(IO)  Patent No.:  US 7,655,379 B2  (45)  Date of Patent:  *Feb. 2, 2010  c12)  United States Patent  Glodde et al.  (54)  IONIC, ORGANIC PHOTOACID  GENERATORS FOR DUV, MUV AND  OPTICAL LITHOGRAPHY BASED ON  PERACEPTOR-SUBSTITUTED AROMATIC  ANIONS  (75)  Inventors:  Martin Glodde,  Mahawah, NJ (US);  Sen Liu,  Highland Park, NJ (US);  Irene  Y. Popova,  Beacon, NY (US)  (73)  Assignee:  International Business Machines  Corporation,  Armonk, NY (US)  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by  O  days.  This patent is subject to a terminal dis› claimer.  (21)  Appl. No.:  11/970,731  (22)  Filed:  Jan.8,2008  (51)  Int. Cl.  (52)  U.S. Cl.  ....................  430/270.1;  430/326; 430/313;  558/427; 558/432; 570/183; 570/187  (58)  Field of Classification Search  .............. 430/270.1,  430/326, 313; 549/70, 78; 558/432, 427;  570/183, 187  See application file for complete search history.  (Continued)  OTHER PUBLICATIONS  (56)  References Cited  U.S. PATENT DOCUMENTS  24 Claims, 1 Drawing Sheet  (57)  ABSTRACT  G03F 71004  (2006.01)  G03F 7130  (2006.01)  C07C 23108  (2006.01)  C07C 23118  (2006.01)  C07C 23134  (2006.01)  C07C 23144  (2006.01)  (65)  Prior Publication Data  US 2009/0176173 Al  Jul. 9, 2009  3,853,943  A  12/1974 Webster ...................... 558/432  6,093,753  A  7/2000 Takahashi .................... 522/25  6,908,722 B2  6/2005 Ebata et al. .............. 430/270.1  7,192,686 B2  3/2007 Meagley .................. 430/270.1  7,217,492 B2  5/2007 Yoneda et al. ........... 430/270.1  U.S. Appl. No. 11/970,827, filed Jan. 8, 2008, Martin Glodde.  Wallraff, et al., Lithographic Imaging Techniques ...  Chem. Rev.,  1999, 99, 1801-1821.  Primary Examiner-John  S Chu  (74)  Attorney, Agent, or Firm-The  Law Offices of Robert J.  Eichel burg  A photoacid generator compound p+ A-, comprises an  antenna group p+ comprising a cation that generates protons  upon interaction with light, and A- comprising a weakly  coordinating peracceptor-substituted aromatic anion that  does not contain fluorine or semi-metallic elements such as  boron. In one embodiment, such anions comprise the follow› ing compounds 4, 5, 6 and 7,  4  E  E  E  E  E  E  E  E  E  E  7  E  E  E  E  E  wherein E comprises an electron-withdrawing group and the  removal of one proton generates aromaticity. p+ comprises an  onium cation that decomposes into a proton and other com› ponents upon interaction with photons. p+ may comprise an  organic chalcogen onium cation or a halonium cation,  wherein the chalcogen onium cation in another embodiment  may comprises an oxonium, sulfonium, selenium, tellurium,  or onium cation, and the halonium cation may comprise an  iodonium, chlorine or bromine onium cation. A novel com› pound comprises TPS  CNS.  A photo lithographic formulation  comprises the photoacid generator in combination with a  photolithographic composition such as a photolithographic  polymer. The formulation, when on a substrate, is exposed to  optical lithographic radiation or ArF (193 nm) or KrF (248  nm) radiation, and developed. A product comprises an article  of manufacture made by the method of the invention.  US007655379B2 