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# 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 

## (65) Prior Publication Data 

## US 2009/0176173 Al Jul. 9, 2009 

(51) Int. Cl. 

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(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. 

## (56) References Cited 

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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 

## U.S. PATENT DOCUMENTS 

## OTHER PUBLICATIONS 

(Continued) 

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# (IO) Patent No.: US 7,655,379 B2 

# (45) Date of Patent: *Feb. 2, 2010 

## (57) ABSTRACT 

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, 

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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 

## 24 Claims, 1 Drawing Sheet 

