. cited by applicant .
Hammond et al., Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers, Macromolecules, vol. 38, (Jul. 2005), pp. 6575-6585. cited by applicant .
Harrison et al., Layer by Layer Imaging of Diblock Copolymer Films with a Scanning Electron Microscope, Polymer, vol. 39, No. 13, (1998), pp. 2733-2744. cited by applicant .
Hawker et al., Facile Synthesis of Block Copolymers for Nanolithographic Applications, Polymer Preprints, American Chemical Society, vol. 46, No. 2, (2005), pp. 239-240. cited by applicant .
Hawker et al., Improving the Manufacturability and Structural Control of Block Copolymer Lithography, Abstracts of Papers, 232nd ACS National Meeting, San Francisco, CA, (Sep. 10-14, 2006), 1 page, (Abstract only). cited by applicant .
Hayward et al., Crosslinked Poly(styrene)-block-Poly(2-vinylpyridine) Thin Films as Swellable Templates for Mesostructured Silica and Titania, Advanced Materials, vol. 17, (2005), pp. 2591-2595. cited by applicant .
He et al., Self-Assembly of Block Copolymer Micelles in an Ionic Liquid, J. Am. Chem. Soc., vol. 128, (2006), pp. 2745-2750. cited by applicant .
Helmbold et al., Optical Absorption of Amorphous Hydrogenated Carbon Thin Films, Thin Solid Films, vol. 283, (1996), pp. 196-203. cited by applicant .
Helmuth et al., High-Speed Microcontact Printing, J. Am. Chem. Soc., vol. 128, No. 29, (2006), pp. 9296-9297. cited by applicant .
Hermans et al., Application of Solvent-Directed Assembly of Block Copolymers to the Synthesis of Nanostructured Materials with Low Dielectric Constants, Angewandte Chem. Int'l. Ed., vol. 45, Issue 40, (Oct. 13, 2006), pp. 6648-6652. cited by applicant .
Horiuchi et al., Three-Dimensional Nanoscale Alignment of Metal Nanoparticles Using Block Copolymer Films as Nanoreactors, Langmuir, vol. 19, (2003), pp. 2963-2973. cited by applicant .
Lacour et al., Stretchable Gold Conductors on Elastomeric Substrates, Applied Physics Letters, vol. 82, No. 15, (Apr. 14, 2003), pp. 2404-2406. cited by applicant .
Huang et al., Using Surface Active Random Copolymers to Control the Domain Orientation in Diblock Copolymer Thin Films, Macromolecules, vol. 31, (1998), pp. 7641-7650. cited by applicant .
Hur et al., Nanotransfer Printing by Use of Noncovalent Surface Forces: Applications to Thin-Film Transistors That Use Single-Walled Carbon Nanotube Networks and Semiconducting Polymers, Applied Physics Letters, vol. 85, No. 23, (Dec. 6, 2004), pp. 5730-5732. cited by applicant .
Hutchison et al., Polymerizable Living Free Radical Initiators as a Platform to Synthesize Functional Networks, Chem. Mater., vol. 17, No. 19, (2005), pp. 4789-4797. cited by applicant .
Ikeda et al., Control of Orientation of Thin Films of Organic Semiconductors by Graphoepitaxy, NanotechJapan Bulletin--NIMS International Center for Nanotechnology Network., vol. 3, No. 3, (Dec. 17, 2010), 23 pages. cited by applicant .
In et al., Side-Chain-Grafted Random Copolymer Brushes as Neutral Surfaces for Controlling the Orientation of Block Copolymer Microdomains in Thin Films, Langmuir, vol. 22, No. 18, (2006), pp. 7855-7860. cited by applicant .
International Preliminary Report on Patentability for International Application No. PCT/US2009/032564 dated Aug. 10, 2010, 12 pages. cited by applicant .
International Search Report for International Application No. PCT/US2009/032564 dated Oct. 7, 2009, 6 pages. cited by applicant .
International Written Opinion for International Application No. PCT/US2009/032564 dated Oct. 7, 2009, 11 pages. cited by applicant .
Ji et al., Generalization of the Use of Random Copolymers to Control the Wetting Behaviors of Block Copolymer Films, Macromolecules, vol. 41, No. 23, (2008), pp. 9098-9103. cited by applicant .
Ji et al., Molecular Transfer Printing Using Block Copolymers, ACS Nano, vol. 4, No. 2, (2010), pp. 599-609. cited by applicant .
Ji et al., Preparation of Neutral Wetting Brushes for Block Copolymer Films from Homopolymer Blends, submitted to Advanced Materials, vol. 20, No. 16, (Jul. 7, 2008), pp. 3054-3060. cited by applicant .
Jiang et al., Electrochemical Desorption of Self-Assembled Monolayers Noninvasively Releases Patterned Cells from Geometrical Confinements, J. Am. Chem. Soc., vol. 125, No. 9, (2003), pp. 2366-2367. cited by applicant .
Johnson et al., Probing the Stability of the Disulfide Radical Intermediate of Thioredoxin Using Direct Electrochemistry, Letters in Peptide Sci., vol. 10, (2003), pp. 495-500. cited by applicant .
Jun et al., Microcontact Printing Directly on the Silicon Surface, Langmuir, vol. 18, No. 9, (2002), pp. 3415-3417, (Abstract only). cited by applicant .
Jun et al., Patterning Protein Molecules on Poly(ethylene glycol) Coated Si(111), Biomaterials, vol. 25, (2004), pp. 3503-3509. cited by applicant .
Karim et al., Control of Ordering Kinetics and Morphology Using Zone Annealing of Thin Block Copolymer Films, Abstract submitted for the Mar. 2007 Meeting of the American Physical Society, (Nov. 20, 2006), 2 pages. cited by applicant .
Kavakli et al., Single and Double-Layer Antireflection Coatings on Silicon, Turk J. Phys., vol. 26, (2002), pp. 349-354. cited by applicant .
Kim et al., Epitaxial Self-Assembly of Block Copolymers on Lithographically Defined Nanopatterned Substrates, Nature, vol. 424, (Jul. 24, 2003), pp. 411-414. cited by applicant .
Kim et al., Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation, Adv. Mater., vol. 16, No. 3, (Feb. 3, 2004), pp. 226-231. cited by applicant .
Kim et al., Hybrid Nanofabrication Processes Utilizing Diblock Copolymer Nanotemplate Prepared by Self-Assembled Monolayer Based Surface Neutralization, J. Vac. Sci. Technol. B, vol. 26, No. 1, (Jan./Feb. 2008), pp. 189-194. cited by applicant .
Kim et al., In Vitro Release Behavior of Dextran-methacrylate Hydrogels Using Doxorubicin and Other Model Compounds, J. Biomater. Appl., vol. 15, No. 1, (Jul. 2000), pp. 23-46, (Abstract only). cited by applicant .
Kim et al., Novel Complex Nanostructure from Directed Assembly of Block Copolymers on Incommensurate Surface Patterns, Adv. Mater., vol. 19, (2007), pp. 3271-3275. cited by applicant .
Kim et al., Salt Complexation in Block Copolymer Thin Films, Macromolecules, vol. 39, No. 24, (2006), pp. 8473-8479. cited by applicant .
Kim et al., Self-Assembled Hydrogel Nanoparticles Composed of Dextran and Poly(ethylene glycol) Macromer, Int. J. Pharm., vol. 205, No. 1-2, (Sep. 15, 2000), pp. 109-116, (Abstract only). cited by applicant .
Kim et al., Solvent-Induced Ordering in Thin Film Diblock Copolymer/Homopolymer Mixtures, Advanced Mater., vol. 16, No. 23-24, (Dec. 17, 2004), pp. 2119-2123. cited by applicant .
Kim et al., Synthesis and Characterization of Dextran-methacrylate Hydrogels and Structural Study by SEM, J. Biomater. Res., vol. 49, No. 4, (Mar. 15, 2000), pp. 517-527, (only). cited by applicant .
Knoll et al., Phase Behavior in Thin Films of Cylinder-Forming Block Copolymers, Physical Review Letters, vol. 89, No. 3, (Jul. 15, 2002), pp. 035501-1-035501-4. cited by applicant .
Krishnamoorthy et al., Block Copolymer Micelles as Switchable Templates for Nanofabrication, Langmuir, vol. 22, No. 8, (2006), pp. 3450-3452. cited by applicant .
Krishnamoorthy et al., Nanopatterned Self-Assembled Monolayers by Using Diblock Copolymer Micelles as Nanometer-Scale Adsorption and Etch Masks, Advanced Materials, (2008), pp. 1-4. cited by applicant .
Krishnamoorthy et al., Nanoscale Patterning with Block Copolymers, Materials Today, vol. 9, No. 9, (Sep. 2006), pp. 40-47. cited by applicant .
Kuhnline et al., Detecting Thiols in a Microchip Device Using Micromolded Carbon Ink Electrodes Modified with Cobalt Phthalocyanine, Analyst, vol. 131, (2006), pp. 202-207. cited by applicant .
La et al., Directed Assembly of Cylinder-Forming Block Copolymers into Patterned Structures to Fabricate Arrays of Spherical Domains and Nanoparticles, Chem. Mater., vol. 19, No. 18, (2007), pp. 4538-4544. cited by applicant .
La et al., Pixelated Chemically Amplified Resists: Investigation of Material Structure on the Spatial Distribution of Photoacids and Line Edge Roughness, J. Vac. Sci. Technol. B, vol. 25, No. 6, (Nov./Dec. 2007), pp. 2508-2513. cited by applicant .
Laracuente et al., Step Structure and Surface Morphology of Hydrogen-Terminated Silicon: (001) to (114), Surface Science, vol. 545, (2003), pp. 70-84. cited by applicant .
Lentz et al., Whole Wafer Imprint Patterning Using Step and Flash Imprint Lithography: A Manufacturing Solution for Sub 100 nm Patterning, SPIE Emerging Lithographic Technologies, vol. 6517, (Mar. 16, 2007), 10 pages. cited by applicant .
Li et al., A Method for Patterning Multiple Types of Cells by Using Electrochemical Desorption of Self-Assembled Monolayers within Microfluidic Channels, Angew. Chem. Int. Ed., vol. 46, (2007), pp. 1094-1096. cited by applicant .
Li et al., Block Copolymer Patterns and Templates, Materials Today, vol. 9, No. 9, (Sep. 2006), pp. 30-39. cited by applicant .
Li et al., Creation of Sub-20-nm Contact Using Diblock Copolymer on a 300 mm Wafer for Complementary Metal Oxide Semiconductor Applications, J. Vac. Sci. Technol. B, vol. 25, No. 6, (Nov./Dec. 2007), pp. 1982-1984. cited by applicant .
Li et al., Morphology Change of Asymmetric Diblock Copolymer Micellar Films During Solvent Annealing, Polymer, vol. 48, (2007), pp. 2434-2443. cited by applicant .
Li et al., "Ordered Block-Copolymer Assembly Using Nanoimprint Lithography," Nano Lett. (2004), vol. 4, No. 9, pp. 1633-1636. cited by applicant .
Lin et al., A Rapid Route to Arrays of Nanostructures in Thin Films, Adv. Mater., vol. 14, No. 19, (Oct. 2, 2002), pp. 1373-1376. cited by applicant .
Lin-Gibson et al., Structure--Property Relationships of Photopolymerizable Poly(ethylene glycol) Dimethacrylate Hydrogels, Macromolecules, vol. 38, (2005), pp. 2897-2902. cited by applicant .
Liu et al., Pattern Transfer Using Poly(styrene-block-methyl methacrylate) Copolymer Films and Reactive Ion Etching, J. Vac. Sci. Technol. B, vol. 25, No. 6, (Nov./Dec. 2007), pp. 1963-1968. cited by applicant .
Loo et al., Additive, Nanoscale Patterning of Metal Films with a Stamp and a Surface Chemistry Mediated Transfer Process: Applications in Plastic Electronics, Applied Physics Letters, vol. 81, No. 3, (Jul. 15, 2002), pp. 562-564. cited by applicant .
Lopes et al., Hierarchical Self-Assembly of Metal Nanostructures on Diblock Copolymer Scaffolds, Nature, vol. 414, (Dec. 13, 2001), pp. 735-738. cited by applicant .
Lutolf et al., Cell-Responsive Synthetic Hydrogels, Adv. Mater., vol. 15, No. 11, (Jun. 2003), pp. 888-892. cited by applicant .
Lutolf et al., Synthetic Biomaterials as Instructive Extracellular Microenvironments for Morphogenesis in Tissue Engineering, Nature Biotechnology, vol. 23, (2005), pp. 47-55, (Abstract only). cited by applicant .
Lutz, 1,3-Dipolar Cycloadditions of Azides and Alkynes: A Universal Ligation Tool in Polymer and Materials Science, Angew. Chem. Int. Ed., vol. 46, (2007), pp. 1018-1025. cited by applicant .
Malenfant et al., Self-Assembly of an Organic-Inorganic Block Copolymer for Nano-Ordered Ceramics, Nature Nanotechnology, vol. 2, (Jan. 2007), pp. 43-46. cited by applicant .
Malkoch et al., Synthesis of Well-Defined Hydrogel Networks Using Click Chemistry, Chem. Commun., (2006), pp. 2774-2776. cited by applicant .
Mansky et al., Controlling Polymer-Surface Interactions with Random Copolymer Brushes, Science, vol. 275, (Mar. 7, 1997), pp. 1458-1460. cited by applicant .
Martens et al., Characterization of Hydrogels Formed from Acrylate Modified Poly(vinyl alcohol) Macromers, Polymer, vol. 41, No. 21, (Oct. 2000), pp. 7715-7722, (Abstract only). cited by applicant .
Matsuda et al., Photoinduced Prevention of Tissue Adhesion, ASAIO J, vol. 38, No. 3, (Jul.-Sep. 1992), pp. M154-7, (Abstract only). cited by applicant .
Maye et al., Chemical Analysis Using Force Microscopy, Journal of Chemical Education, vol. 79, No. 2, (Feb. 2002), pp. 207-210. cited by applicant .
Melde et al., Silica Nanostructures Templated by Oriented Block Copolymer Thin Films Using Pore-Filling and Selective-Mineralization Routes, Chem. Mater., vol. 17, No. 18, (Aug. 13, 2005), pp. 4743-4749. cited by applicant .
Metters et al., Network Formation and Degradation Behavior of Hydrogels Formed by Michael-Type Addition Reactions, Biomacromolecules, vol. 6, (2005), pp. 290-301. cited by applicant .
Meyer et al., Controlled Dewetting Processes on Microstructured Surfaces--a New Procedure for Thin Film Microstructuring, Macromollecular Mater. Eng., vol. 276/277, (2000), pp. 44-50. cited by applicant .
Mezzenga et al., On the Role of Block Copolymers in Self-Assembly of Dense Colloidal Polymeric Systems, Langmuir, vol. 19, No. 20, (2003), pp. 8144-8147. cited by applicant .
Mindel et al., A Study of Bredig Platinum Sols, The Chemical Laboratories of New York University, vol. 65, (Jun. 10, 1943), p. 2112. cited by applicant .
Naito et al., 2.5-Inch Disk Patterned Media Prepared by an Artificially Assisted Self-Assembling Method, IEEE Transactions on Magnetics, vol. 38, No. 5, (Sep. 2002), pp. 1949-1951. cited by applicant .
Nealey et al., Self-Assembling Resists for Nanolithography, 2005 Electron Devices Meeting, IEDM Technical Digest, (2005), 2 pages. cited by applicant .
Nguyen et al., Photopolymerizable Hydrogels for Tissue Engineering Applications, Biomaterials, vol. 23, (2002), pp. 4307-4314. cited by applicant .
Nishikubo, T., Chemical Modification of Polymers via a Phase-Transfer Catalyst or Organic Strong Base, American Chemical Society Symposium Series, (1997), pp. 214-230. cited by applicant .
Niu et al., Selective Assembly of Nanoparticles on Block Copolymer by Surface Modification, Nanotechnology, vol. 18, (2007), pp. 1-4. cited by applicant .
Niu et al., Stability of Order in Solvent-Annealed Block Copolymer Thin Films, Macromolecules, vol. 36, No. 7, (2003), pp. 2428-2440, (Abstract and Figures only). cited by applicant .
Olayo-Valles et al. Large Area Nanolithographic Templates by Selective Etching of Chemically Stained Block Copolymer Thin Films, J. Mater. Chem., vol. 14, (2004), pp. 2729-2731. cited by applicant .
Parejo et al., Highly Efficient UV-Absorbing Thin-Film Coatings for Protection of Organic Materials Against Photodegradation, J. Mater. Chem., vol. 16, (2006), pp. 2165-2169. cited by applicant .
Park et al., Block Copolymer Lithography: Periodic Arrays of.about.1011 Holes in 1 Square Centimeter, Science, vol. 276, No. 5317, (May 30, 1997), pp. 1401-1404. cited by applicant .
Park et al., Block Copolymer Multiple Patterning Integrated with Conventional ArF Lithography, Soft Matter, vol. 6, (2010), pp. 120-125. cited by applicant .
Park et al., Controlled Ordering of Block Copolymer Thin Films by the Addition of Hydrophilic Nanoparticles, Macromolecules 2007, vol. 40, No. 22, (2007), pp. 8119-8124. cited by applicant .
Park et al., Directed Assembly of Lamellae-Forming Block Copolymers by Using Chemically and Topographically Patterned Substrates, Advanced Materials, vol. 19, No. 4, (Feb. 2007), pp. 607-611. cited by applicant .
Park et al., Enabling Nanotechnology with Self Assembled Block Copolymer Patterns, Polymer, vol. 44, No. 22, (2003), pp. 6725-6760. cited by applicant .
Park et al., Fabrication of Highly Ordered Silicon Oxide Dots and Stripes from Block Copolymer Thin Films, Advanced Materials, vol. 20, (2008), pp. 681-685. cited by applicant .
Park et al., High-Aspect-Ratio Cylindrical Nanopore Arrays and Their Use for Templating Titania Nanoposts, Advanced Materials, vol. 20, (2008), pp. 738-742. cited by applicant .
Park et al., The Fabrication of Thin Films with Nanopores and Nanogrooves from Block Copolymer Thin Films on the Neutral Surface of Self-Assembled Monolayers, Nanotechnology, vol. 18, (2007), pp. 1-7. cited by applicant .
Peng et al., Development of Nanodomain and Fractal Morphologies in Solvent Annealed Block Copolymer Thin Films, Macromol. Rapid Commun., vol. 28, (2007), pp. 1422-1428. cited by applicant .
Yang et al., Nanoscopic Templates Using Self-assembled Cylindrical Diblock Copolymers for Patterned Media, J. Vac. Sci. Technol. B 22(6), (Nov./Dec. 2004), pp. 3331-3334. cited by applicant .
Yu et al., Contact Printing Beyond Surface Roughness: Liquid Supramolecular Nanostamping, Advanced Materials, vol. 19, (2007), pp. 4338-4342. cited by applicant .
Yurt et al., Scission of Diblock Copolymers into Their Constituent Blocks, Macromolecules 2006, vol. 39, No. 5, (2006), pp. 1670-1672. cited by applicant .
Zaumseil et al., Three-Dimensional and Multilayer Nanostructures Formed by Nanotransfer Printing, Nano Letters, vol. 3, No. 9,(2003), pp. 1223-1227. cited by applicant .
Zehner et al., Selective Decoration of a Phase-Separated Diblock Copolymer with Thiol-Passivated Gold Nanocrystals, Langmuir, vol. 14, No. 2, (Jan. 20, 1998), pp. 241-244. cited by applicant .
Zhang et al., Highly Ordered Nanoporous Thin Films from Cleavable Polystyrene-block-poly(ethylene oxide),Adv. Mater., vol. 19, (2007), pp. 1571-1576. cited by applicant .
Zhang et al., Phase Change Nanodot Arrays Fabricated Using a Self-Assembly Diblock Copolymer Approach, Applied Physics Letter, vol. 91, (2007), pp. 013104-013104-3. cited by applicant .
Zhang et al., Self-Assembled Monolayers of Terminal Alkynes on Gold, J. Am. Chem. Soc., vol. 129, No. 16, (2007), pp. 4876-4877. cited by applicant .
Zhao et al., Colloidal Subwavelength Nanostructures for Antireflection Optical Coatings, Optics Letters, vol. 30, No. 14, (Jul. 15, 2005), pp. 1885-1887. cited by applicant .
Zhou et al., Nanoscale Metal/Self-Assembled Monolayer/Metal Heterostructures, Appl. Phys. Lett., vol. 71, No. 5, (Aug. 4, 1997), pp. 611-613. cited by applicant .
Zhu et al., Grafting of High-Density Poly(Ethylene Glycol) Monolayers on Si(111), Langmuir, vol. 17, (2001), pp. 7798-7803. cited by applicant .
Zhu et al., Molecular Assemblies on Silicon Surfaces via Si--O Linkages, Langmuir, vol. 16, (2000), pp. 6766-6772. cited by applicant .
Peters et al., Combining Advanced Lithographic Techniques and Self-Assembly of Thin Films of Diblock Copolymers to Produce Templates for Nanofabrication, J. Vac. Sci. Technol. B, vol. 18, No. 6, (Nov./Dec. 2000), pp. 3530-3532. cited by applicant .
Peters et al., Morphology of Thin Films of Diblock Copolymers on Surfaces Micropatterned with Regions of Different Interfacial Energy, Macromolecules, vol. 35, No. 5, (2002), pp. 1822-1834. cited by applicant .
Potemkin et al., Effect of the Molecular Weight of AB Diblock Copolymers on the Lamellar Orientation in Thin Films: Theory and Experiment, Macromol. Rapid Commun., vol. 28, (2007), pp. 579-584. cited by applicant .
Reed et al., Molecular Random Access Memory Cell, Appl. Phys. Lett., vol. 78, No. 23, (Jun. 4, 2001), pp. 3735-3737. cited by applicant .
Resnick et al., Initial Study of the Fabrication of Step and Flash Imprint Lithography Templates for the Printing of Contact Holes, J. Micro/Nanolithography, MEMS, and MOEMS, vol. 3, No. 2, (Apr. 2004), pp. 316-321. cited by applicant .
Rogers, J. A., Slice and Dice, Peel and Stick: Emerging Methods for Nanostructure Fabrication, ACS Nano, vol. 1, No. 3, (2007), pp. 151-153. cited by applicant .
Rozkiewicz et al., "Click" Chemistry by Microcontact Printing, Angew. Chem. Int. Ed., vol. 45, No. 32, (Jul. 12, 2006), pp. 5292-5296. cited by applicant .
Ruiz et al., Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly, Science, vol. 321, (Aug. 15, 2008), pp. 936-939. cited by applicant .
Ruiz et al., Induced Orientational Order in Symmetric Diblock Copolymer Thin-Films, Advanced Materials, vol. 19, No. 4, (2007), pp. 587-591. cited by applicant .
Ryu et al., Surface Modification with Cross-Linked Random Copolymers: Minimum Effective Thickness, Macromolecules, vol. 40, No. 12, (2007), pp. 4296-4300. cited by applicant .
Saraf et al., Spontaneous Planarization of Nanoscale Phase Separated Thin Film, Applied Physics Letters, vol. 80, No. 23, (Jun. 10, 2002), pp. 4425-4427. cited by applicant .
Sato et al., Novel Antireflective Layer Using Polysilane for Deep Ultraviolet Lithography, J. Vac. Sci. Technol. B, vol. 17, No. 6, (Nov./Dec. 1999), pp. 3398-3401. cited by applicant .
Sawhney et al., Bioerodible Hydrogels Based on Photopolymerized Poly(ethylene glycol)-co-poly(a-hydroxy acid) Diacrylate Macromers, Macromolecules 1993, vol. 26, (1993), pp. 581-587, abstract only. cited by applicant .
Search Report of the Taiwanese Application No. 098103713, dated Aug. 9, 2012, 2 pages. cited by applicant .
Segalman, R. A., Patterning with Block Copolymer Thin Films, Materials Science and Engineering R 48, (2005), pp. 191-226. cited by applicant .
Shahrjerdi et al., Fabrication of Ni Nanocrystal Flash Memories Using a Polymeric Self-Assembly Approach, IEEE Electron Device Letters, vol. 28, No. 9, (Sep. 2007), pp. 793-796. cited by applicant .
Sharma et al., Ultrathin Poly(ethylene glycol) Films for Silicon-based Microdevices, Applied Surface Science, vol. 206, (2003), pp. 218-229. cited by applicant .
Sigma-Aldrich, 312-315 Tutorial regarding Materials for Lithography/Nanopatterning, http://www.sigmaaldrich.com/Area_of_Interest/Chemistry/Materials_Science/- Micro_and_Nanoelectronic website, (retrieved Aug. 27, 2007), 8 pages. cited by applicant .
Sivaniah et al., Observation of Perpendicular Orientation in Symmetric Diblock Copolymer Thin Films on Rough Substrates, Macromolecules 2003, vol. 36, (2003), pp. 5894-5896. cited by applicant .
Sivaniah et al., Symmetric Diblock Copolymer Thin Films on Rough Substrates, Kinetics and Structure Formation in Pure Block Copolymer Thin Films, Macromolecules 2005, vol. 38, (2005), pp. 1837-1849. cited by applicant .
Sohn et al., Fabrication of the Multilayered Nanostructure of Alternating Polymers and Gold Nanoparticles with Thin Films of Self-Assembling Diblock Copolymers, Chem. Mater., vol. 13, (2001), pp. 1752-1757. cited by applicant .
Solak, H. H., Nanolithography with Coherent Extreme Ultraviolet Light, Journal of Physics D: Applied Physics, vol. 39, (2006), pp. R171-R188. cited by applicant .
Srinvivasan et al., Scanning Electron Microscopy of Nanoscale Chemical Patterns, ACS Nano, vol. 1, No. 3, (2007), pp. 191-201. cited by applicant .
Stoykovich et al., Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures, Science, vol. 308, (Jun. 3, 2005), pp. 1442-1446. cited by applicant .
Stoykovich, M. P., et al., Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries, ACS Nano, vol. 1, No. 3, (2007), pp. 168-175. cited by applicant .
Sundrani et al., Guiding Polymers to Perfection: Macroscopic Alignment of Nanoscale Domains, Nano Lett., vol. 4, No. 2, (2004), pp. 273-276. cited by applicant .
Sundrani et al., Hierarchical Assembly and Compliance of Aligned Nanoscale Polymer Cylinders in Confinement, Langmuir 2004, vol. 20, No. 12, (2004), pp. 5091-5099. cited by applicant .
Tadd et al, Spatial Distribution of Cobalt Nanoclusters in Block Copolymers, Langmuir, vol. 18, (2002), pp. 2378-2384. cited by applicant .
Tang et al., Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays, Science, vol. 322, No. 5900, (Sep. 25, 2008), pp. 429-432. cited by applicant .
Trimbach et al., Block Copolymer Thermoplastic Elastomers for Microcontact Printing, Langmuir, vol. 19, (2003), pp. 10957-10961. cited by applicant .
Truskett et al., Trends in Imprint Lithography for Biological Applications, Trends in Biotechnology, vol. 24, No. 7, (Jul. 2006), pp. 312-315. cited by applicant .
Tseng et al., Enhanced Block Copolymer Lithography Using Sequential Infiltration Synthesis, J. of Physical Chemistry, (Jul. 11, 2011), 16 pgs. cited by applicant .
Van Poll et al., Self-Assembly Approach to Chemical Micropatterning of Poly(dimethylsiloxane), Angew. Chem. Int. Ed. 2007, vol. 46, (2007), pp. 6634-6637. cited by applicant .
Wang et al., One Step Fabrication and characterization of Platinum Nanopore Electrode Ensembles formed via Amphiphilic Block Copolymer Self-assembly, Electrochimica Acta 52, (2006), pp. 704-709. cited by applicant .
Wathier et al., Dendritic Macromers as in Situ Polymerizing Biomaterials for Securing Cataract Incisions, J. Am. Chem. Soc., vol. 126, No. 40, (2004), pp. 12744-12745, abstract only. cited by applicant .
Winesett et al., Tuning Substrate Surface Energies for Blends of Polystyrene and Poly(methyl methacrylate), Langmuir 2003, vol. 19, (2003), pp. 8526-8535. cited by applicant .
WIPF, Handbook of Reagents for Organic Synthesis, John Wiley & Sons Ltd., (2005), p. 320. cited by applicant .
Wu et al., Self-Assembled Two-Dimensional Block Copolymers on Pre-patterned Templates with Laser Interference Lithography, IEEE, (2007), pp. 153-154. cited by applicant .
Xia et al., An Approach to Lithographically Defined Self-Assembled Nanoparticle Films, Advanced Materials, vol. 18, (2006), pp. 930-933. cited by applicant .
Xia et al., Soft Lithography, Annu. Rev. Mater. Sci., vol. 28, (1998), pp. 153-184. cited by applicant .
Xiao et al., Graphoepitaxy of Cylinder-forming Block Copolymers for Use as Templates to Pattern Magnetic Metal Dot Arrays, Nanotechnology 16, IPO Publishing Ltd, UK (2005), pp. S324-S329. cited by applicant .
Xu et al., Electric Field Alignment of Symmetric Diblock Copolymer Thin Films, Macromolecules, (2003), 5 pgs. cited by applicant .
Xu et al., Interfacial Interaction Dependence of Microdomain Orientation in Diblock Copolymer Thin Films, Macromolecules, vol. 38, (2005), pp. 2802-2805. cited by applicant .
Xu et al., Surface-Initiated Atom Transfer Radical Polymerization from Halogen-Terminated Si(111)(Si-X, X = Cl, Br) Surfaces for the Preparation of Well-Defined Polymer--Si Hybrids, Langmuir, vol. 21, No. 8, (2005), pp. 3221-3225. cited by applicant .
Xu et al., The Influence of Molecular Weight on Nanoporous Polymer Films, Polymer 42, Elsevier Science Ltd., (2001), pp. 9091-9095. cited by applicant .
Yamaguchi et al., Resist-Pattern Guided Self-Assembly of Symmetric Diblock Copolymer, Journal of Photopolymer Science and Technology, vol. 19, No. 3, (2006), pp. 385-388. cited by applicant .
Yamaguchi et al., Two-dimensional Arrangement of Vertically Oriented Cylindrical Domains of Diblock Copolymers Using Graphoepitaxy with Artificial Guiding Pattern Layout, Microprocesses and Nanotechnology, 2007, Conference date Nov. 5-8, 2007, pp. 434-435. cited by applicant .
Yan et al., Preparation and Phase Segregation of Block Copolymer Nanotube Multiblocks, J. Am. Chem. Soc., vol. 126, No. 32, (2004), pp. 10059-10066. cited by applicant .
Yang et al., Covalently Attached Graft Polymer Monolayer on Organic Polymeric Substrate via Confined Surface Inhibition Reaction, J. Polymer Sci.--A--Polymer Chemistry Ed., vol. 45, Issue 5, (2007), pp. 745-755. cited by applicant .
Yang et al., Guided Self-Assembly of Symmetric Diblock Copolymer Films on Chemically Nanopatterned Substrates, Macromolecules 2000, vol. 33, No. 26, (2000), pp. 9575-9582. cited by applicant .
Ali et al., Properties of Self-Assembled ZnO Nanostructures, Solid-State Electronics, vol. 46, (2002), pp. 1639-1642. cited by applicant .
Anonymous, Electronegativity, <http://www.princeton.edu/.about.achaney/tmve/wiki100k/docs/Electroneg- ativity.html>, (visited Aug. 28, 2013), 1 page. cited by applicant .
Arshady et al., The Introduction of Chloromethyl Groups into Styrene-Based Polymers, 1, Makromol. Chem., vol. 177, (1976), pp. 2911-2918. cited by applicant .
Asakawa et al., Fabrication of Subwavelength Structure for Improvement in Light-Extraction Efficiency of Light-Emitting Devices Using a Self-Assembled Pattern of Block Copolymer, Applied Optics, vol. 44, No. 34, (Dec. 1, 2005), pp. 7475-7482. cited by applicant .
Bae et al., Surface Modification Using Photo-Crosslinkable Random Copolymers, Abstract submitted for the Mar. 2006 meeting of The American Physical Society, (submitted Nov. 30, 2005) (accessed online Apr. 5, 2010) <http://absimage.aps.org/image/MWS_MAR06-2005-003641.pdf>. cited by applicant .
Balsara et al., Synthesis and Application of Nanostructured Materials, CPIMA, IRG Technical Programs, Leland Stanford Junior Univ., (2006), <http://www.stanford.edu/group/cpima/irg/irg_1.htm>, 9 pages. cited by applicant .
Bang et al., The Effect of Humidity on the Ordering of Tri-block Copolymer Thin Films, Abstract submitted for the Mar. 2007 meeting of The American Physical Society, (submitted Nov. 20, 2006), 1 page. cited by applicant .
Bass et al., Microcontact Printing with Octadecanethiol, Applied Surface Science, vol. 226, No. 4, (Apr. 2004), pp. 335-340. cited by applicant .
Bearinger et al., Chemisorbed Poly(propylene sulphide)-Based Copolymers Resist Biomolecular Interactions, Nature Materials, vol. 2, (2003), pp. 259-264. cited by applicant .
Berry et al., Effects of Zone Annealing on Thin Films of Block Copolymers, National Institute of Standards and Technology, Polymers Division, Maryland, USA, (2007), 2 pages. cited by applicant .
Berry et al., Orientational Order in Block Copolymer Films Zone Annealed Below the Order--Disorder Transition Temperature, Nano Letters, vol. 7, No. 9, (Aug. 2007), pp. 2789-2794. cited by applicant .
Black et al., High-Capacity, Self-Assembled Metal-Oxide-Semiconductor Decoupling Capacitors, IEEE Electron Device Letters, vol. 25, No. 9, (Sep. 2004), pp. 622-624. cited by applicant .
Black, Integration of Self Assembly for Semiconductor Microelectronics, IEEE 2005 Custom Integrated Circuits Conference, (2005), pp. 87-91. cited by applicant .
Black et al., Integration of Self-Assembled Diblock Copolymers for Semiconductor Capacitor Fabrication, Applied Physics Letters, vol. 79, No. 3, (2001), pp. 409-411. cited by applicant .
Black et al., Nanometer-Scale Pattern Registration and Alignment by Directed Diblock Copolymer Self-Assembly, IEEE Transactions on Nanotechnology, vol. 3, No. 3, (Sep. 2004), pp. 412-415. cited by applicant .
Black et al., Polymer Self Assembly in Semiconductor Microelectronics, IBM J. Res. & Dev., vol. 51, No. 5, (Sep. 2007), pp. 605-633. cited by applicant .
Black et al., Self Assembly in Semiconductor Microelectronics: Self-Aligned Sub-Lithographic Patterning Using Diblock Copolymer Thin Films, Proc. of SPIE, vol. 6153, (2006), pp. 615302-1-615302-11. cited by applicant .
Black, C. T., Polymer Self-Assembly as a Novel Extension to Optical Lithography, American Chemical Society, ACSNano, vol. 1, No. 3, (2007), pp. 147-150. cited by applicant .
Black, C. T., Self-Aligned Self-Assembly of Multi-Nanowire Silicon Field Effect Transistors, Appl. Phys. Lett., vol. 87, (2005), pp. 163116-1-163116-3. cited by applicant .
Botelho Do Rego et al., Diblock Copolymer Ultrathin Films Studied by High Resolution Electron Energy Loss Spectroscopy, Surface Science, 482-485, (2001), pp. 1228-1234. cited by applicant .
Brydson et al. (chapter authors), Generic Methodologies for Nanotechnology: Classification and Fabrication, Nanoscale Science and Technology, John Wiley & Sons, Ltd., (Dec. 20, 2005), pp. 1-55. cited by applicant .
Bulpitt et al., New Strategy for Chemical Modification of Hyaluronic Acid: Preparation of Functionalized Derivatives and Their Use in the Formation of Novel Biocompatible Hydrogels, Journal of Biomedical Materials Research, vol. 47, Issue 2, (Aug. 1999), pp. 152-169, (Abstract only). cited by applicant .
Canaria et al., Formation and Removal of Alkylthiolate Self-Assembled Monolayers on Gold in Aqueous Solutions, Royal Society of Chemistry, Lab Chip, vol. 6, (2006), pp. 289-295, (Abstract only). cited by applicant .
Candau et al., Synthesis and Characterization of Polystyrene-polyethylene oxide) Graft Copolymers, Polymer, vol. 18, (1977), pp. 1253-1257. cited by applicant .
Cavicchi et al., Solvent Annealed Thin Films of Asymmetric Polyisoprene--Polylactide Diblock Copolymers, Macromolecules, vol. 40, (2007), pp. 1181-1186. cited by applicant .
Cha et al., Biomimetic Approaches for Fabricating High-Density Nanopatterned Arrays, Chem. Mater., vol. 19, (2007), pp. 839-843. cited by applicant .
Chai et al., Assembly of Aligned Linear Metallic Patterns on Silicon, Nature Nanotechnology, vol. 2, (Aug. 2007), pp. 500-506. cited by applicant .
Chai et al., Using Cylindrical Domains of Block Copolymers to Self-Assemble and Align Metallic Nanowires, American Chemical Society, www.acsnano.org, (2008), pp. A-M. cited by applicant .
Chandekar et al., Template-Directed Adsorption of Block Copolymers on Alkanethiol-Patterned Gold Surfaces, (2006), http://www.nano.neu.edu/industry/industry_showcase/industry_day/documents- /Chandekar.pdf) (Powerpoint template for scientific posters (Swarthmore College)), 1 page. cited by applicant .
Chang et al., Diblock Copolymer Directed Self-Assembly for CMOS Device Fabrication, Proc. of SPIE, vol. 6156, (2006), pp. 615611-1-615611-6. cited by applicant .
Chang, et al., Experimental Demonstration of Aperiodic Patterns of Directed Self-Assembly by Block Copolymer Lithography for Random Logic Circuit Layout, IEEE International Electron Devices Meeting (IEDM), paper 33.2, (Dec. 6-8, 2010), pp. 33.2.1-33.2.4. cited by applicant .
Chen et al., Highly Ordered Arrays of Mesoporous Silica Nanorods with Tunable Aspect Ratios from Block Copolymer Thin Films, Advanced Materials, vol. 20, (2008), pp. 763-767. cited by applicant .
Cheng et al., Rapid Directed Self Assembly of Lamellar Microdomains from a Block Copolymer Containing Hybrid, Applied Physics Letters, vol. 91, (2007), pp. 143106-1-143106-3. cited by applicant .
Cheng et al., Self-Assembled One-Dimensional Nanostructure Arrays, Nano Letters, vol. 6, No. 9, (2006), pp. 2099-2103. cited by applicant .
Cheng et al., Templated Self-Assembly of Block Copolymers: Effect of Substrate Topography, Adv. Mater., vol. 15, No. 19, (2003), pp. 1599-1602. cited by applicant .
Cheng et al., "Templated Self-Assembly of Block Copolymers: Top-Down Helps Bottom-Up," Adv. Mater. (2006), vol. 18, pp. 2505-2521. cited by applicant .
Cho et al., Nanoporous Block Copolymer Micelle/Micelle Multilayer Films with Dual Optical Properties, J. Am. Chem. Soc., vol. 128, No. 30, (2006), pp. 9935-9942. cited by applicant .
Choi et al., Magnetorheology of Synthesized Core-Shell Structured Nanoparticle, IEEE Transactions on Magnetics, vol. 41, No. 10, (Oct. 2005), pp. 3448-3450. cited by applicant .
Clark et al., Selective Deposition in Multilayer Assembly: SAMs as Molecular Templates, Supramolecular Science, vol. 4, (1997), pp. 141-146. cited by applicant .
Daoulas et al., Fabrication of Complex Three-Dimensional Nanostructures from Self-Assembling Block Copolymer Materials on Two-Dimensional Chemically Patterned Templates with Mismatched Symmetry, Physical Review Letters, vol. 96, (Jan. 24, 2006), pp. 036104-1-036104-4. cited by applicant .
Darling, Directing the Self-Assembly of Block Copolymers, Progress in Polymer Science, vol. 32, No. 10, (Jun. 2, 2007), pp. 1152-1204. cited by applicant .
Desai et al., Engineered Silicon Surfaces for Biomimetic Interfaces, Business Briefing: Medical Device Manufacturing & Technology, (2002), pp. 1-4. cited by applicant .
Edwards et al., Mechanism and Kinetics of Ordering in Diblock Copolymer Thin Films on Chemically Nanopatterned Substrates, Journal of Polymer Science: Part B: Polymer Physics, vol. 43, (2005), pp. 3444-3459. cited by applicant .
Edwards et al., Precise Control over Molecular Dimensions of Block-Copolymer Domains Using the Interfacial Energy of Chemically Nanopatterned Substrates, Advanced Mater., vol. 16, No. 15, (Aug. 4, 2004), pp. 1315-1319. cited by applicant .
Elisseeff et al., Photoencapsulation of Chondrocytes in Polyethylene oxide)-Based Semi-interpenetrating Networks, Journal of Biomedical Materials Research, vol. 51, No. 2, (Aug. 2000), pp. 164-171, (Abstract only). cited by applicant .
Erlandsson et al., Metallic Zinc Reduction of Disulfide Bonds Between Cysteine Residues in Peptides and Proteins, Int'l J. Peptide Res. & Therapeutics, vol. 11, No. 4, (Dec. 2005), pp. 261-265. cited by applicant .
Fasolka et al., Block Copolymer Thin Films: Physics and Applications, Annual Review of Materials Res., vol. 31, (Aug. 2001), pp. 323-355. cited by applicant .
Fasolka et al., Morphology of Ultrathin Supported Diblock Copolymer Films: Theory and Experiment, Macromolecules, vol. 33, No. 15, (2000), pp. 5702-5712. cited by applicant .
Fujita et al., Thin Silica Film with a Network Structure as Prepared by Surface Sol-Gel Transcription on the Poly (styrene-b-4-vinylpyridine) Polymer Film, Chemistry Letters, vol. 32, No. 4, (Mar. 13, 2003), pp. 352-353. cited by applicant .
Fukunaga et al., Self-Assembly of Block Copolymer Thin Films Having a Half-Domain-Spacing Thickness: Nonequilibrium Pathways to Achieve Equilibrium Brush Layers Parallel to Substrate, Macromolecules, vol. 39, (Aug. 2006), pp. 6171-6179. cited by applicant .
Chinese Office Action for Chinese Application No. 200980104066.2 dated Apr. 5, 2012, 10 pages, with translation. cited by applicant .
Chinese Second Office Action for Chinese Application No. 200980104066.2 dated Oct. 15, 2012, 19 pages with translation. cited by applicant .
Chinese Third Office Action for Chinese Application No. 200980104066.2 dated May 10, 2013, 10 pages, with translation. cited by applicant .
Chinese Fourth Office Action for Chinese Application No. 200980104066.2 dated Aug. 27, 2013, 8 pages, with translation. cited by applicant .
Chinese Fifth Office Action for Chinese Application No. 200980104066.2 dated Jan. 21, 2014, 8 pages, with translation. cited by applicant .
European Office Action for European Application No. 09707891.9 dated Apr. 5, 2013, 4 pages. cited by applicant .
Korean Office Action for Korean Application No. 10-2010-7019788 dated May 30, 2012, 7 pages, with translation. cited by applicant .
Korean Second Office Action for Korean Application No. 10-2010-7019788 dated Dec. 31, 2012, 11 pages, with translation. cited by applicant .
Korean Written Opinion for Korean Application No. 10-2010-7019788 dated Mar. 29, 2013, 9 pages with translation. cited by applicant .
Korean Third Office Action for Korean Application No. 10-2010-7019788 dated Dec. 4, 2013, 10 pages, with translation. cited by applicant .
Korean Written Opinion for Korean Application No. 10-2010-7019788 dated Mar. 4, 2014, 4 pages, with translation. cited by applicant .
Korean Final Office Action for Korean Application No. 10-2010-7019788 dated Aug. 26, 2013, 5 pages, with translation. cited by applicant .
Korean Written Opinion for Korean Application No. 10-2010-7019788 dated Jul. 30, 2012, 6 pages, with translation. cited by applicant.
Primary Examiner: Polley; Christopher
This application is a continuation of U.S. patent application Ser. No. 12/026,214, filed Feb. 5, 2008, now U.S. Pat. No. 8,999,492, issued Apr. 7, 2015, the disclosure of which is hereby incorporated herein in its entirety by this reference.
1. A stamp, comprising: a structure having a first surface and a second surface, and comprising: transparent regions comprising a material formulated to transmit ultraviolet radiation therethrough; and non-transparent regions adjacent the transparent regions; and a polymerizable material directly on surfaces of the transparent regions and the non-transparent regions defining the first surface of the structure.
2. The stamp of claim 1, wherein the transparent regions comprise glass, calcium fluoride, diamond, a transparent plastic, or a transparent polymer material.
3. The stamp of claim 1, wherein the non-transparent regions comprise an elastomeric polymer material.
4. The stamp of claim 1, wherein the transparent regions and the non-transparent regions each extend from the first surface to the second surface.
5. The stamp of claim 1, wherein the polymerizable material comprises a neutral wetting material.
6. The stamp of claim 1, wherein the transparent regions and the non-transparent regions exhibit substantially the same widths as one another.
7. The stamp of claim 1, wherein the polymerizable material comprises a random block copolymer.
8. The stamp of claim 1, wherein the polymerizable material comprises PS-r-PMMA.
9. The stamp of claim 1, wherein the polymerizable material is formulated to be cross-linked upon exposure to at least one of ultraviolet radiation and deep ultraviolet radiation.
10. The stamp of claim 1, wherein the non-transparent regions comprise poly(dimethylsiloxane).
11. The stamp of claim 1, wherein the transparent regions comprise SiO.sub.2.
12. The stamp of claim 1, wherein the transparent regions comprise calcium fluoride.
13. The stamp of claim 1, wherein the transparent regions comprise diamond.
14. The stamp of claim 1, wherein: the transparent regions of the structure comprise quartz, calcium fluoride, or diamond; the non-transparent regions of the structure comprise poly(dimethylsiloxane); and the polymerizable material comprises PS-r-PMMA.
15. A method of forming a pattern on a substrate, comprising: forming a stamp comprising: a structure comprising: transparent regions comprising a material formulated to transmit ultraviolet radiation therethrough; and non-transparent regions adjacent the transparent regions; and a polymerizable material directly on surfaces of the transparent regions and the non-transparent regions of the structure; contacting the substrate with the stamp to apply the polymerizable material to the substrate; transmitting radiation through the transparent regions of the structure to polymerize portions of the polymerizable material and form a polymeric material comprising polymerized portions and non-polymerized portions; and removing the structure from the polymeric material.
16. The method of claim 15, further comprising, removing the non-polymerized portions of the polymeric material relative to the polymerized portions of the polymeric material to expose portions of the substrate.
17. The method of claim 16, further comprising: forming a block copolymer material over the polymerized portions of the polymeric material and the exposed portions of the substrate; and annealing the block copolymer material to form a self-assembled block copolymer material.
18. The method of claim 17, further comprising selectively removing one block of the self-assembled block copolymer material relative to another block of the self-assembled block copolymer material.
Embodiments of the invention relate to methods, a stamp and a system for patterning a substrate by use of self-assembling block copolymers, and devices resulting from those methods.
Lithography is a key process in the fabrication of semiconductor integrated circuits. Photolithography typically involves projecting an image through a reticle or mask onto a thin film of photoresist or other material that covers a semiconductor wafer or other substrate, and developing the film to remove exposed or unexposed portions of the resist to produce a pattern in subsequent processing steps. In semiconductor processing, the continual shrinking in feature sizes and the increasing development of nanoscale mechanical, electrical, chemical and biological devices requires systems to produce nanoscale features. However, with conventional photolithography using light, the minimum feature size and spacing between patterns is generally on the order of the wavelength of the radiation used to expose the film. This limits the ability to produce sub-lithographic features of about 60 nm using conventional lithography.
Microcontact printing has been developed to create sublithographic features in semiconductor devices. This technique generally involves stamping or pressing a soft template or stamp bearing small scale topographic features onto a receptor substrate to form a pattern on the substrate. The features on the template are typically prepared by photolithography or electron (e-beam) lithography. For example, FIG. 1 illustrates a conventional soft template or stamp 10 formed, for example, from polydimethylsiloxane, with defined features 12 structured with a stamping surface 14 and sidewalls 16. The stamping surface 14 defines a dimension (d) of the pattern to be stamped onto a substrate. As shown in FIG. 2, the features 12 of the stamp are wetted with an ink 18 that is physisorbed or chemisorbed onto the stamping surface 14 and the sidewalls 16 of the features 12. As depicted in FIG. 3, the inked stamp 10 is brought into contact with a receptor substrate 20 (e.g., silicon wafer) and the ink 18 is transferred to regions of the substrate 20 where the ink 18 forms self-assembled monolayers (SAMs) 22 (FIG. 4).
However, resolution of small features is problematic because of inconsistent printing due to capillary forces that pull ink 18 sorbed to surfaces of the features 12 adjacent to the stamping surface 14 (e.g., the sidewalls 16) onto the substrate 20 (e.g., areas 24). Such wicking of the ink 18 material onto the substrate 20 also alters the intended dimension (d) of the stamped features (SAMs) 22, as defined by the stamping surfaces 14 of the stamp/template. In addition, the size and dimension of the stamped features 22 on the receptor substrate 20 are limited to the dimensions (d) of the lithographically formed features 12 defined on the stamp.
Other processes such as e-beam lithography and extreme ultraviolet (EUV) lithography have been used in attempts to form sub-lithographic features. However, the high costs associated with such lithographic tools have hindered their use.
Self-assembled block copolymer films have been prepared by patterning the surface of a substrate with chemical stripes (chemical templating), each stripe being preferentially wetted by the alternate blocks of a block copolymer. A block copolymer film with lamellar morphology, a periodicity matching the stripe pattern and both blocks being neutral wetting at the air interface (e.g., PS-PMMA) that is cast on the patterned substrate and thermally annealed will self-assemble so that the domains orient themselves above the preferred stripes and perpendicular to the surface. However, the process has no advantage over EUV lithography or other sub-lithographic patterning techniques since one of these patterning techniques must be used to form the substrate template pattern, and with the use of expensive patterning tools, the low-cost benefits of using block copolymers are lost.
It would be useful to provide a method and system for preparing sub-lithographic features that overcome existing problems.
FIG. 1 illustrates an elevational, cross-sectional view of a conventional stamp used in a microcontact printing application.
FIG. 2 illustrates a diagrammatic view of the stamp of FIG. 1, with ink physisorbed or chemisorbed onto the surface of the stamp, and a receptor substrate to be contacted by the inked stamp.
FIG. 3 illustrates the inked stamp of FIG. 2, brought into contact with the receptor substrate, according to a conventional microcontact printing process.
FIG. 4 illustrates a subsequent processing step with the formation of SAMs from the transferred ink on the receptor substrate.
FIG. 5 illustrates a diagrammatic top plan view of a portion of a substrate of a stamp at a preliminary processing stage according to an embodiment of the present disclosure, showing the substrate with trenches. FIGS. 5A and 5B are elevational, cross-sectional views of the substrate depicted in FIG. 5 taken along lines 5A-5A and 5B-5B, respectively.
FIG. 6 is a top plan view of a portion of a substrate according to another embodiment showing the substrate with trenches for forming a stamp with a hexagonal close-packed array of perpendicular cylinders.
FIGS. 7 and 8 illustrate diagrammatic top plan views of the stamp of FIG. 5 at various stages of the fabrication of a self-assembled block copolymer film according to an embodiment of the present disclosure. FIGS. 7A-8A illustrate elevational, cross-sectional views of embodiments of a portion of the substrate depicted in FIGS. 7 and 8 taken, respectively, along lines 7A-7A and lines 8A-8A. FIG. 7B is a cross-sectional view of the substrate depicted in FIG. 7 taken along lines 7B-7B.
FIG. 9 is a top plan view of the stamp of FIG. 6 at a subsequent stage of fabrication showing a self-assembled polymer film composed of a hexagonal array of cylinders within the trenches.
FIG. 10 is a top plan view of the stamp of FIG. 5 at a subsequent stage of fabrication according to another embodiment of the invention, showing a self-assembled polymer film composed of a single row of cylinders with the trenches. FIG. 10A is a cross-sectional view of the substrate depicted in FIG. 10 taken along lines 10A-10A.
FIG. 11 is a top plan view of the stamp of FIG. 5 at a subsequent stage of fabrication according to another embodiment of the invention, showing a self-assembled polymer film composed of a parallel row of half-cylinders with the trenches. FIG. 11A is a cross-sectional view of the substrate depicted in FIG. 10 taken along lines 11A-11A.
FIG. 12 illustrates a diagrammatic top plan view of a portion of a stamp at a preliminary processing stage according to another embodiment of the disclosure, showing a chemically differentiated stamping surface. FIG. 12A is an elevational, cross-sectional view of the substrate depicted in FIG. 12 taken along lines 12A-12A.
FIGS. 13 and 14 illustrate diagrammatic top plan views of the stamp of FIG. 12 at subsequent processing stages. FIGS. 13A and 14A illustrate elevational, cross-sectional views of a portion of the substrate depicted in FIGS. 13 and 14 taken, respectively, along lines 13A-13A and lines 14A-14A. FIGS. 13B and 14B are cross-sectional views of the substrate of FIGS. 13-14 taken, respectively, along lines 13B-13B and lines 14B-14B.
FIGS. 15-18 illustrate subsequent steps in the use of the stamp of FIGS. 8 and 8A in a contact printing process to form a pattern on a substrate according to an embodiment of the invention. FIG. 18A is a cross-sectional view of the substrate shown in FIG. 18, taken along lines 18A-18A.
FIGS. 19 and 20 illustrate an embodiment of the use of a chemically differentiated surface of the substrate shown in FIG. 18A for the selective deposit and formation of a self-assembled block copolymer film, shown in a cross-sectional view.
FIGS. 21 and 22 illustrate the use of the self-assembled block copolymer film of FIG. 20 after removal of one of the polymer blocks, as a mask to etch the substrate and filling of the etched opening.
FIG. 23 illustrates another embodiment of the use of the stamped pattern of an ink material shown in FIG. 18A to guide deposition of a material onto exposed portions of the substrate to form a chemically differentiated surface, shown in a cross-sectional view.
FIG. 24 illustrates the use of the deposited material of the structure shown in FIG. 23 as a mask to etch the underlying substrate.
FIG. 25 illustrates yet another embodiment of the use of the stamped pattern of an ink material shown in FIG. 18A as a seed material for selective deposition of an additional material to increase the thickness and/or hardness of the ink elements on the substrate, shown in a cross-sectional view.
FIG. 26 illustrates the use of the ink pattern with added material shown in FIG. 25 as a mask to etch openings in the underlying substrate.
FIGS. 27-32 illustrate steps in another embodiment of a method according to the invention to chemically pattern a substrate, shown in a cross-sectional view. FIGS. 31 and 32 illustrate the removal of non-crosslinked polymer material and the use of the inked pattern to direct self-assembly of a block copolymer material.
FIG. 33 illustrates an elevational, cross-sectional view of an embodiment of a substrate bearing a neutral wetting layer at a preliminary processing step.
FIG. 34 illustrates the substrate of FIG. 33 at a subsequent processing step.
FIGS. 35-39 illustrate an embodiment of a process according to the invention for forming a chemically patterned master template for forming a stamp for use in inducing self-assembly of a lamellar-phase block copolymer material on a substrate. FIG. 35 illustrates a perspective view of a base substrate at a preliminary processing stage bearing a hydrophilic material on the surface. FIGS. 36-39 illustrate the substrate of FIG. 35 at subsequent processing stages to form a patterned master template. FIGS. 37A, 38A, and 39A illustrate top plan views and FIGS. 37B, 38B, and 39B illustrate elevational, cross-sectional views of the substrates shown in FIGS. 37, 38, and 39, respectively.
FIGS. 40-43 illustrate another embodiment of a process for forming a chemically patterned master template for use in forming a stamp for directing self-assembly of a lamellar-phase block copolymer material. FIG. 40 illustrates a perspective view of a base substrate at a preliminary processing stage bearing a hydrophobic material on the surface. FIGS. 41-43 illustrate the substrate of FIG. 40 at subsequent processing stages to form a patterned master template. FIGS. 41A, 42A, and 43A illustrate top plan views and FIGS. 41B, 42B, and 43B illustrate elevational, cross-sectional views of the substrates shown in FIGS. 41, 42, and 43, respectively.
FIGS. 44-47 illustrate an embodiment according to the invention for forming a stamp on a master template as illustrated in FIG. 39. FIG. 44 illustrates a perspective view of a master template with a material for forming the stamp in a preliminary processing stage. FIG. 45 illustrates the master template/stamp material complex at a subsequent processing step. FIGS. 44A and 45A illustrate top plan views and FIGS. 44B and 45B illustrate elevational, cross-sectional views of the master template/stamp material complex shown in FIGS. 44 and 45, respectively. FIGS. 46 and 47 illustrate elevational, cross-sectional views of the master template/stamp material complex of FIG. 45 at subsequent processing steps showing the removal of the chemically patterned stamp from the master template. FIG. 47A illustrates a perspective view of the stamp of FIG. 47, showing the chemically patterned surface of the stamp.
FIGS. 48-52 illustrate an embodiment of the invention for using the stamp illustrated in FIGS. 47 and 47A for directing ordering of a lamellar-phase block copolymer material. FIGS. 48 and 49 illustrate elevational, cross-sectional views of the stamp brought into contact with the block copolymer material on a substrate. FIG. 50 illustrates an elevational, cross-sectional view of the annealing of the block copolymer material in contact with the stamp. FIG. 50A illustrates a top plan view of the surface of the annealed block copolymer material of FIG. 50. FIGS. 51 and 52 illustrate the removal of the chemically patterned stamp from the annealed and self-assembled block copolymer material of FIG. 50, shown in an elevational, cross-sectional view.
FIGS. 53-55 illustrate the use of the self-assembled lamellar-phase block copolymer material of FIG. 52 to mask and etch an underlying substrate. FIG. 53 illustrates an elevational, cross-sectional view of the block copolymer material of FIG. 52 at a subsequent processing step to selectively remove polymer domains to form a mask with openings to the substrate. FIGS. 54 and 55 illustrate the substrate shown in FIG. 53 at subsequent processing stages to form and fill openings in the substrate. FIGS. 53A, 54A, and 55A are top plan views of the substrate shown in FIGS. 53, 54, and 55, respectively.
FIGS. 56-58 illustrate another embodiment of a process for forming a chemically patterned master template and stamp for directing self-assembly of a cylinder-phase block copolymer material. FIG. 56 illustrates a perspective view of a master template having a surface bearing dots composed of a hydrophilic material amidst a hydrophobic material. FIG. 56A is a top plan view and FIG. 56B is an elevational, cross-sectional view of the master template shown in FIG. 56.
FIG. 57 illustrates an embodiment of a stamp formed from the master template of FIG. 56 in an elevational, cross-sectional view. FIG. 57A is a top plan view of the surface of the stamp of FIG. 57.
FIG. 58 illustrates an embodiment of the use of the stamp of FIG. 57 to direct ordering of a cylindrical-phase block copolymer material in an elevational, cross-sectional view. FIG. 58A illustrates a top plan view of the surface of the annealed and ordered block copolymer material of FIG. 58.
FIG. 59 illustrates an elevational, cross-sectional view of the use of the self-assembled cylindrical-phase block copolymer material of FIGS. 58 and 58A to mask and etch an underlying substrate.
FIG. 60 illustrates the substrate shown in FIG. 59 at a subsequent processing stage to fill the cylindrical openings in the substrate. FIG. 60A is a top plan view of the substrate shown in FIG. 60.
FIG. 61 illustrates geometries for an integrated circuit layout that can be prepared using embodiments of the invention.
In the context of the current application, the term "semiconductor substrate" or "semiconductive substrate" or "semiconductive wafer fragment" or "wafer fragment" or "wafer" will be understood to mean any construction comprising semiconductor material, including, but not limited to, bulk semiconductive materials such as a semiconductor wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term "substrate" refers to any supporting structure, including, but not limited to, the semiconductive substrates, wafer fragments or wafers described above.
"L.sub.o" is the inherent periodicity or pitch value (bulk period or repeat unit) of structures that self-assemble upon annealing from a self-assembling (SA) block copolymer or a blend of a block copolymer with one or more of its constituent homopolymers.
The term "chemical affinity" means the tendency of molecules to associate with each other based upon chemical forces between the molecules. The term "physiosorbed" means the physical adsorption of a molecule (e.g., ink material) to a surface, for example, through weak intermolecular interactions such as Van der Waals forces. The term "chemisorbed" means the chemical adsorption of a molecule (e.g., ink material) to a surface, for example, through chemically bonding such as through hydrogen bonds, ionic bonds, dithiol linkages, electrostatic bonds or other "weak" chemical bond.
In embodiments of the invention, a stamp or template is prepared by guided self-assembly of block copolymers, with both polymer domains at the air interface. Block copolymer films spontaneously assemble into periodic structures by microphase separation of the constituent polymer blocks after annealing, forming ordered domains at nanometer-scale dimensions. One of the polymer blocks has affinity for and is swelled by absorption of an ink chemical and a second polymer domain has substantially no affinity for the ink chemical and remains unchanged. The chemical ink can then be transferred from the stamp to a receptor substrate where the ink forms SAMs. The resolution of the imprinted SAMs exceed other microcontact techniques using self-assembled polymer films, and processing costs using the technique is significantly less than using electron beam lithography or EUV photolithography, which have comparable resolution.
The two-dimensional (2D) inked pattern that is formed on the receptor substrate can then be used, for example, as a template or pattern for self-assembled ordering of a block copolymer film that is cast onto the patterned receptor substrate. Following self-assembly on the receptor substrate, one block of the copolymer can then be selectively removed and the remaining patterned film used as an etch mask for patterning nanosized features into the underlying substrate.
Methods for fabricating a stamp composed of a self-assembled block copolymer thin film that defines nanometer-scale cylindrical and linear array patterns according to embodiments of the invention are illustrated in FIGS. 5-14B.
In some embodiments, the stamp is prepared under processing conditions that use a graphoepitaxy technique utilizing the sidewalls of trenches as constraints to induce orientation and registration of a film of a self-assembling diblock copolymer to form an ordered array pattern registered to the trench sidewalls. Graphoepitaxial techniques can be used to order cylindrical-phase diblock copolymers in one dimension, for example, parallel lines of half-cylinders, hexagonal close-packed arrays of perpendicular cylinders, or a single row of perpendicular cylinders within lithographically defined trenches. A desired pattern of cylinders on the stamp can be prepared by providing trenches having walls that are selective to one polymer block of a block copolymer and a floor composed either of a material that is block-sensitive or preferentially wetting to one of the blocks of the block copolymer in trenches where lines of parallel half-cylinders are desired, or a material that is neutral wetting to both blocks in trenches where an array of perpendicular cylinders are desired.
Additionally, in some embodiments, the trench floors can be chemically differentiated to provide a wetting pattern to control orientation of the microphase separated and self-assembling cylindrical domains in a second dimension, for example, parallel lines of half-cylinders or perpendicular-oriented cylinders. The trench floors are structured or composed of surface materials to provide a neutral wetting surface or preferential wetting surface to impose ordering on a block copolymer film that is then cast on top of the substrate and annealed to produce desired arrays of nanoscaled lines and/or cylinders.
As illustrated in FIGS. 5-5B, a base substrate 28 is provided, which can be silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, among other materials. In some embodiments, a neutral wetting material 30 is formed over the base substrate 28. A material layer 32 to be etched can then be formed over the neutral wetting material 30 and etched to form trenches 34. Portions of the material layer 32 form a spacer 36 between the trenches 34. The trenches 34 are structured with opposing sidewalls 38, opposing ends 40, a floor 42, a width (w.sub.t), a length (l.sub.t) and a depth (D.sub.t).
As illustrated in FIG. 6, in embodiments for forming a stamp 26' with a hexagonal close-packed array of perpendicular cylinders, ends 40' of trenches 34' are angled to sidewalls 38', for example, at an about 60.degree. angle, and in some embodiments, the trench ends are slightly rounded. In other embodiments, the material layer 32 can be formed on the base substrate 28, etched to form the trenches 34, and then a neutral wetting material (e.g., random copolymer) 30 can be applied to the trench floors 42 and crosslinked. Non-crosslinked random copolymer material outside the trenches 34 (e.g., on the spacers 36) can be subsequently removed.
The trenches can be formed using a lithographic tool having an exposure system capable of patterning at the scale of L.sub.o (10-100 nm). Such exposure systems include, for example, extreme ultraviolet (EUV) lithography, proximity X-rays and electron beam (e-beam) lithography, as known and used in the art. Conventional photolithography can attain (at smallest) about 58 nm features.
A method called "pitch doubling" or "pitch multiplication" can also be used for extending the capabilities of photolithographic techniques beyond their minimum pitch, as described, for example, in U.S. Pat. No. 5,328,810 (Lowrey et al.), U.S. Pat. No. 7,115,525 (Abatchev et al.), US 2006/0281266 (Wells), now U.S. Pat. No. 7,396,781, issued Jul. 8, 2008, and US 2007/0023805 (Wells), now U.S. Pat. No. 7,776,715, issued Aug. 17, 2010. Briefly, a pattern of lines is photolithographically formed in a photoresist material overlying a layer of an expendable material, which in turn overlies a substrate, the expendable material layer is etched to form placeholders or mandrels, the photoresist is stripped, spacers are formed on the sides of the mandrels, and the mandrels are then removed, leaving behind the spacers as a mask for patterning the substrate. Thus, where the initial photolithography formed a pattern defining one feature and one space, the same width now defines two features and two spaces, with the spaces defined by the spacers. As a result, the smallest feature size possible with a photolithographic technique is effectively decreased down to about 30 nm or less.
The boundary conditions of the trench sidewalls 38 in both the x- and y-axis impose a structure wherein each trench contains "n" number of features (e.g., cylinders, lamellae, etc.). Factors in forming a single array or layer of nanostructures within the trenches include the width and depth of the trench, the formulation of the block copolymer to achieve the desired pitch (L.sub.o), and the thickness (t) of the copolymer film. The length (l) of the trenches is at or about nL.sub.o where n is an integer multiple of L.sub.o, typically within a range of about n*10-n*100 nm (with n being the number of features or structures (i.e., cylinders)). The depth (D.sub.t) of the trenches 34 is about equal to L.sub.o (D.sub.t.about.L.sub.0) such that a cast block copolymer material 44 of about L.sub.o will fill the trenches, and is generally over a range of about 10-100 nm. The trenches 34 are constructed with a width (w.sub.t) such that a block copolymer (or blend) will self-assemble upon annealing into a single layer of n elements (e.g., cylinders, lamellae, etc.) spanning the width (w.sub.t) of the trench, with the center-to-center distance of adjacent identical elements being at or about L.sub.o. The width of the spacer 36 between adjacent trenches can vary and is generally about L.sub.o to about nL.sub.o. In some embodiments, the trench dimension is about 100-1,500 nm wide (w.sub.t) and about 100-25,000 nm in length (l.sub.t), with a depth (D.sub.t) of about 10-100 nm.
To form a single layer of n lamellae from a lamellar-phase block copolymer (inherent pitch value of L.sub.o), which spans the width registered to the sidewalls 38 for the length of the trench 34, the width (w.sub.t) of the trenches can be a multiple of the inherent pitch value (L.sub.o) of the polymer, being equal to or about nL.sub.o ("n*L.sub.o") and typically ranging from about n*10 to about n*100 nm (with n being the number of features or structures). For forming a 1D array of perpendicular-oriented cylinders with a center-to-center pitch of at or about L.sub.o (e.g., a width of about 65-75 nm for an L.sub.o value of about 36-42 nm), the trenches 34 can be constructed with a width (w.sub.t) of about 2*L.sub.o or less, e.g., about 1.0*L.sub.o to about 2*L.sub.o (e.g., about 1.75*L.sub.o). For forming parallel lines of half-cylinders or a periodic, hexagonal close-pack or honeycomb array of perpendicular cylinders, the trenches 34, 34' can be constructed with a width (w.sub.t) at or about an integer multiple of the L.sub.o value or nL.sub.o where n=3, 4, 5, etc. (e.g., a width of about 120-2,000 nm for an L.sub.o value of about 36-42 nm).
For example, a block copolymer having a 35 nm pitch (L.sub.o value) deposited into a 75 nm wide trench having a neutral wetting floor will, upon annealing, result in a zigzag pattern of 35 nm diameter perpendicular cylinders that are offset by a half distance for the length (l.sub.b) of the trench, rather than a single line of perpendicular cylinders aligned with the sidewalls down the center of the trench. As the L.sub.o value of the copolymer is increased, for example, by forming a ternary blend by the addition of both constituent homopolymers, there is a shift from two rows to one row of the perpendicular cylinders within the center of the trench.
A block copolymer material of about L.sub.o is deposited to about fill the trenches 34 and, upon annealing, the block copolymer film will self-assemble into morphologies to foim an array of elements that are oriented in response to the wetting properties of the trench surfaces. Entropic forces drive the wetting of a neutral wetting surface by both blocks, and enthalpic forces drive the wetting of a preferential-wetting surface by the preferred block (e.g., the minority block). The trench sidewalls 38 and ends 40 are structured to be preferential wetting by one block of the block copolymer to induce registration of elements (e.g., cylinders, half-cylinders, lamellae, etc.) as the polymer blocks self-assemble. Upon annealing, the preferred block of the block copolymer will segregate to the sidewalls and edges of the trench to assemble into a thin (e.g., 1/4 pitch) interface (wetting) layer, and will self-assemble to form elements according to the wetting surface of the trench floor 42.
For example, in response to neutral wetting properties of the trench floor surface material (e.g., crosslinked neutral wetting random copolymer mat) and preferential wetting sidewalls and ends, an annealed cylinder-phase block copolymer film will self-assemble to form cylinders in a perpendicular orientation to the trench floors in the center of a polymer matrix, and a lamellar-phase block copolymer film will self-assemble into a lamellar array of alternating polymer-rich blocks (e.g., PS and PMMA) that extend across the width and for the length of the trench and are oriented perpendicular to the trench floor and parallel to the sidewalls. In a trench having a preferential wetting floor, sidewalls and ends, an annealed cylinder-phase block copolymer film will self-assemble to form lines of half-cylinders in a polymer matrix extending the length of the trench and parallel to the trench floor.
The structuring of the trench sidewalls 38 and ends 40 to be preferential wetting causes one of the blocks of the copolymer material to form a thin wetting layer on those surfaces. To provide preferential wetting surfaces, for example, in the use of a PS-b-PMMA block copolymer, the material layer 32 can be composed of silicon (with native oxide), oxide (e.g., silicon oxide, SiO.sub.x), silicon nitride, silicon oxycarbide, indium tin oxide (ITO), silicon oxynitride, and resist materials such as methacrylate-based resists, among other materials, which exhibit preferential wetting toward the PMMA block. In the use of a cylinder-phase copolymer material, the material will self-assemble to form a thin (e.g., 1/4 pitch) interface layer of PMMA and PMMA cylinders or half-cylinders (e.g., 1/2 pitch) in a PS matrix. In the use of a lamellar-phase block copolymer material, the material will assemble into alternating PMMA and PS lamellae (e.g., 1/2 pitch) within each trench, with PMMA at the sidewall interface (e.g., 1/4 pitch).
In other embodiments, a preferential wetting material such as a polymethylmethacrylate (PMMA) polymer modified with an --OH containing moiety (e.g., hydroxyethylmethacrylate) can be applied onto the surfaces of the trenches 34, for example, by spin coating and then heating (e.g., to about 170.degree. C.) to allow the terminal OH groups to end-graft to oxide sidewalls 38 and ends 40 of the trenches 34. Non-grafted material can be removed by rinsing with an appropriate solvent (e.g., toluene). See, for example, Mansky et al., Science, 1997, 275, 1458-1460, and In et al., Langmuir, 2006, 22, 7855-7860.
The structuring of the trench floors 42 to be neutral wetting (equal affinity for both blocks of the copolymer) allows both blocks of the copolymer material to wet the floor of the trench. A neutral wetting material 30 can be provided by applying a neutral wetting polymer (e.g., a neutral wetting random copolymer) onto the base substrate 28, forming the material layer 32 and then etching the trenches to expose the underlying neutral wetting material, as illustrated in FIGS. 5-5B. A neutral wetting random copolymer can also be applied after forming the trenches, for example, as a blanket coat by casting or spin-coating into the trenches and thermally processing to flow the material into the bottom of the trenches by capillary action, which results in a layer (mat) composed of the crosslinked, neutral wetting random copolymer. In another embodiment, the random copolymer material within the trenches can be photo-exposed (e.g., through a mask or reticle) to crosslink the random copolymer within the trenches to form the neutral wetting material layer. Non-crosslinked random copolymer material outside the trenches (e.g., on the spacers 36) can be subsequently removed.
For example, in the use of a poly(styrene-block-methyl methacrylate) block copolymer (PS-b-PMMA), a thin film of a photo-crosslinkable random PS:PMMA copolymer (PS-r-PMMA) which exhibits non-preferential or neutral wetting toward PS and PMMA can be cast onto the base substrate 28 (e.g., by spin coating). The polymer material can be fixed in place by grafting (on an oxide substrate) or by thermally or photolytically crosslinking (any surface) to form a mat that is neutral wetting to PS and PMMA and insoluble due to the crosslinking.
In another embodiment, a neutral wetting random copolymer of polystyrene (PS), polymethacrylate (PMMA) with hydroxyl group(s) (e.g., 2-hydroxyethyl methacrylate (P(S-r-MMA-r-HEMA)) (e.g., about 58% PS) can be can be selectively grafted to a base substrate 28 (e.g., an oxide) as a layer 30 about 5-10 nm thick by heating at about 160.degree. C. for about 48 hours. See, for example, In et al., Langmuir, 2006, 22, 7855-7860.
A surface that is neutral wetting to PS-b-PMMA can also be prepared by spin coating a blanket layer of a photo- or thermally crosslinkable random copolymer such as a benzocyclobutene- or azidomethylstyrene-functionalized random copolymer of styrene and methyl methacrylate (e.g., poly(styrene-r-benzocyclobutene-r-methyl methacrylate (PS-r-PMMA-r-BCB)). For example, such a random copolymer can comprise about 42% PMMA, about (58-x) % PS and x % (e.g., about 2-3%) of either polybenzocyclobutene or poly(para-azidomethylstyrene)). An azidomethylstyrene-functionalized random copolymer can be UV photo-crosslinked (e.g., 1-5 MW/cm^2 exposure for about 15 seconds to about 30 minutes) or thermally crosslinked (e.g., at about 170.degree. C. for about 4 hours) to form a crosslinked polymer mat as a neutral wetting layer 30. A benzocyclobutene-functionalized random copolymer can be thermally crosslinked (e.g., at about 200.degree. C. for about 4 hours or at about 250.degree. C. for about 10 minutes).
In another embodiment in which the base substrate 28 is silicon (with native oxide), another neutral wetting surface for PS-b-PMMA can be provided by hydrogen-terminated silicon. For example, the floors 42 of trenches 34 can be etched, for example, with a hydrogen plasma, to remove the oxide material and form hydrogen-terminated silicon 30, which is neutral wetting with equal affinity for both blocks of a block copolymer material such as PS-b-PMMA. H-terminated silicon can be prepared by a conventional process, for example, by a fluoride ion etch of a silicon substrate (with native oxide present, about 12-15 .ANG.) by exposure to an aqueous solution of hydrogen fluoride (HF) and buffered HF or ammonium fluoride (NH.sub.4F), by HF vapor treatment, or by a hydrogen plasma treatment (e.g., atomic hydrogen). An H-terminated silicon substrate can be further processed by grafting a random copolymer such as PS-r-PMMA selectively onto the substrate resulting in a neutral wetting surface, for example, by an in situ free radical polymerization of styrene and methyl methacrylate using a di-olefinic linker such as divinylbenzene which links the polymer to the surface to produce an about 10-15 nm thick film.
In other embodiments, to induce formation of parallel half-cylinders in the trenches, the trenches are structured with a floor surface that is preferential wetting by one of the polymer blocks of a block copolymer. Annealing of a cylindrical-phase block copolymer material having an inherent pitch value of about L.sub.o will result in "n" rows or lines of half-cylinders (parallel to the sidewalls and trench floor) extending the length (l.sub.t) and spanning the width (w.sub.t) of the trenches.
Preferential wetting floors 42 can be provided by a silicon material with an overlying layer 30 of native oxide, or by forming a layer 30 of oxide (e.g., silicon oxide, SiO.sub.x), silicon nitride, silicon oxycarbide, ITO, silicon oxynitride, resist material such as methacrylate-based resists, etc., over the base substrate 28.
Referring now to FIGS. 7-7B, a film of a self-assembling block copolymer material 44 having an inherent pitch at or about L.sub.o (or a ternary blend of block copolymer and homopolymers blended to have a pitch at or about L.sub.o) is then deposited into the trenches 34 and onto the trench floors 42, and processed such that the copolymer material 44 will then self-assemble. The block copolymer material 44 can be deposited by spin casting or spin-coating from a dilute solution (e.g., about 0.25-2 wt % solution) of the copolymer in an organic solvent such as dichloroethane (CH.sub.2Cl.sub.2) or toluene, for example.
Capillary forces pull excess of the block copolymer material 44 (e.g., greater than a monolayer) into the trenches 34. In a trench having a depth (D.sub.t) at or about the L.sub.o value of the copolymer material 44, the block copolymer is deposited to fill the trench 34 such that the film thickness (t.sub.1) of the deposited block copolymer 44 is generally at or about L.sub.o and the film will self-assemble to form a single layer of elements (e.g., cylinders, lamellae, etc.) across the width (w.sub.t) of the trench, the elements having a diameter/width at or about 0.5 L.sub.o (e.g., about 20 nm). For example, a typical thickness (t.sub.1) of a lamellar-phase PS-b-PMMA block copolymer film 44 is about .+-.20% of the L.sub.o value of the copolymer (e.g., about 10-100 nm) to form alternating polymer-rich lamellar blocks having a width of about 0.5 L.sub.o (e.g., 5-50 nm) within each trench. In the use of a solvent anneal, the film can be much thicker than L.sub.o, e.g., up to about +1000% of the L.sub.o value. The thickness of the block copolymer material 44 can be measured, for example, by ellipsometry techniques. As shown, a thin film 44a of the block copolymer material 44 can be deposited onto the spacers 36 of the material layer 32; this film will form a monolayer of elements with no apparent structure from a top-down perspective (e.g., lamellae in a parallel orientation).
The block copolymer material is fabricated such that each of the self-assembled polymer domains has a different solubility for a given ink chemical. The ink chemical is applied as an organic solution, either neat (undissolved) or combined with a solvent that will be selectively absorbed into and cause one of the polymer domains to swell and become impregnated with the ink chemical material. In some embodiments, the ink but not the solvent will be selectively absorbed into one of the polymer domains.
In some embodiments, the block copolymer can be chemically modified to include a functional group having chemical affinity for the ink material, for example, a thiol or amine group. For example, one of the blocks can inherently contain a thiol or amine functional group, for example, polyvinylpyridine.
The film morphology, including the domain sizes and periods (L.sub.o) of the microphase-separated domains, can be controlled by chain length of a block copolymer (molecular weight, MW) and volume fraction of the AB blocks of a diblock copolymer to produce lamellar, cylindrical, or spherical morphologies, among others.
For example, for volume fractions at ratios greater than about 80:20 of the two blocks (AB) of a diblock polymer, a block copolymer film will microphase separate and self-assemble into periodic spherical domains with spheres of polymer B surrounded by a matrix of polymer A. For ratios of the two blocks generally between about 60:40 and 80:20, the diblock copolymer assembles into periodic cylindrical domains of polymer B within a matrix of polymer A. For ratios between about 50:50 and 60:40, lamellar domains or alternating stripes of the blocks are formed. Domain size typically ranges from 5-50 nm.
An example of a lamellae-forming PS-b-PMMA diblock copolymer (L.sub.o=32 nm) to form about 16 nm wide lamellae is composed of a weight ratio of about 50:50 (PS:PMMA) and total molecular weight (M.sub.n) of about 51 kg/mol. An example of a cylinder-forming PS-b-PMMA copolymer material (L.sub.o=35 nm) to form about 20 nm diameter cylindrical PMMA domains in a matrix of PS is composed of about 70% PS and 30% PMMA with a total molecular weight (M.sub.n) of 67 kg/mol.
Although PS-b-PMMA diblock copolymers are used in the illustrative embodiments, other types of block copolymers (i.e., triblock or multiblock copolymers) can be used. Examples of diblock copolymers include poly(styrene-block-methyl methacrylate) (PS-b-PMMA), polyethyleneoxide-polyisoprene, polyethyleneoxide-polybutadiene, polyethyleleoxide-polystyrene, polyetheleneoxide-polymethylmethacrylate, polystyrene-polyvinylpyridine, polystyrene-block-polyisoprene (PS-b-PI), polystyrene-polybutadiene, polybutadiene-polyvinylpyridine, polyisoprene-polymethylmethacrylate, and polystyrene-polylactide, among others. Examples of triblock copolymers include poly(styrene-block methyl methacrylate-block-ethylene oxide).
The block copolymer material can also be formulated as a binary or ternary blend comprising a SA block copolymer and one or more homopolymers of the same type of polymers as the polymer blocks in the block copolymer, to produce blends that swell the size of the polymer domains and increase the L.sub.o value of the polymer. The volume fraction of the homopolymers can range from 0% to about 40%. An example of a ternary diblock copolymer blend is a PS-b-PMMA/PS/PMMA blend, for example, 46K/21K PS-b-PMMA containing 40% 20K polystyrene and 20K poly(methylmethacrylate). The L.sub.o value of the polymer can also be modified by adjusting the molecular weight of the block copolymer.
The block copolymer film 44 is then annealed to cause the polymer blocks to phase separate and self-assemble according to the preferential and neutral wetting of the trench surfaces to form a self-assembled polymer film. The resulting morphology of the annealed film 46 (e.g., perpendicular orientation of lamellae) can be examined, for example, using atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM).
In some embodiments, the deposited block copolymer film 44 can be solvent annealed. In embodiments of a solvent anneal, the film 44 can be swollen by exposure to a vapor of a "good" solvent for both blocks, and the vapor can then be removed. Vapors of a solvent such as benzene, chloroform or a chloroform/octane mixture, for example, can be exposed to the film 44 to slowly swell both blocks (PS, PMMA) of the film 44. The solvent and solvent vapors are then allowed to slowly evaporate to dry the film 44, resulting in self-assembled polymer domains.
The block copolymer film 44 can also be thermally annealed at the annealing temperature (e.g., about 150.degree. C.-250.degree. C.) in an atmosphere that is saturated or nearly saturated (but not supersaturated) with a solvent in which both blocks are soluble. The solvent-saturated vapor maintains a neutral air interface in conjunction with the surface interface with a neutral wetting floor 42. The existence of both neutral wetting air and surface interfaces induces the formation of perpendicular features throughout the film 44.
Referring to FIGS. 8-8A, upon annealing a lamellar-phase block copolymer film 44 (e.g., PS-b-PMMA of about L.sub.0) within a trench 34 with preferential wetting sidewalls 38 and a neutral wetting trench floor 42 (exhibits neutral or non-preferential wetting toward both blocks, e.g., a random graft copolymer), the polymer material will self-assemble into a film 46 composed of alternating polymer-rich blocks 48, 50 (e.g., PS and PMMA). The lamellar blocks 48, 50 are oriented perpendicular to the trench floor 42 and parallel to the sidewalls 38, extending the length of the trench 34 and spanning the width (w.sub.t) at an average pitch value at or about L.sub.o. The constraints provided by the width (w.sub.t) of the trenches 34 and the character of the copolymer composition combined with preferential or neutral wetting surfaces within the trenches result, upon annealing, in a single layer of n lamellae 48, 50 across the width (w.sub.t) of the trench. The number "n" or pitches of lamellar blocks within a trench is according to the width (w.sub.t) of the trench and the molecular weight (MW) of the block copolymer. For example, depositing and annealing an about 50:50 PS:PMMA block copolymer film (e.g., M.sub.n=51 kg/mol; L.sub.o=32 nm) in an about 160 nm wide trench will subdivide the trench into about 5 lamellar pitches. The stamping surface of a stamp 26 is thus defined by a lamellar array of polymer domains that define a linear pattern of lamellar blocks, each about 14-18 nm wide and several microns in length (e.g., about 10-4000 .mu.m), and a center-to-center pitch of about 32 nm. A smaller pitch can be dialed in by using lower molecular weight diblock copolymers.
In embodiments in which a film of a cylindrical-phase block copolymer is deposited into trenches with preferential wetting sidewalls and a neutral wetting trench floor, upon annealing, the cylinder-phase copolymer film will self-assemble into a film composed of perpendicular-oriented cylinders of one of the polymer blocks (e.g., PMMA) within a polymer matrix of the other polymer block (e.g., PS) registered to the sidewalls of the trench.
FIG. 9 illustrates an embodiment of a stamp 26' composed of an annealed cylinder-phase copolymer film 46' in the formation of an array of hexagonal close-packed array of perpendicular-oriented cylinders 52' within a polymer matrix 54'. The sidewalls 38' and angled ends 40' of the trenches 34' are used as constraints to induce orientation and registration of cylindrical copolymer domains to achieve the hexagonal cylindrical array registered to the trench sidewalls. The width (w.sub.t) of the trenches 34' is at or about L.sub.o*cos(.pi./6) or L.sub.o*0.866, which defines the number of rows of cylinders, and the trench length (l.sub.t) is at or about mL.sub.o, which defines the number of cylinders per row. The ends 40' of the trenches are angled to the sidewalls 38', for example, at an about 60.degree. angle, and in some embodiments can be slightly rounded. A cylindrical-phase diblock copolymer material having an inherent pitch at or about L.sub.o (or blend with homopolymers) and a thickness (t) of about L.sub.o will self-assemble upon annealing to form a hexagonal array of cylindrical domains 52' of the minor (preferred) polymer block (i.e., like domains such as PMMA) that are oriented perpendicular to the neutral wetting floor 42' of the trench 34' within a matrix 54' of the major polymer block (e.g., PS). The minor (preferred) polymer block (e.g., PMMA) will segregate to the preferential wetting sidewalls 38' and ends 40' to form a wetting layer 52a'. The hexagonal array contains n single rows of cylinders according to the width (w.sub.t) of the trench with the cylinders 52' in each row being offset from the cylinders in the adjacent rows. Each row contains a number of cylinders, generally m cylinders, which number can vary according to the length (l.sub.t) of the trench and the shape of the trench end (e.g., rounded, angled, etc.) with some rows having greater or less than III cylinders. The cylinders 52' are generally spaced apart at a pitch distance (p.sub.1) at or about L.sub.o between each cylinder in the same row and an adjacent row (center-to-center distance), and at a pitch distance (p.sub.2) at or about L.sub.o*cos(.pi./6) or 0.866 L.sub.o being the distance between two parallel lines where one line bisects the cylinders in a given row and the other line bisects the cylinders in an adjacent row. The stamping surface 64' of the stamp 26' is thus defined by an array of polymer domains that define a hexagonal or honeycomb pattern of perpendicular-oriented cylinders 52', each about 20-22 nm in diameter with a center-to-center pitch of about 42 nm.
In another embodiment using a cylindrical-phase copolymer material, the trench dimensions can be modified to use the trench sidewalls and ends as constraints to induce orientation and registration of cylindrical copolymer domains in a single row parallel to the trench sidewalls. The trenches are structured to have a width (w.sub.t) that is at or about 1.0-1.75* the L.sub.o value of the block copolymer material, a neutral wetting floor, and sidewalls and ends that are preferential wetting by the minority (preferred) block (e.g., the PMMA block) of the diblock copolymer (e.g., PS-b-PMMA). A cylindrical-phase diblock copolymer (or blend with homopolymers) having an inherent pitch at or about L.sub.o can be deposited into the trenches to a thickness (t.sub.1) of about the L.sub.o value of the copolymer material (as in FIGS. 7 and 7A). As illustrated in FIGS. 10 and 10A, the annealed block copolymer film self-assembles to form film 46''. The constraints provided by the width (w.sub.t) of trench 34'' and the character of the block copolymer composition combined with a neutral wetting trench floor 42'' and preferential wetting sidewalls 38'' results in a one-dimensional (1D) array or single row of perpendicular-oriented cylindrical domains 52'' of the minority (preferred) polymer block (e.g., PMMA) within a matrix 54'' of the major polymer block (e.g., PS), with the preferred block segregating to the sidewalls 38'' of the trench 34'' to form a wetting layer 52a''. In some embodiments, the cylinders have a diameter at or about 0.5 L.sub.o (e.g., about 20 nm), the number n of cylinders in the row is according to the length of the trench, and the center-to-center distance (pitch distance) (p) between each like domain (cylinder) is at or about L.sub.o (e.g., about 40 nm). The resulting stamping surface 64'' of the stamp 26'' is defined by an array of polymer domains that define a single row of perpendicular-oriented cylinders 52'', each about 20-22 nm in diameter with a center-to-center pitch of about 42 nm.
Referring now to FIGS. 11 and 11A, in yet another embodiment using a cylindrical-phase copolymer material, the trenches 34''' can be structured with preferential wetting surfaces 38, 40, 42 to induce formation of half-cylinder copolymer domains 56''' in a polymer matrix 54''' that are in a parallel orientation to the trench floors 42''' and registered to the sidewalls 38'''. A preferentially wetting floor 42''' can be provided, for example, by a layer 58''' of oxide, silicon nitride, silicon oxycarbide, among others. The stamping surface 64''' of the stamp 26'''' is defined by an array of polymer domains that define lines of half-cylinders, each about 20-22 nm wide and several microns in length (e.g., about 10-4000 .mu.m), and a center-to-center pitch of about 42 nm.
In another embodiment of the invention, graphoepitaxy (topographic features, e.g., sidewalls, ends, etc.) is used to influence the formation of arrays in one dimension, and the trench floors provide a wetting pattern that can be used to chemically control formation of the arrays in a second dimension. For example, as illustrated in FIGS. 12 and 12A, a neutral wetting material 30'''' (e.g., random copolymer) can be formed on the base substrate 28'''' and crosslinked in select regions 60'''', such as by photo-exposure through a reticle or a patterned mask (e.g., photoresist). As shown, the non-crosslinked regions of the neutral wetting material 30'''' have been removed (e.g., by wet processing using a solvent) to expose the sections 62'''' of the underlying base substrate 28'''', resulting in a pattern of discrete regions 60'''' of the crosslinked neutral-wetting material 30'''' (random copolymer) and sections 62'' of the exposed preferential-wetting base substrate 28''.
As depicted in FIGS. 13-13B, the material layer 32'''' can then be formed and trenches 34'''' etched to expose the sections 60'''' of the neutral wetting material 30'''' and sections 62'''' of the exposed base substrate 10'''' on the trench floors 18'''' as a series of stripes oriented perpendicular to the trench sidewalls 38''''. The trench floors 42'''' are thus defined by alternating preferential wetting sections 62'''' (base substrate 28'''') and neutral wetting sections 60'''' (a mat of the crosslinked random copolymer 30''''). In some embodiments, each of the sections can have a width (w.sub.r1) at or about L.sub.o, and in other embodiments, the neutral wetting sections 60'''' can have a width (w.sub.r2) at or about nL.sub.o and the preferential wetting sections 62'' have a width at or about L.sub.o. The trench sidewalls 38'''' and ends 40'''' (e.g., of oxide) are preferential wetting to the minority (preferred) block of the block copolymer.
A cylindrical-phase block copolymer film (e.g., pitch L.sub.o) can then be cast or spin-coated into the trenches 34'''' to a film thickness (t) of about L.sub.o and annealed. As illustrated in FIGS. 14-14B, the differing wetting patterns on the trench floor 42'''' imposes ordering on the cylindrical-phase block copolymer film as it is annealed, resulting in a 1D array of alternating perpendicular-oriented cylinders 52'''' and parallel-oriented half-cylinders 56'''' for the length (nL.sub.o) of each trench.
After the copolymer film is annealed and ordered, the film can then be treated to crosslink the polymer segments (e.g., the PS segments) to fix and enhance the strength of the self-assembled polymer blocks. The polymers can be structured to inherently crosslink (e.g., upon exposure to ultraviolet (UV) radiation, including deep ultraviolet (DUV) radiation), or one or both of the polymer blocks of the copolymer material can be formulated to contain a crosslinking agent.
Optionally, the unstructured thin film 44a of the block copolymer material outside the trenches (e.g., lamellae in a parallel orientation on spacer 36 in FIG. 7A) can then be removed, as illustrated in FIGS. 8 and 8A. In embodiments in which the ink chemical would be absorbed by the film 44a, the film would be removed.
For example, the trench regions can be selectively exposed through a reticle (not shown) to crosslink only the annealed and self-assembled film 46 within the trenches 34, and a wash can then be applied with an appropriate solvent (e.g., toluene) to remove the non-crosslinked portions of the block copolymer material 44a on the spacers 36, leaving the registered self-assembled film within the trench and exposing the surface of material layer 32 on the spacers 36 above/outside the trenches. In another embodiment, the annealed film 46 can be crosslinked globally, a photoresist material can be applied to pattern and expose the areas of the film 44a over the spacers 36 outside the trench regions, and the exposed portions of the copolymer film can be removed, for example, by an oxygen (O.sub.2) plasma treatment.
The resulting stamp is structured with a stamping surface 64 composed of an ordered array of polymer domains (e.g., 48, 50) in the desired pattern for stamping onto a receptor substrate. The stamp can then be inked and brought into contact with the receptor substrate to produce the pattern on the substrate.
The ink chemical material is selected such that it will be absorbed selectively into a polymer domain of the self-assembled polymer film by Van der Waals forces or other non-covalent force or bond (e.g., hydrogen bond, etc.) and will form a self-assembled monolayer (SAM) on the receptor substrate. The ink chemical can include one or more functional groups that chemically react with the receptor substrate. The chemical affinity between the ink material and the receptor substrate is greater than the chemical affinity between the ink material and the polymer domain in which it is absorbed.
In embodiments of the invention, the ink chemical can have amino, thiol, alcohol or alkyne functional groups. Examples of ink chemicals include thiols such as 2-aminoethanethiol, aminothiophenol, cysteine, homocysteine, leucinethiol, 2-butylaminoethanethiol, 2-cylcohexylaminoethanethiol, etc.; mercaptoalcohols such as mercaptoethanols (e.g., 2-mercaptoethanol (HS--CH.sub.2CH.sub.2OH)), mercaptopropanols (e.g., 2-mercaptopropanol) and mercaptobutanols (e.g., 4-mercapto-1-butanol, 2-mercaptobutanol); and acetylenics with hydrocarbon tails or other functional groups such as alcohols, thiols, amines, halides, etc., (e.g., carboxylates such as propiolic acid, 4-butynoic acid, 5-pentynoic acid), and the like.
The ink chemical material is in the form of an organic solution such that it will diffuse into and be selectively absorbed by one of the polymer domains causing the polymer domain to swell. The ink chemical material can be in the form of a neat (undiluted) solution or combined with an organic solvent that will promote diffusion of the material selectively into the selected polymer domain. Examples of solvents that can be utilized include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol and acetic acid. Typically, the concentration of the ink chemical material in solution is about 1-10 k mM.
In another embodiment, the ink chemical material can be provided in a vaporous form, which can provide a higher level of control with respect to the amount of ink material that is absorbed into the stamp. The stamp would be exposed to a vapor of the ink chemical for a sufficient time period for absorption of an adequate quantity of the ink chemical by the polymer domain.
FIGS. 15-18 illustrate an embodiment of a stamping process utilizing a stamp 26 according to the invention, as depicted in FIGS. 8 and 8A.
Referring to FIG. 15, a stamping process can be conducted by applying (arrows .dwnarw.) a solution of the ink chemical material (either neat or in a solvent) 66 onto the stamping surface 64 or, in other embodiments, by exposing the stamping surface 64 to a vapor of the ink chemical. The contact of the ink chemical solution with the stamping surface 64 of the stamp is for a time effective to enable the ink material to diffuse into and be selectively absorbed by the targeted polymer domain.
Upon contact of the stamp with the ink chemical, the polymer domain 50 with affinity for the ink chemical solution (e.g., PS domain) is swelled by absorption of the ink chemical solution, as illustrated in FIG. 16. The other polymer domain 48 with substantially no affinity for the ink chemical (e.g., PMMA domain) remains unchanged. This results in the stamping surface 64 of the stamp 26 having a relatively corrugated surface that defines the lines of the swollen polymer domains 50.
As illustrated in FIG. 17, a receptor substrate 68 is then brought into contact (arrows .dwnarw.) with the swollen and ink-containing polymer domains 50 situated on the stamping surface 64 of the stamp 26 to effect transfer of the ink material 66 onto the receptor substrate 68, resulting in a pattern 70 on the receptor substrate, as shown in FIGS. 18 and 18A. The ink chemical material 66 is transferred from the stamp 26 by chemical bonding of one or more functional groups of the ink material with a functional group(s) on the surface of the receptor substrate 68.
Examples of the receptor substrate 68 include silicon oxide, silicon wafers, silicon-on-insulator ("SOI") substrates, silicon-on-sapphire ("SOS") substrates, and other semiconductor substrates such as silicon-germanium, germanium, gallium arsenide and indium phosphide, chalcogenide-class of materials, magnetic materials (e.g., Ni, Fe, Co, Cu, Ir, Mn, Pt, Tu, etc.), and other substrates used in disk drives or optical storage devices. Optionally, the receptor substrate 68 can be modified to incorporate functional groups that enhance chemical bonding and transfer of the ink material from the stamp/template (e.g., stamp 26), as indicated in Table 1 (below). Substrates modified with a glycidoxy functionality will be reactive to inks having amine or thiol functional groups. Substrates modified with an isocyanate functionality will be reactive to inks having alcohol or amino functional groups. Substrates modified with chlorosilyl groups will be reactive to inks with amino, alcohol or thiol functional groups. Alkylazido-modified substrates will be reactive to inks with alkyne functional groups. For example, a silicon oxide substrate can be modified with azide groups to facilitate binding of an acetylenic carboxylate ink.
Table 1 (below) provides examples of ink chemical materials that can be used for selective absorption by one of the polymer block domains (i.e., PMMA) of a stamp according to the invention, and embodiments of receptor substrate modifications that can be used in combination with the ink chemical material to effect transfer of the ink onto the receptor substrate to form SAMs in a stamped pattern.
TABLE-US-00001 Ink Material Receptor Substrate modification Thiols, such as: Glycidoxy-modified substrates such as SiO.sub.2 2-aminoethanethiol grafted with a glycidoxypropyl(trialkoxy) aminothiophenol silane (e.g., glycidoxypropyl cysteine trimethoxysilane) homocysteine Isocyanato-modified substrates such as SiO.sub.2 leucinethiol grafted with a isocyanatopropyl(trialkoxy) 2-butylaminoethanethiol silane (e.g., isocyanatopropyl triethoxysilane, 2-cylcohexylamino- isocyanatopropyl trimethoxysilane, etc.) ethanethiol Chlorosilyl-modified substrates such as chlorine-terminated silicon (Si--Cl) (e.g., from H-terminated silicon exposed to Cl.sub.2 gas) Mercaptoalcohols, Isocyanato-modified substrates such as SiO.sub.2 such as: grafted with a isocyanatopropyl(trialkoxy) mercaptoethanols silane (e.g., isocyanatopropyl triethoxysilane, mercaptopropanols isocyanatopropyl trimethoxysilane, etc.) mercaptobutanols Chlorosilyl-modified substrates such as chlorine-terminated silicon (Si--Cl) Acetylenics with Alkylazido -modified substrates such as hydrocarbontails or other SiO.sub.2 grafted with 6-azidosulfonylhexyl functional groups such as (triethoxy) silane, or with an alcohols, thiols, amines, 11-azidoundecyl group halides, etc., such as: (e.g., formed from 11-bromoundecyl propiolic acid (triethyoxy) silane reacted with sodium (or acetylene azide). monocarboxylic acid) butynoic acid pentynoic acid
An alkylazido-modified receptor substrate 68 can be prepared, for example, as a silicon dioxide (SiO.sub.2) substrate grafted with 6-azidosulfonylhexyl (triethoxy)silane or with an 11-azidoundecyl group monolayers that can be formed by grafting 11-bromoundecyl (triethyoxy)silane to a SiO.sub.2 substrate then derivatizing with sodium azide, as described, for example, by Rozkiewicz et al., Angew. Chem. Int. Ed. Eng., 2006, 45, 5292-5296. A chlorosilyl-modified receptor substrate 68 can be prepared, for example, as chlorine-terminated silicon (Si--Cl) by chlorination of hydrogen-terminated silicon surfaces by exposure to chlorine gas (Cl.sub.2) (e.g., at 80.degree. C. or exposure to a tungsten lamp), as described, for example, by Zhu et al., Langmuir, 2006, 16, 6766-6772.
The temperature during the stamping process generally ranges from about room temperature (20.degree. C.) to near the boiling point of the ink chemical solution. Contact of the stamp 26 with the receptor substrate 68 is for a time effective to enable chemical bonds to form between functional groups on the receptor substrate and the ink chemical material 66, generally about 1 minute to about 4 hours, and typically about 1-15 minutes.
The receptor substrate and the ink material may react to form a urea or urethane linkage through a mercapto alcohol, a disulfide linkage through a thiol (R--SH) functional group, a bond involving acid/base groups, or an amine linkage through an amine/epoxide reaction of a triazole image through reaction between an azide and alkyne. Diffusion (or other transfer mechanism) of the ink material from the polymer domains of the stamp onto the receptor substrate (where the ink reacts) can create a concentration gradient, which then draws additional ink onto the surface of the receptor substrate from the inked polymer domains.
Upon completion of the ink transfer to the receptor substrate, the stamp is then removed leaving the ink chemical material 66 as a pattern 70 on portions of the receptor substrate 68 corresponding to the inked polymer domains 50 on the stamping surface 64 of the stamp 26 and exposed portions 72 of the substrate, as shown in FIGS. 18 and 18A. In some embodiments, the ink chemical material is processed to form a self-assembled monolayer (SAM) on the surface of the receptor substrate 68. The stamp 26 may then be re-inked, if needed, for further stamping of the same or another receptor substrate.
The ink pattern 70 on the receptor substrate 68 has identical or substantially identical resolution to the pattern of the inked polymer domains on the stamping surface 64 of the stamp 26. The patterned stamp 26 can be used to produce features (pattern 70) on the receptor substrate that are sub-lithographic, for example, a thickness of about 1-10 angstroms, and lateral width (w.sub.p) that corresponds to the dimension (width (w.sub.pd)) of the pattern of the "inked" polymer domains on the stamping surface 64 of the stamp 26 (FIG. 17).
In the embodiment illustrated in FIGS. 18 and 18A, the ink (e.g., SAM) pattern 70 formed using the stamp 26 having a stamping surface 64 composed of a lamellar array of polymer domains defines a linear pattern of fine, parallel lines of nanometer-scale to sublithographic dimensions about 5-50 nm wide and several microns in length (e.g., about 10-4000 .mu.m), and a center-to-center pitch of about 10-100 nm. Stamp 26''' (FIGS. 11 and 11A), for example, also provides a stamping surface having parallel lines of polymer domains. In other embodiments, the stamp can have a stamping surface composed of a cylindrical array of polymer domains as described, for example, with respect to stamps 26' and 26'' (FIGS. 9-10A).
After applying the ink pattern on the receptor substrate, further processing may be conducted as desired.
For example, the inked pattern 70 of the stamped regions or elements 66 shown in FIG. 18A, can be used to guide the formation of etch masks to pattern portions of the underlying receptor substrate 68.
In one embodiment, the inked pattern 70 of elements 66 can be formed as a chemically differentiated surface in a pattern of hydrophobic and hydrophilic materials (or neutral and preferential-wetting materials), which can be used as a template to guide and chemically control the self-assembly of a block copolymer to match the template pattern of elements on the receptor substrate. For example, as depicted in FIGS. 18 and 18A, using a template such as stamp 26 (FIG. 16), an ink material that will form a SAM composed of a hydrophobic material such as octadecylthiol (ODT) can be transferred as a pattern 70 of elements 66 (e.g., parallel lines) onto a receptor substrate 68 that has an epoxide surface. Unstamped regions 72 of the substrate adjacent to the line elements 66 can be made hydrophilic by reacting the exposed substrate with a material such as 11-hydroxyundecylthiol. The pattern of hydrophobic material line elements 66 and the hydrophilic substrate regions 72 on the substrate can then be used as a template for guided self-assembly of a block copolymer material.
Referring to FIG. 19, a block copolymer material having domains that are selectively wetting to the template (seed layer) formed by the hydrophobic line elements 66 and the hydrophilic substrate regions 72, can be deposited as a film 74 onto the substrate. The copolymer film 74 can then be annealed to form a self-assembled polymer film 76 with lamellae 78, 80 registered to the hydrophobic and hydrophilic regions 66, 72 of the template below, as illustrated in FIG. 20. Then, as shown in FIG. 21, one of the polymer domains (e.g., lamellae 80) of the self-assembled film 76 can be selectively removed and the resulting film 82 can be used as a mask to etch (arrows .dwnarw..dwnarw.) the underlying substrate 68, for example, by a non-selective RIE etching process, to delineate a series of openings 84 (shown in phantom). Further processing can then be performed as desired, such as filling the openings 84 with a material 86 as shown in FIG. 22, for example, with a dielectric material to separate active areas, or with a conductive material such as a metal or other conductive material to form nanowire channel arrays for transistor channels, semiconductor capacitors, and other structures that can extend to an active area or element in the substrate or an underlayer. Further processing can then be performed as desired. The self-assembly of block copolymers to an underlying chemical pattern is rapid relative to other methods of "top-down" or graphoepitaxy ordering and registration.
In other embodiments, the inked pattern of elements 66 can be used as a template for selective deposition of a hydrophobic or hydrophilic material onto either the inked elements 66 or the unstamped areas 72 of the substrate.
For example, referring to FIG. 23, the inked pattern of elements 66' can be used as an "anti-seed" guide or template for the global application and selective deposition of a material 74' that is chemically different from the stamped regions (elements) 66' onto adjacent exposed regions 72' of the substrate 68'. For example, elements 66' composed of a hydrophobic ink material (e.g., octadecyl thiol) can be stamped onto the substrate 68', and a hydrophilic material 74' (e.g., an oxide) can be selectively applied to the non-stamped substrate areas 72', for example, by a vapor deposition, resulting in the structure shown in FIG. 23. The resulting film 82' can be used as a mask to etch (arrows .dwnarw..dwnarw.) the underlying substrate 68' to form openings 84', as depicted in FIG. 24.
In another embodiment, as shown in FIG. 25, elements 66'' can be used as a seed material for the selective deposition of additional material 74'' to increase the thickness and/or hardness of the elements 66'' and produce a hard mask for etching the substrate 68''. For example, elements 66'' can be formed from acetylenic hydrocarbons or esters of acetylenic carboxylates with hydrocarbon conjugates (e.g., hexylpropynoate ester), with subsequent selective deposition of an inorganic material 74'' such as silicon oxide to increase the thickness and/or hardness of the elements 66''. In another example, a material 74'' such as silicon nitride can be selectively deposited onto the elements 66'' by ALD methods to form a hardmask 82'' composed, for example, of a series of lines according to the pattern of the elements 66''. In other embodiments, elements 66'' can be formed as a seed layer from an ink material having a functional group on its tail end (e.g., ink chemical with a bromine functional group) that will selectively initiate polymer growth, and an atom transfer radical polymerization (ATRP) can then be conducted to add additional polymer material 74'' to increase the thickness and/or hardness of the elements 66'' and produce a hard mask for etching openings 84''. The hardmask 82'' can be then used, for example, to mask the etch of the underlying substrate 68'' (e.g., film stack, etc.) to form openings 84'', as shown in FIG. 26.
Another embodiment of the invention illustrated in FIGS. 27-32, utilizes chemical patterning of a substrate to direct self-assembly of a block copolymer. In some embodiments, the process utilizes a stamp/template 88 that is formed with transparent sections 90, non-transparent sections 92, and a stamping surface 94. The transparent sections 90 are composed of a material that is substantially transparent to UV or DUV radiation in order to allow light to pass therethrough, for example, glass (e.g., quartz (SiO.sub.2)), calcium fluoride (CaF.sub.2), diamond, or a transparent plastic or polymeric material, and the non-transparent (opaque) sections 92 can be composed, for example, of a elastomeric polymer material such as poly(dimethylsiloxane) (PDMS).
As shown in FIG. 27, the stamping surface 94 can be coated with a thin film 96 of a polymerizable neutral wetting material that exhibits non-preferential or neutral wetting toward the blocks of a block copolymer, such as a random block copolymer (e.g., PS-r-PMMA). The template 88 can then be pressed (arrow .dwnarw.) onto a receptor substrate 68 (e.g., a preferential wetting material such as silicon (with native oxide), oxide, etc.) as shown in FIG. 28 to transfer the polymer material 96 onto the substrate 68. Then, as illustrated in FIG. 29, a radiation source (e.g., UV or DUV radiation) can then be transmitted (arrows .dwnarw..dwnarw.) through the transparent sections 90 of the stamp/template 88 to photolytically crosslink discrete sections 98 of the polymer material 96 on the substrate 68. The template 88 can then be removed from contact with the receptor substrate 68, leaving the crosslinked polymer sections 98 and non-crosslinked polymer material 100, as depicted in FIG. 30.
Further processing can then be conducted as desired. For example, as shown in FIG. 31, the non-crosslinked polymer material 100 can be removed, for example, by wet processing by a chemical dissolution process using a solvent to expose sections 102 of the receptor substrate 68, resulting in discrete neutral wetting sections 98 composed of the crosslinked polymer material (e.g., crosslinked random copolymer) and preferential wetting sections 102 composed of the exposed receptor substrate (e.g., oxide). A block copolymer material can then be cast or spin-coated onto the chemically differentiated surface and annealed to form a self-assembled block copolymer layer 104. As illustrated in FIG. 32, the annealed block copolymer film 104 will register to the differing wetting patterns (98, 102) on the receptor substrate 68, for example, to form lamellae 106, 108 as shown. The resulting film 104 can be further processed, for example, to selectively remove one of the polymer blocks to produce a hard mask for use in a dry etch to transfer the pattern into the underlying substrate material.
Patterning a substrate using conventional lithographic techniques has been hampered by difficulties such as high costs and/or incompatibility with high throughput production methods. With embodiments of the present invention, a stamp can be prepared using conventional lithography (to form the trenches) but, because the stamp can be used repeatedly to pattern multiple substrates, the production cost per stamped substrate is reduced. In addition, the use of the stamped pattern (e.g., SAM ink pattern 70) for chemically controlling the formation of a self-assembled block copolymer film, can subsequently provide an etch mask on a nanoscale level that can be prepared more inexpensively than by electron beam lithography or EUV photolithography. The feature sizes produced and accessible by this invention cannot be prepared by conventional photolithography.
In another embodiment of the invention illustrated in FIGS. 33-60A, the ordering of a self-assembling block copolymer material (e.g., film) is induced and directed by overlaying a topographically flat stamp that is chemically patterned on its surface. The chemically patterned stamp overlaid on a BCP film cast onto a substrate that has been globally modified to be equally wetting to both blocks of the BCP will direct self-assembly of the BCP film to match the pattern on the stamp. The present embodiment of the invention achieves a pattern transfer to a block copolymer (BCP) without leaving a physically formed impression in the substrate and without a transfer of material to the substrate or the BCP material.
FIG. 33 illustrates a substrate (generally 110) to be patterned. The substrate 110 can be composed of a base material 112, which can be, for example, silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, among other material. As shown, a non-preferential or neutral wetting material 114 (equal affinity for blocks of the copolymer) is formed over the base material.
The neutral wetting material 114 can be formed, for example, by blanket coating a random copolymer material onto the base material 112 by casting or spin-coating, and fixing the polymer material in place by grafting (on an oxide substrate) or by thermally or photolytically crosslinking (any surface). For example, a material that is neutral wetting to a PS-b-PMMA block copolymer can be formed from a thin film of a photo-crosslinkable random PS:PMMA copolymer, for example, PS-r-PMMA (60% PS) grafted to an oxide substrate.
As previously described, a neutral wetting layer can also be formed on a base material 112 such as an oxide by grafting and heating a random copolymer of polystyrene (PS) and polymethacrylate (PMMA) with a few % (e.g., less than or equal to about 5%) hydroxyl group(s) (e.g., 2-hydroxyethyl methacrylate (P(S-r-MMA-r-HEMA)) on the base material. In another embodiment, a surface that is neutral wetting to PS-b-PMMA can also be prepared by spin coating and crosslinking a benzocyclobutene- or azidomethylstyrene-functionalized random copolymer of styrene and methyl methacrylate (e.g., poly(styrene-r-benzocyclobutene-r-methyl methacrylate (PS-r-PMMA-r-BCB)) on the base material.
In yet another embodiment, a base material 112 of silicon (with native oxide) can be treated by a fluoride ion etch (e.g., with aqueous HF, buffered HF or NH.sub.4F, HF vapor treatment, etc.) or a hydrogen plasma etch as previously described, to form hydrogen-terminated silicon, which is neutral wetting to a block copolymer material such as PS-b-PMMA. An H-terminated silicon material 114 can be further processed by grafting of a random copolymer such as PS-r-PMMA onto the material 114 (e.g., in situ free radical polymerization of styrene and methyl methacrylate with a di-olefinic linker).
Referring now to FIG. 34, a lamellar- or cylindrical-phase block copolymer material 116 is then cast as a film onto the neutral wetting material 114 on the substrate 110. The block copolymer material 116 has an inherent pitch at or about L.sub.o (or a ternary blend of block copolymer and homopolymers blended to have a pitch at or about L.sub.o). The block copolymer material 116 can be deposited by spin casting or spin-coating from a dilute solution (e.g., about 0.25-2 wt % solution) of the copolymer in an organic solvent such as dichloroethane (CH.sub.2Cl.sub.2) or toluene, for example. The thickness (t) of the block copolymer material 116 is at or about L.sub.o.
The block copolymer material 116 is then induced to self-assemble by contact with a stamp, which, according to the invention, is topographically flat and chemically patterned on its surface.
FIGS. 35-39B illustrate an embodiment of a process for forming a master template for forming a stamp for use in inducing self-assembly of a block copolymer material on a substrate. The master template (generally 118), which is topographically flat, is prepared by forming a pattern of chemically differentiated areas on the surface of a base substrate 120. The base substrate 120 can be composed, for example, of silicon dioxide or gold.
Referring to FIG. 35, in one embodiment, a hydrophilic material 122 on the base substrate 120 can be micropatterned to form the chemical master template 118. The hydrophilic material 122 can be, for example, silicon (with native oxide), oxide (e.g., silicon oxide, SiO.sub.x), indium tin oxide (ITO), silicon nitride, silicon oxycarbide, silicon oxynitride. In another embodiment, the hydrophilic material 122 can be composed of a metal, for example, gold, silver, copper, palladium or platinum, on the base substrate 122 and an overlying SAM of an alkane thiol such as hydroxyundecylthiol (HUT), or other hydrophilic alkane thiol. The hydrophilic material 122 can be formed on the base substrate 120 as a monolayer (SAM) of about 0.5-5 nm thick.
As shown in FIG. 36, a layer of resist material 124 can be formed on the hydrophilic material 122, and then developed in a desired pattern and removed (FIGS. 37-37B) to expose portions of the hydrophilic material 122. The resist material 124 can be patterned using a lithographic tool having an exposure system capable of patterning at the scale of at or about L.sub.o (10-100 nm). The material for the resist 124 is selected based on the required sensitivity and compatibility with the exposure system that is used. Such exposure systems include, for example, extreme ultraviolet (EUV) lithography, electron beam (e-beam) lithography, immersion lithography, and proximity X-rays as known and used in the art. The pattern formed in the resist material 124 can be composed, for example, of a series of linear openings (stripes) 126, as shown in FIGS. 37-37B.
Referring now to FIGS. 38-38B, a hydrophobic material 128 can then be deposited onto the exposed sections of the hydrophilic material 122 using the resist 124 as a mask. The hydrophobic material 128 can be, for example, an alkyl trialkoxysilane such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane and n-propyltriethoxysilane; an alkylthiolate such as dodecanethiol or octadecanethiol (ODT); among others. The hydrophobic material 128 can be deposited as a monolayer (e.g., self-assembled monolayer (SAM)) of about 0.5-5 nm thick.
As illustrated in FIGS. 39-39B, the resist 124 can then be stripped to expose the previously masked portions of the hydrophilic material 122. The resulting master template 118 now bears a chemically patterned surface 130 composed of lines of the hydrophobic material 128 (e.g., alkyl trialkoxysilane) adjacent to lines of the hydrophilic material 122 (e.g., oxide). For example, a master template 118 can be prepared with a surface patterned with hydrophobic SAM 128 of octadecanethiol (ODT) adjacent to a hydrophilic SAM 122 of 11-hydroxyundecane-1-thiol (HUT), as described by van Poll et al., Angew. Chem. Int. Ed.: 46, 6634-6637 (2007).
The hydrophilic 122 and hydrophobic 128 material elements on the surface of the master template 118 are dimensioned with a width (w.sub.1) that matches or substantially matches the inherent self-assembled structure (e.g., L.sub.o value) of the block copolymer material (BCP) 116 that is deposited on the substrate 110 (FIG. 34) in those sections of the polymer material 116 where self-assembly into perpendicular-oriented structures (e.g., lamellae, cylinders) is desired. In areas of the polymer material 116 where a lack of formation of perpendicular-oriented elements is desired, a hydrophobic region 128a (FIG. 39) (or hydrophilic region) can be formed with dimensions (i.e., width (w.sub.2)) that are greater than the L.sub.o value of the BCP material 116.
Referring to FIG. 40, in another embodiment of forming a chemical master template 118', a hydrophobic material 128' (e.g., an alkyl trialkoxysilane) can be blanket deposited onto a base substrate 120' such as silicon or silicon oxide, for example. The hydrophobic material 128' can then be patterned and removed using a resist 124' as a mask as shown in FIGS. 41-41B, to expose portions of the base substrate 120'. Then, as depicted in FIGS. 42-42B, the exposed base substrate 120' can then be selectively oxidized to form a hydrophilic monolayer (SAM) 122', or in other embodiments, a hydrophilic material (e.g., oxide, SiN, alkane thiol, etc.) can be deposited onto the exposed base substrate 120'. Then, as illustrated in FIGS. 43-43B, the resist 124' can be stripped, with the surface 130' of the master template 118' now bearing a pattern of lines of the hydrophobic material 128a' adjacent to lines of the hydrophilic material 122'.
Using the master template 118 (e.g., FIG. 39) as a guide, a stamp (generally 132) is then formed with hydrophilic and hydrophobic elements in a mirror image of the pattern of elements on the master template surface. The chemically differentiated surface of the stamp 132 can then be used to direct self-assembly of the block copolymer material 116 on the substrate 110 (FIG. 33).
Referring to FIGS. 44-44B, in some embodiments, a soft, flexible or rubbery material 134 such as a polydimethylsiloxane (PDMS) elastomer or other elastomeric, crosslinkable polymer material (e.g., silicones, polyurethanes, etc.) is deposited onto the chemically patterned surface 130 of the master template 118 to form a stamp 132. The unmodified surface of a PDMS material is hydrophobic. To modify the surface of the stamp, the polymer material can be prepared as a mixture of the elastomeric polymer with different functional small molecules, e.g., a hydrophilic molecule 136a and a hydrophobic molecule 136b. As illustrated in FIGS. 45-45B, preferential wetting by molecules 136a, 136b over the polymer material 133 against the master template 117 (arrow .dwnarw.) directs the migration and preferential accumulation (self-assembly) of the small molecules 136a, 136b at the surface 138 of the polymer stamp 132 in response to the hydrophilic 122 and hydrophobic 128 regions or elements on the functionalized surface 130 of the master template 118. During curing, a crosslinking agent of the polymer material 134 reacts with the small molecules 136a, 136b and with functional groups of the polymer to "freeze" the pattern of small hydrophilic and hydrophobic molecules 136a, 136b into the polymer (e.g., PDMS elastomer) stamp 132 against the hydrophilic 122 and hydrophobic 128 surfaces, respectfully, of the master template 118. The resulting stamp 132 has a flat surface 138 that bears a pattern of sub-micrometer features of different chemical functionalities (hydrophilic 136a and hydrophobic 136b) that replicates the pattern of hydrophilic (122) and hydrophobic (128) elements on the master template 118.
For example, a PDMS elastomer material, such as SYLGARD.RTM. 184 (Dow Corning), can prepared as a mixture of PDMS and small functional hydrophobic and hydrophilic molecules (e.g., vinyl-terminated molecules with different head groups), as described by van Poll et al., Angew. Chem. Int. Ed.: 46, 6634-6637 (2007). Examples of small hydrophobic molecules include perfluorinated alkenes (e.g., 1H, 1H, 2H-perfluorodecene), vinyl esters (e.g., alky 2-bromo-2-methyl propionic acid ester), and hydrocarbon alkenes (e.g., 11-undecene), among others. Examples of small hydrophilic molecules include oligo(ethylene glycol) methacrylate (OEGMA), undec-11-enyl hexaethylene glycol monomethyl ether (PEG.sub.6 derivative), and vinylic (mono- or divinyl) poly(ethylene glycol), among others. The PDMS can be mixed, for example, with equimolar amounts of a small amount of the small molecules, generally less than about 5 wt % (e.g., about 2-3 wt %). During curing, the molecules will self-assemble according to the functionalized monolayer on the template surface and react with the PDMS backbone by a hydrosilylation reaction during curing.
Referring now to FIGS. 46 and 47 and 47A, the now chemically functionalized polymer stamp 132 can then be removed (arrows .uparw..uparw.) from the surface 130 of the master template 118. For example, a solvent such as water (arrows .dwnarw..dwnarw.) can be applied or the stamp/template complex soaked in the solvent, which will permeate and swell the stamp body 132 and weaken the interfacial bonds on the hydrophilic areas, and the stamp can then be peeled from the surface of the master template, as shown in FIG. 46.
As illustrated, the surface 138 of the stamp 132 is chemically differentiated according to the pattern of hydrophilic and hydrophobic elements on the master template 118. The surface of the stamp 132 is composed of hydrophilic lines 136a that are preferential wetting to one domain of the block copolymer (e.g., PMMA) and hydrophobic lines 136b that are preferential wetting to the other block of the block copolymer (e.g., PS). As on the master template, the dimensions (i.e., width (w.sub.1)) of the lines 136a, 136b match or substantially match the dimensions (i.e., w.sub.1) of the hydrophilic lines 122 and hydrophobic lines 128, respectively, on the surface 130 of the master template 118, as well as the L.sub.o value of the block copolymer material (BCP) 116 on the substrate 110 (FIG. 34). The stamp 132 includes a hydrophobic section 136b.sub.1 that has a width (w.sub.2) that corresponds to the dimensions (w.sub.2) of the hydrophobic section 128a on the chemical master 118, which is greater than the BCP L.sub.o value.
Referring now to FIG. 48, the chemically patterned surface 138 of the stamp 118 is now brought into contact with a surface 140 of the block copolymer material 116 situated on the neutral wetting material 114 on the substrate 110, for example, by pressing the stamp surface 138 onto the block copolymer material (FIG. 49). The rubbery or flexible body of the stamp 132 allows the stamp to conform to the topography of the block copolymer material 116. As depicted in FIG. 50, the block copolymer material 116 is then annealed (arrows .dwnarw..dwnarw.) while in contact with the chemically patterned stamp surface to form a self-assembled polymer material 142.
The chemical pattern of hydrophilic and hydrophobic lines 136a, 136b on the surface of the stamp 132 will direct the self-assembly and perpendicular ordering of the polymer domains of the block copolymer material 116 in regions in which the pitch (w.sub.1) of the elements 136a, 136b on the stamp surface is at or about the inherent pitch or L.sub.o value of the block copolymer material 116.
For example, as depicted in FIGS. 50 and 50A, in the use of a lamellar-phase block copolymer (e.g., PS-b-PMMA), during the anneal, the PMMA block will align with and preferentially wet the hydrophilic material (lines) 136a on the surface of the stamp 132 and the PS block will align with and preferentially wet the hydrophobic material (lines) 136b to form lines of PMMA lamella 144a and PS lamella 144b. The neutral wetting material 114 on the substrate 110 ensures that the perpendicular-oriented lamellae extend completely through the self-assembled polymer material 142 from the interface with the neutral wetting material 114 to the surface 138 of the stamp 132 on those lines 136a, 136b that have a pitch (w.sub.1) that is at or about the L.sub.o value of the block copolymer material.
In regions of the substrate 110 where subsequent patterning (using the self-assembled BCP layer as a mask) is not desired, the contact of the block copolymer material with a stamp region (e.g., 136b.sub.1) which has a width (w.sub.2) that is greater than the L.sub.o value of the block copolymer and is preferential wetting to only one domain of the block copolymer, will result in the formation of parallel-oriented lamellae 144a.sub.1, 144b.sub.1 for a corresponding width (w.sub.2) within the self-assembly polymer material 142.
Referring now to FIGS. 51 and 52, the stamp 132 is then removed from contact (.uparw..uparw.) with the surface of the self-assembled polymer layer 142. To break the adhesive forces (e.g., Van der Waals forces) and lift the stamp from the polymer surface, in some embodiments, the stamp/solvent complex can be soaked in a solvent (e.g., water, isopropyl alcohol, acetic acid, etc.) that will permeate and swell the body of the stamp 132 (e.g., PDMS) but not the polymer domains 144a, 144b of the annealed, self-assembled polymer material 142. In some embodiments, a solvent can be used that also swells one but not both of the polymer domains of the self-assembled polymer material, e.g., the polymer domain that is subsequently selectively removed (e.g., PMMA lamellae 144a). After separation and removal of the stamp 132 from the self-assembled polymer material, the stamp 132 can then be re-used for further templating on another area or substrate bearing a BCP material layer.
The self-assembled polymer material 142 can then be developed to selectively remove one of the polymer domains (e.g., PMMA lamellae 144a) to produce a mask 146 composed of the remaining polymer domain (e.g., PS lamellae 144b) with openings 148 in the desired pattern of lines exposing the substrate 112, as shown in FIGS. 53 and 53A. The underlying substrate 112 can then be etched (arrows .dwnarw..dwnarw.) using the mask 146, as shown in FIGS. 54 and 54A, to form openings 150 to an underlying active area or element 152. The residual mask 146 (i.e., PS lamellae 144b, 144b.sub.1 and PMMA lamella 144a) can then be removed and the openings 150 filled with a material 154, e.g., a metal or conductive alloy such as Cu, Al, W, Si, and Ti.sub.3N.sub.4, among others, as shown in FIGS. 55 and 55A to form arrays of parallel conductive lines 154 having a width over a range of about 5-50 nm, to the underlying active area, contact, or conductive line 152. Further processing can be conducted as desired.
In other embodiments, the block copolymer material 116 can be cylindrical-phase block copolymer (BCP) on a neutral wetting layer 114 (FIG. 34). Referring to FIGS. 56 and 56B, a master template 118'' can be formed with "dots" of a hydrophilic material 122'' (e.g., oxide) surrounded by a hydrophobic material 128'' (e.g., an alkyl trialkoxysilane). The dots of the hydrophilic material 122'' are formed in regions where perpendicular cylinders in the BCP material are desired, and have a diameter (d) and pitch (p) equal to the L.sub.o value of the cylindrical-phase block copolymer (BCP) material or within about 10% or less than the L.sub.o value. Other regions (128'') of the master template 118'' where perpendicular cylinders are not desired are chemically patterned to be hydrophobic.
As shown in FIGS. 57 and 57A, a polymer material (e.g., PDMS) composed of hydrophilic 136a'' and hydrophobic 136b'' components (e.g., molecules) is formed and cured (arrows .dwnarw..dwnarw.) on the master template 118''. Upon curing, the hydrophilic components 136a'' of the stamp material 134'' align with the hydrophilic dots 122'' and the hydrophobic components 136b'' align with the hydrophobic regions 128'' on the master template 118''. The cured stamp 132'' is then removed from the master template 118'' and applied to a cylindrical-phase block copolymer material (e.g., 116 in FIG. 34), which is annealed while in contact with the stamp (FIGS. 58 and 58A (arrow .dwnarw.).
Upon annealing, the cylindrical-phase BCP (116), will self-assemble into perpendicular-oriented cylinders 156'' composed of one polymer block (e.g., PMMA) in response to and aligned with the hydrophilic dots 136a'' on the surface 138'' of the stamp 132'', surrounded by a matrix 158'' of the other polymer block (e.g., PS) in response to the hydrophobic areas 136b'' on the stamp surface. In response to areas where the hydrophobic area 136b'' has a width (w'') that is greater than or equal to 1.5*L.sub.o, the block copolymer material will self-assemble to form one or more lines of half-cylinders 156a'', which are oriented parallel to and in contact with the neutral wetting layer 114''. The number of lines of half-cylinders 156a'' can vary according to the width (w''), for example, a single line of a parallel half-cylinder will form from a block copolymer (L.sub.o=50 nm) where the hydrophobic area 136b'' has a width (w'') of about 70-80 nm. The stamp 132'' is then removed (arrow .uparw.) from the surface of the annealed and self-assembled block copolymer material 142''.
As depicted in FIG. 59, the cylinders 156'' (e.g., PMMA block) can then be selectively removed to form a mask 146'' composed of cylindrical openings 148'' within the matrix 158'' of the other polymer block (e.g., of PS) to expose the base substrate 112''. The substrate 112'' can then be etched using the mask 146'' to form cylindrical openings 150'' (shown in phantom) to active areas 152'' in the substrate 112''. The etched openings 150'' can be filled with an appropriate material 154'' to form contacts to the underlying active areas 152'' (e.g., conductive lines), as depicted in FIGS. 60 and 60A. The substrate can then be additionally processed as needed.
The present embodiment of the invention of overlying a chemically patterned stamp to direct self-assembly of a BCP film eliminates the need for forming a substrate template pattern, which requires the use of a patterning technique such as EUV lithography or other sub-lithographic patterning techniques to physically or chemically pattern the surface of a substrate, e.g., with chemical stripes (chemical templating), each stripe being preferentially wetted by the alternate blocks of a block copolymer to cause polymer domains to orient themselves above the preferred stripes and perpendicular to the surface. The present embodiment of a chemically patterned stamp provides a low cost and re-usable method to provide registered self-assembled block copolymers with long-range order without the need for patterning a substrate.
The use of a chemically patterned stamp to direct ordering of a self-assembling block copolymer material does not require patterning of the substrate to form a topographically varied surface as required by graphoepitaxial self-assembly, which significantly reduces costs. Also, only an original master template requires patterning using sub-lithographic tools (e.g., EUV, e-beam, etc.), and at least two levels of amplification result including the fabrication of multiple stamps from a single master template, and the ability to use each stamp multiple times to direct ordering of BCP materials. As a result, the cost of preparing the master template is significantly amortized. In addition, since the stamp is topographically flat, problems of lift-off from a self-assembled polymer film are minimized in conjunction with the surface areas in contact, which provides a significant advantage over nanoimprint lithography. Long-range order and defectivity of a self-assembled block copolymer film is also improved as the stamp templates and directs the proper order in each region of the film. By comparison, graphoepitaxy requires force fields generated from topographic features to impose order from a distance.
As depicted in FIG. 61, the present stamp embodiments can be used to form a variety of geometries for integrated circuit layouts 154, including periodic conductive lines 156 and contacts 158, lines with bends 160, isolated lines and contacts, etc., as needed for the circuit design. Dies comprising the conductive lines and contacts can be incorporated into a circuit module, device or electronic system, including processor systems.
Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement that is calculated to achieve the same purpose may be substituted for the specific embodiments shown. This application is intended to cover any adaptations or variations that operate according to the principles of the invention as described. Therefore, it is intended that this invention be limited only by the claims and the equivalents thereof. The disclosures of patents, references and publications cited in the application are incorporated by reference herein.
Previous Patent US 10,005,307 | Next Patent US 10,005,309