US009360753B2  (10)  Patent No.:  US 9,360,753 B2  (45)  Date of Patent:  Jun.7,2016  c12)  United States Patent  Hatakeyama  (54)  RESIST COMPOSITION AND PATTERNING  PROCESS  (75)  Inventor:  Jun Hatakeyama,  Joetsu (JP)  (73)  Assignee:  SHIN-ETSU CHEMICAL CO., LTD.,  Tokyo (JP)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by 61 days.  (21)  Appl. No.:  13/542,014  (22)  Filed:  Jul. 5, 2012  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ............  G03F  710043  (2013.01);  G03F  710045  (2013.01);  G03F  710046  (2013.01);  G03F  710392  (2013.01);  G03F  710397  (2013.01)  ( 58)  Field of Classification Search  None  See application file for complete search history.  FOREIGN PATENT DOCUMENTS  OTHER PUBLICATIONS  (57)  ABSTRACT  (56)  References Cited  U.S. PATENT DOCUMENTS  (30)  Foreign Application Priority Data  (65)  Prior Publication Data  US 2013/0029270Al  Jan. 31, 2013  Jul. 25, 2011  (JP) ................................. 2011-161640  G03F  71004  G03F  71039  (2006.01)  (2006.01)  EP  0473547 Al  3/1992  EP  2090931 Al  8/2009  EP  2112554 A2  10/2009  JP  53126929  A  * 11/1978  JP  58202441 A  * 11/1983  JP  4-230645  A  8/1992  JP  9-309874  A  12/1997  JP  2000-327633  A  11/2000  JP  2000-336121  A  12/2000  JP  2001-281849 A  10/2001  JP  2001-329228  A  11/2001  JP  3429592 B2  7/2003  JP  2004-115630 A  4/2004  JP  2004-175755  A  6/2004  JP  2005-008766  A  1/2005  JP  2005-084365  A  3/2005  JP  2006-045311 A  2/2006  JP  2006-169302  A  6/2006  JP  2006-178317 A  7/2006  JP  3865048 B2  1/2007  JP  2007-114728 A  5/2007  JP  2007-297590  A  11/2007  JP  2008-095009  A  4/2008  (Continued)  2010/0316955 Al*  2011/0212391 Al  2011/0294070 Al  2012/0108043 Al  2012/0135349 Al  2012/0202153 Al  12/2010 Masunaga et al. ......... 430/285.1  9/2011 Masunaga et al.  12/2011 Hatakeyama et al.  5/2012 Hatakeyama et al.  5/2012 Hatakeyama et al.  8/2012 Hatakeyama  Translation of JP 53-126929. Nov. 6, 1978.*  Machine translation JP 2010-152136. Jul. 8, 2010.*  Translation JP 58-202441. Nov. 25, 1983.*  Bodner Research Web, Transition Metals, Purdue Chem, http://  chemed.chem.purdue.edu/genchem/topicreview/bp/chl2/trans.php,  access date Jan. 26, 2014. *  Kishikawa et al., "Assessment of trade-off between resist resolution  and sensitivity for optimization of hyper-NA immersion lithogra› phy", Proc. of SPIE, 2007, pp. 65203Ll-L9, vol. 6520.  Hinsberg et  al., "Extendibility of Chemically Amplified Resists:  Another Brick wall?", Proc. of SPIE, 2003, pp. 1-14, vol. 5039.  (Continued)  Primary Examiner  - Cynthia H Kelly  Assistant Examiner  - Alyssa L Cepluch  (74)  Attorney,  Agent,  or Firm  - Westerman,  Hattori,  Daniels  & Adrian, LLP  A resist composition is provided comprising a ( co )polymer  comprising recurring units of acid labile group-substituted  (meth)acrylic acid, styrenecarboxylic acid or vinylnaphtha› lenecarboxylic acid and/or recurring units having an acid  labile group-substituted phenolic hydroxyl group, an acid  generator, and a metal salt of carboxylic acid or a metal  complex of ~-diketone. Due to a high contrast of alkaline  dissolution rate before and after exposure, high resolution,  high sensitivity, and controlled acid diffusion rate, the com› position forms a pattern with satisfactory profile and minimal  LER.  8 Claims, No Drawings  5,415,749 A *  5/1995 Hamilton ...................... 204/492  5,879,851  A  3/1999 Takahashi et al.  5,989,776  A  *  11/1999 Felter et al. ................ 430/270.1  6,312,867 Bl  11/2001 Kinsho et al.  6,448,420 Bl  9/2002 Kinsho et al.  6,485,883 B2  11/2002 Kodama et al.  6,746,817 B2  6/2004 Takeda et  al.  7,449,277 B2  11/2008 Hatakeyama et al.  7,482,108 B2  1/2009 Matsumaru et al.  7,501,223 B2  3/2009 Takeda et  al.  7,537,880 B2  5/2009 Harada et al.  7,569,326 B2  8/2009 Ohsawaet al.  7,598,016 B2  10/2009 Kobayashi et al.  7,771,914 B2  8/2010 Hatakeyama et al.  8,288,076 B2  10/2012 Masunaga et al.  2004/0197702 Al*  10/2004 Shirakawa et al. ........ 430/270.1  2004/0260031 Al  12/2004 Takeda et al.  2007 /0231738 Al  10/2007 Kaneko et al.  2008/0090172 Al  4/2008 Hatakeyama et al.  2008/0096128 Al  4/2008 Takeda et al.  2008/0096131 Al  4/2008 Hatakeyama et al.  2008/0214011 Al  9/2008 Colburn et al.  2008/0241736 Al  10/2008 Kobayashi et al.  2008/0311507 Al  12/2008 Isono et al.  2009/0233223 Al *  9/2009 Tachibana et al . ......... 430/270.1  2009/0269696 Al *  10/2009 Ohsawaet al. ............ 430/270.1  2009/0274978 Al  11/2009 Ohashi et al.  2009/0317742 Al*  12/2009 Toriumi et al. ............ 430/270.1  2010/0035185 Al  2/2010 Hagiwara et al.  2010/0159392 Al  6/2010 Hatakeyama et al.  2010/0304302 Al  12/2010 Masunaga et al. 