US009869931B2  c12)  United States Patent  Hatakeyama  (IO)  Patent No.:  US 9,869,931 B2  (45)  Date of Patent:  Jan.16,2018  (54)  RESIST COMPOSITION AND PATTERNING  PROCESS  (71)  Applicant:  Shin-Etsu Chemical Co., Ltd.,  Tokyo  (JP)  (72)  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 0 days.  (21)  Appl. No.:  15/016,920  Feb. 5, 2016  (22)  Filed:  (51)  Int. Cl.  (52)  U.S. Cl.  CPC ..........  G03F  710397  (2013.01);  G03F  710045  (2013.01);  G03F  710046  (2013.01);  G03F  710392  (2013.01);  G03F  712004  (2013.01);  G03F  712059  (2013.01);  YJ0S 522/904  (2013.01)  ( 58)  Field of Classification Search  CPC .... G03F 7/0397; G03F 7/2004; G03F 7/2059;  G03F 7/0392; G03F 7/0045; G03F  7/0046; Yl0S 522/904  See application file for complete search history.  To a resist composition comprising a polymer comprising  recurring units having an acid labile group and an acid  generator is added a metal-acid complex. The metal is Ce,  Cu, Zn, Fe, In,  Y,  Yb, Sn, Tm, Sc, Ni, Nd, Hf, Zr, Ti, La, Ag,  Ba, Ho, Tb, Lu, Eu, Dy, Gd, Rb, Sr or Cs. The acid is a  fluoroalkylsulfonic acid, fluorinated arylsulfonic acid, fluo› rinated tetraphenylboric acid, fluoroalkylsulfonimidic acid  or fluoroalkylsulfonemethide acid. Due to a high contrast of  alkaline dissolution rate before and after exposure, high  resolution, high sensitivity, and controlled acid diffusion  rate, the composition forms a pattern with satisfactory  profile and minimal line edge roughness.  * cited by examiner  Primary Examiner  - Cynthia Hamilton  (74)  Attorney, Agent, or Firm  - Westerman, Hattori,  Daniels & Adrian, LLP  Hinsberg et al., "Extendibility of Chemically Amplified Resists :  Another Brick Wall?", Advances in Resist Technology and Process› ing XX, 2003, Proceedings of SPIE vol. 5039, pp. 1-14, (14 pages).  Kishikawa et al., "Assessment of trade-off between resist resolution  and sensitivity for optimization of hyper-NA immersion lithogra› phy", Optical Mlcrolfthography XX, 2007, Proceedings of SPIE  vol. 6520, pp. 65203L-l-65203L-9, (10 pages).  Office Action dated Oct. 13, 2016, issued in counterpart Taiwanese  application No. 105103904 (6 pages).  US 2016/0231652 Al  Aug. 11, 2016  14 Claims, No Drawings  (56)  References Cited  U.S. PATENT DOCUMENTS  (57)  ABSTRACT  (30)  Foreign Application Priority Data  (65)  Prior Publication Data  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  Feb. 9, 2015  Aug. 12, 2015  Nov. 26, 2015  (JP) ................................. 2015-023149  (JP) ................................. 2015-159402  (JP) ................................. 2015-230189  G03F  71039  G03F  7120  G03F  7132  G03F  7116  G03F  71004  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  JP  JP  JP  JP  JP  2001-329228  2006-178317  2009-237150  2010-152136 A  2013-25211 A  11/2001  7/2006  10/2009  7/2010  2/2013  2012/0202153  Al*  8/2012 Hatakeyama ......... G03F 7/0045  430/283.1  2012/0208125  Al*  8/2012 Hatakeyama ......... G03F 7/0043  430/281.1  2012/0208127 Al*  8/2012 Hatakeyama ........... G03F 7/038  430/283.1  2013/0029270 Al  1/2013 Hatakeyama  2013/0224652 Al*  8/2013 Bass ..................... G03F 7/0042  430/270.1  2015/0099228 Al*  4/2015 Hatakeyama ........... G03F 7/039  430/270.1  2009/0317742 Al* 12/2009 Toriumi ................ G03F 7/0042  430/270.1  2012/0058429 Al*  3/2012 Nishino ................ G03F 7/0045  430/283.1 