US010155921B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 , 155 , 921 B2 Cui ( 45 ) Date of Patent: * Dec. 18 , 2018 ( 54 ) REMOVAL COMPOSITION FOR (52 ) U . S . CI. SELECTIVELY REMOVING HARD MASK CPC .. .. CIID 11/ 0047 ( 2013 .01 ) ; B08B 3 /08 AND METHODS THEREOF ( 2013. 01 ); B08B 3 /10 ( 2013. 01 ) ; CIID 3 /2082 ( 2013. 01 ) ; ( 71 ) Applicant: EKC TECHNOLOGY INC , Hayward , ( Continued ) CA (US ) (58 ) Field of Classification Search ( 72 ) Inventor: Hua Cui, Castro Valley , CA (US ) CPC .. .. C11D 11 /0047 ; COOK 13 /00 (Continued ) ( 73 ) Assignees : E I DUPONT NE NEMOURS AND COMPANY, Wilmington , DE (US ) ; (56 ) References Cited EKC TECHNOLOGY INC . CA (US ) U . S . PATENT DOCUMENTS ( * ) Notice: Subject to any disclaimer , the term of this 6 , 319 , 801 B1 11 /2001 Wake et al . patent is extended or adjusted under 35 7 , 141 , 121 B2 11 /2006 Aoki U . S . C . 154 (b ) by 0 days . ( Continued ) This patent is subject to a terminal dis FOREIGN PATENT DOCUMENTS claimer . CN 103282549 A 9 / 2013 ( 21 ) Appl. No. : 15 / 028, 501 EP 0292057 Al 11 / 1988 ( 22 ) PCT Filed : Oct. 9 , 2014 (Continued ) ( 86 ) PCT No. : PCT/ US2014 / 059840 OTHER PUBLICATIONS $ 371 ( c ) ( 1 ) , International Search Report dated Feb . 18 , 2015 for International ( 2 ) Date : Apr. 11, 2016 Patent Application No . PCT/ US2014 /059840 . (Continued ) ( 87 ) PCT Pub . No. : W02015 /054460 Primary Examiner — Gregory E Webb PCT Pub . Date : Apr. 16 , 2015 (74 ) Attorney , Agent, or Firm — Simon L . Xu (65 ) Prior Publication Data ( 57 ) ABSTRACT The present disclosure relates to a removal composition for US 2016 /0312162 A1 Oct 27, 2016 selectively removing an hard mask consisting essentially of TiN , Tan , TiNxOy, TiW , W , Ti and alloys of Ti and W Related U . S . Application Data relative to low - k dielectric material from a semiconductor (63 ) Continuation of application No . substrate . The semiconductor substrate comprises a low - k PCT/ US2013 /074356 , filed on Dec . 11 , 2013 , which dielectric material having a TiN , TAN , TiNxOy, TiW , W , Ti or alloy of Ti or W hard mask thereon . The removal ( Continued ) composition comprises 0 . 1 wt % to 90 wt % of an oxidizing (51 ) Int. Cl. agent ; 0 .0001 wt % to 50 wt % of a carboxylate ; and the COOK 13 /06 ( 2006 .01 ) balance up to 100 wt % of the removal composition com CIID 11 /00 ( 2006 . 01 ) prising deionized water . ( Continued ) 20 Claims, 4 Drawing Sheets TINi Soobelpoor too opost sobe US 10 , 155 ,921 B2 Page 2 Related U . S . Application Data 2006 / 0115970 A1* 6 /2006 Lee .. .. CIID438 7 /3209 /584 is a continuation of application No . 14 / 103 , 303 , filed 2006 /0154839 A1 7 /2006 Ilardi et al. on Dec . 11, 2013 , now abandoned . 2007 /0060490 A1 * 3 / 2007 Skee . .. .. C11D 3 /0073 510 / 175 (60 ) Provisional application No .61 / 889 , 968 , filed on Oct . 2008 / 0004197 A1* 1/ 2008 Kneer .. .. .. .. .. .. C11D 1 / 54 11 , 2013 . 510 / 245 2008 /0139436 A1 * 6 / 2008 Reid C11D 3 /044 (51 ) Int. Ci. 510 / 176 2009 / 0099051 AL 4 / 2009 Aoyama et al. GO3F 742 ( 2006 .01 ) 2009 /0131295 A1 * 5 /2009 Cui . .. .. .. .. .. .. HO1L 21/ 02063 HOIL 21/ 02 ( 2006 .01 ) 510 / 176 HOIL 21/ 3213 (2006 .01 ) 2009 / 0239777 A1 * 9 /2009 Angst C11D 3 /0084 C23F 1 / 18 ( 2006 .01 ) 510 / 175 C23F 1 / 26 ( 2006 .01 ) 2009/ 0281017 A1 * 11 /2009 Suzuki .. .. .. GO3F 7 / 425 C23F 1 / 28 ( 2006 .01 ) 510 / 176 C23F 1 /34 ( 2006 . 01) 2010 /0112728 Al * 5 / 2010 Korzenski .. .. C09K 13 /08 C23F 1 / 38 ( 2006 . 01 ) 438 / 3 C23F 1 /40 ( 2006 .01 ) 2010 / 0160200 A1* 6 /2010 Seki .. C11D 1 /008 510 / 175 CIID 3 / 39 ( 2006 .01 ) 2010 /0163788 A1 * 7 /2010 Visintin .. C11D 1/ 62 ciID 7 / 26 ( 2006 .01 ) 252 / 79 . 3 CIID 732 ( 2006 .01 ) 2010 /0190347 A17 /2010 Ramachandrarao et al . B08B 3 /08 ( 2006 .01 ) 2011/ 0147341 A1 * 6 / 2011 Sato . .. .. .. .. C23F 1 / 38 CIID 7 /04 ( 2006 . 01 ) 216 / 13 B08B 3 / 10 ( 2006 . 01 ) 2011/ 0230053 A1 * 9 /2011 Matsuda . .. .. C23F 1/ 38 438 / 745 CID 3 / 20 ( 2006 .01 ) 2011/ 0275164 A1* 11/ 2011 Visintin .. HO1L 21/ 02079 HOIL 21/ 768 ( 2006 . 01) 438 / 4 HOIL 21311 ( 2006 .01 ) 2012 /0153287 A1 6 /2012 Park et al. (52 ) U . S . Ci. 2013 /0157472 A1 6 /2013 Cui CPC . .. .. .. CIID 3 / 3942 ( 2013 .01 ) ; CIID 3 / 3947 2013 /0171829 Al 7 / 2013 Fitzsimmons et al. ( 2013 . 01 ) ; CIID 7 / 04 (2013 .01 ) ; C11D 7 / 265 2013 /0200040 A1 * 8 /2013 Fitzsimmons . .. HOIL 21 /02063 (2013 .01 ) ; CIID 7 /3209 ( 2013. 01 ) ; CUID 216 / 17 7 /3218 ( 2013 .01 ) ; CIID 7 /3245 (2013 .01 ) ; 2013 /0203231 A1 8 /2013 Fitzsimmons et al. 2013/ 0280916 A1* 10 / 2013 Matsuda . C23F 1/ 38 CIID 73281 ( 2013 .01 ) ; C23F 1 / 18 ( 2013 .01 ) ; 438 / 745 C23F 1 /26 ( 2013 .01 ) ; C23F 1 /28 ( 2013 .01 ) ; 2014 /0128307 A1 * 5 /2014 Chhabra .. .. .. .. .. .. C11D 3 /042 C23F 134 ( 2013 .01 ) ; C23F 1 /38 ( 2013 . 01 ) ; 510 / 175 C23F 1 / 40 ( 2013 .01 ) ; GO3F 7423 ( 2013 .01 ) ; 2015 /0027978 A1 * 1 /2015 Barnes . .. .. .. CO9K 13/ 00 GO3F 7 /425 ( 2013 .01 ) ; GO3F 7 /426 216 / 13 ( 2013 .01 ) ; HOIL 21/ 02057 ( 2013 .01 ) ; HOIL 21 /02063 ( 2013 .01 ) ; HOIL 21/ 31111 FOREIGN PATENT DOCUMENTS ( 2013 .01 ) ; HOIL 21/ 32134 ( 2013 . 01 ) ; HOIL EP 2234145 A1 9 / 2010 21 /76807 ( 2013 .01 ) ; HOIL 21/ 76814 EP 2322692 A1 5 / 2011 (2013 .01 ) ; HOIL 21/ 31144 ( 2013 .01 ) JP 2003 - 339509 A 12 / 2003 (58 ) Field of Classification Search JP 2006339509 A 12 /2006 USPC KR 20120051488 A 5 / 2012 510 /175 TW 200505975 A 2 / 2005 See application file for complete search history . TW 200536936 A 11 /2005 TW 201014927 A 4 / 2010 ( 56 ) References Cited TW 201333171 A 8 / 2013 WO 2012 /009639 A2 1 /2012 U . S . PATENT DOCUMENTS Wo 2013 / 101907 A1 7 / 2013 7 ,922 ,824 B2 4 / 2011 Minsek et al. 8 ,080 ,475 B2 12 /2011 RamachandraRao et al . OTHER PUBLICATIONS 2001/ 0003061 A1 6 /2001 Chen et al. 2002/ 0077259 Al * 6 / 2002 Skee . .. .. .. .. .. C11D 3 / 0073 Steven Verhaverbeke , PH . D . et al ., “ A Model for the Etching of Ti 510 / 175 and TiN in SC - 1 Solutions” , Mat . Res. Soc. Symp. Proc ., vol. 447 , 2002/ 0132745 A1* 9 / 2002 Honda .. .. C11D 7 / 10 510 / 175 1997 Materials Research Society . 2005/ 0263743 A1* 12 / 2005 Lee . .. .. .. C11D 7 / 3218 International Search Report dated Apr. 23 , 2015 for International 252 / 364 Patent Application No . PCT/ US2013 /074356 . 2006 / 0094613 A1* 5 / 2006 Lee .. C11D 7 / 32 International Search Report dated Jan . 15 , 2015 for International 510 / 175 Patent Application No. PCT/ US2014 /059848 . 2006 /0094614 A1* 5 / 2006 Honda .. .. .. C11D 7 / 10 510 /175 * cited by examiner U . S . Patent Dec. 18, 2018 Sheet 1 of 4 US 10 , 155, 921 B2 goodoBand - Residue SEXE WWW FIG . 1A Some . Sooool FIG . 1B U . S . Patent Dec. 18, 2018 Sheet 2 of 4 TIN XXXXXX FIG . 2A FIG . 2B U . S . Patent moDec. 18, 2018 . Sheet 3 of 4 US 10 , 155, 921 B2 2 000 We www w XOXO FIG . 3A FIG . 3B U . S . Patent Dec. 18, 2018 Sheet 4 of 4 US 10 , 155, 921 B2 FIG . 4B US 10 , 155 , 921 B2 REMOVAL COMPOSITION FOR baking, and /or ashing ) by which it was created , and whether SELECTIVELY REMOVING HARD MASK batch or single wafer removal processes can be used . Some AND METHODS THEREOF residues may be cleaned in a very short period of time, while some residues require much longer removal procedures . CROSS REFERENCE TO RELATED 5 Compatibility with both the low - k dielectric and with the APPLICATIONS/ INCORPORATION BY copper conductor over the duration of contact with the REFERENCE STATEMENT removal composition is a desired characteristic . During back - end - of - line (BEOL ) IC fabrication pro This application claims the benefit of U . S . provisional cesses, i. e . , dual damascene processes , TiN , TAN , TiNxOy, application Ser. No . 61/ 889 , 968 , filed Oct . 11, 2013 , the 10 TiW , Ti , and /or W ( including alloys of Ti and W ) are used entire contents of which are hereby incorporated herein by as an hard mask in the formation of vias and trenches to gain reference . high selectivity to low - k dielectric materials during dry etching steps . Effective removal compositions are required BACKGROUND OF THE DISCLOSURE that can selectively remove the Tin , Tan , TiNxOy, TiW , Ti 15 or W , be compatible with low - k materials , copper, cobalt and The presently disclosed and claimed inventive concept( s ) other dielectric materials , and also simultaneously remove relates to compositions and methods for selectively remov unwanted etching residues and Cu oxide from the resulting ing hard mask and other residues from integrated circuit ( IC ) dual damascene structure . Beyond selective removal, it is device substrates , and , more particularly , to compositions also highly desirable that the achievable removal rate of a and methods useful for selectively removing Tin , TaN , 20 hard mask ( Å /min ) for the removal composition be main TiNxOy, TiW , Ti and W hard mask , and hard masks com tained substantially constant for an extended period of time. prising alloys of the foregoing , as well as other residues with the continuing reduction in device critical dimen from such substrates comprising low - k dielectric materials , sions and corresponding requirements for high production TEOS, copper, cobalt and other low - k dielectric materials efficiency and reliable device performance , there is a need using a carboxylate compound . 25 for such improved removal compositions. Plasma dry etching is commonly used to fabricate vertical sidewall trenches and anisotropic interconnecting vias in SUMMARY copper (Cu ) / low - k dual damascene fabrication processes .