(45)  Date of Patent:  Apr. 22, 2014  (IO)  Patent No.:  US 8,703,386 B2  c12)  United States Patent  Bass et al.  (54)  METAL PEROXO COMPOUNDS WITH  ORGANIC CO-LIGANDS FOR ELECTRON  BEAM, DEEP UV AND EXTREME UV  PHOTORESIST APPLICATIONS  (75)  Inventors:  John David Bass,  Union City, CA (US);  Ho-Cheol Kim,  San Jose, CA (US);  Robert Dennis Miller,  San Jose, CA  (US);  Qing Song,  San Jose, CA (US);  Linda Karin Sundberg,  Los Gatos, CA  (US);  Gregory Michael Wallraff,  San  Jose, CA (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 54 days.  (21)  Appl. No.:  13/405,587  (22)  Filed:  Feb.27,2012  (51)  Int. Cl.  (52)  U.S. Cl.  USPC ...............  430/270.1;  556/40; 556/42; 556/55  ( 58)  Field of Classification Search  USPC .............................. 430/270.1; 556/40, 42, 55  See application file for complete search history.  14 Claims, 15 Drawing Sheets  (57)  ABSTRACT  OTHER PUBLICATIONS  FOREIGN PATENT DOCUMENTS  (56)  References Cited  U.S. PATENT DOCUMENTS  (65)  Prior Publication Data  6,965,045 B2  7,077,895 B2  7,312,013 B2  2011/0045406 Al  11/2005 Jung et al.  7/2006 Akui et al.  12/2007 Takahashi et al.  2/2011 Keszler et al.  G03F 7100  G03F 71004  G03F 71029  C07C 49192  C07C 7100  (2006.01)  (2006.01)  (2006.01)  (2006.01)  (2006.01)  5,061,599  A  * 10/1991 Kudo eta!. ................ 430/270.1  5,178,989  A  *  1/1993 Heller et al. .................. 430/323  wherein x is an integer of 1 to 4, y is an integer of 1 to 4,  Ta(O$_{2}$)x(L’)y has a charge ofO to -3, C’ is a counterion having  a charge of +1 to +3, k is an integer of  O  to 3, L’ is an  oxidatively stable organic ligand having a charge of  O  to -4,  and L’ comprises an electron donating functional group  selected from the group consisting of carboxylates, alkox› ides, amines, amine oxides, phosphines, phosphine oxides,  arsine oxides, and combinations thereof. The compositions  have utility as high resolution photoresists.  Compositions are disclosed having the formula (3):  Primary Examiner  - Amanda C. Walke  (74)  Attorney, Agent, or Firm  - Michael R. Roberts  (Continued)  Bayot et al, "Vibrational Spectra ofEoght-Coordinate Niobium and  Tantalum Complexes with Peroxo Ligands:A Theorretcial Simula› tion", J. Inorganic Chem (2005), 4118-4123.*  Bayot et al, "Peroxo complexes of niobium (V) and tantalum (V)",  Coordination Chemistry Reviews 250 (2006), 2610-2626.*  Djordjevic et al, "Coordination Complexes of Niobium and Tanta› lum. Eight-coordinated Di- and Triperoxoniobates (V) and tantalates  (V) with Some Nitrogen and Oxygen Bidentate Ligands", Inorganic  Chemistry, vol. 7, No. 9 (1968), 1864-1868.*  Anderson, et al., "The SEMATECH Berkeley MET: extending EUV  learning down to 16nmhalfpitch", Proc. SPIE 7969, 79690R(201 l),  Feb. 28, 2011.  JP  61273539  12/1986  US008703386B2  US 2013/0224652 Al  Aug. 29, 2013  36 \  34,  22 ,  34 \  ~  \  ~  ... >~’\;’•  ..  •’8••••.•.:  \  -~  10---/  ~~~  ~  .... _-_---~~~~~----~~~~.,;.I  1) Optional PEB  2) Develop  l  ~32  )  (3), 