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(12) United States Patent (10) Patent No.: US 8,900,802 B2 Allen Et Al

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(12) United States Patent (10) Patent No.: US 8,900,802 B2 Allen Et Al USOO8900802B2 (12) United States Patent (10) Patent No.: US 8,900,802 B2 Allen et al. (45) Date of Patent: Dec. 2, 2014 (54) POSITIVE TONE ORGANIC SOLVENT (56) References Cited DEVELOPED CHEMICALLY AMPLIFIED U.S. PATENT DOCUMENTS RESIST 3,586,504 A 6/1971 Coates et al. (71) Applicants:International Business Machines 4,833,067 A 5/1989 Tanaka et a1. Corporation, Armonk, NY (US); JSR 5,126,230 A 6/1992 Lazarus et al. Corporation, Tokyo (JP) 5,185,235 A 2/1993 Sato et a1. 5,266,424 A 11/1993 Fujino et a1. 5,554,312 A 9/1996 Ward (72) Inventors: Robert D. Allen, San Jose, CA (US); 5,846,695 A 12/1998 Iwata et a1. Ramakrishnan Ayothi, San Jose, CA 6,599,683 B1 7/2003 Torek et a1. (US); Luisa D. Bozano, Los Gatos, CA 7,585,609 B2 9/2009 Larson et al. (US); William D. Hinsberg, Fremont, (Continued) CA (US); Linda K. Sundberg, Los Gatos, CA (US); Sally A. Swanson, San FOREIGN PATENT DOCUMENTS Jose, CA (US); Hoa D. Truong, San Jose, CA (US); Gregory M. Wallraff, JP 54143232 8/1979 JP 58219549 12/1983 San Jose, CA (US) JP 63259560 10/1988 (73) Assignees: International Business Machines OTHER PUBLICATIONS Corporation, Armonk, NY (US); JSR Corporation, Tokyo (JP) Ito et al., P0 sitive/negative mid UV resists with high thermal stability, SPIE 0771:24-31 (1987). (*) Notice: Subject to any disclaimer, the term of this (Continued) patent is extended or adjusted under 35 U.S.C. 154(b) by 99 days. Primary Examiner * Brittany Raymond (74) Attorney, Agent, 0rFirm * Karen Canaan; CanaanLaW, (21) Appl. No.: 13/775,122 PC. (22) Filed: Feb. 23, 2013 (57) ABSTRACT (65) Prior Publication Data Provided is a method for developing positive-tone chemically ampli?ed resists With an organic developer solvent having at US 2014/0242526 A1 Aug. 28, 2014 least one polyhydric alcohol, such as ethylene glycol and/or glycerol, alone or in combination With an additional organic (51) Int. Cl. solvent, such as isopropyl alcohol, and/or water. The organic G03F 7/26 (2006.01) solvent developed positive tone resists described herein are G03F 7/32 (2006.01) useful for lithography pattern forming processes; for produc (52) U.S. Cl. ing semiconductor devices, such as integrated circuits (IC); CPC .................................... .. G03F 7/325 (2013.01) and for applications Where basic solvents are not suitable, USPC ........................................................ .. 430/326 such as the fabrication of chips patterned With arrays of bio (58) Field of Classi?cation Search molecules or deprotection applications that do not require the CPC ........ .. G03F 7/0392; G03F 7/20; G03F 7/325 presence of acid moieties. USPC ................................................ .. 430/322, 326 See application ?le for complete search history. 36 Claims, 14 Drawing Sheets I m M Do US 8,900,802 B2 Page 2 (56) References Cited 2007/0269749 A1 11/2007 Schenker U.S. PATENT DOCUMENTS OTHER PUBLICATIONS R1542,7,851,140 128 EB2 12/20102/201 1 EgbeTsubaki Maltabes et 211., 1X Deep UV thhography. Wlth. Chemlcal. Ampll?ca. 2002/0106589 A1 8/2002 Rodney et 31, tion for l-Microti DRAM Production, SPIE 1262:3-7 (1990). US. Patent Dec. 2, 2014 Sheet 2 0f 14 US 8,900,802 B2 Kr? imaging Results for NQREA-MAdMA Resists iPA Deveioper (000); CD = 200 nm LS HG. 2A KrF imaging Results for NOREA-MAGMA Resists EG (1G0) Deveioper; CD = 260 nm LS Fi?. 28 US. Patent Dec. 2, 2014 Sheet 3 0f 14 US 8,900,802 B2 KrF imaging Resuits for NORiA-MAGMA Resists EGHPA Deveioper (YOfSO); CD = 200 nm LS FIG. 2C KrF imaging Resuits for NORiA-MAGMA Resists EG/Water Devsiopsr (90/19); CD = 206 nm LS FEG. 2D US. Patent Dec. 2, 2014 Sheet 4 0f 14 US 8,900,802 B2 Dose (ml/cm?) FEG. 3 US. Patent Dec. 2, 2014 Sheet 5 0f 14 US 8,900,802 B2 YMAH Deveioper {0.26M}; CD = 69 am LS FEG. 4A E-Beam imaging Resuits for NORiA-MAdMA Resists TMAH Deveioper (0.2601); CE) = 49 mm LS HS. 48 US. Patent Dec. 2, 2014 Sheet 6 0f 14 US 8,900,802 B2 E-Beam imaging Resuits far NOREA-MAdMA Resists ES Deveiaper (100); CD = 60 nm LS FEG. 4Q E-Beam imaging Ressuits for NGREA-MAdMA Reaisis EG Deveioper (100); CD = 46 nm L8 HG. 4S US. Patent Dec. 2, 2014 Sheet 7 0f 14 US 8,900,802 B2 L8CD32nm= forNOREAMAdMAi.ResuitsResists:Q 100)7 PEG.5C oper EGDex/e EUVimag 39LSnm 30>: - " A b forNORIAMAdMAResuitsRes?g 100) F56.58 oper EGDeva , , “01:. FEG.5A ResuitsforNORIAMAGMAResists09 EEG(102)};CDDeveioper2= EUVimam US. Patent (A)Thickness FEG, 6 US. Patent Dec. 2, 2014 Sheet 9 0f 14 US 8,900,802 B2 EUV imaqing Resuits for PHS-t‘AAdI‘AA Resists ' Results for PHS-MAGMA Resists EG Deveioper (106); CD I 32 nm LS EEG Deveéoper (189); CD 1 36 nm LS FEG. m FEG. 7B US. Patent Dec. 2, 2014 Sheet 10 0f 14 US 8,900,802 B2 = 0 ; 'liill 458101214161826222426283032 Dose (mJ/cmz) US. Patent Dec. 2, 2014 Sheet 12 0f 14 US 8,900,802 B2 2mm8magsManagua?ganH 03.Qw 2mmSMamet20mg$6Ma:H m3.QE 23SMamas2%;me?gECH US. Patent Dec. 2, 2014 Sheet 13 0f 14 US 8,900,802 B2 ArF Contrast Curve Data for Methacrylate Type Resists 01234567891011121314 Dose ng/cm, , “)m FEG. 11 US. Patent 6 8101214161829222426283032 Dose (mi/cm 2') FIG. 12 US 8,900,802 B2 1 2 POSITIVE TONE ORGANIC SOLVENT water or another organic solvent. In one embodiment, the DEVELOPED CHEMICALLY AMPLIFIED developer comprises a mixture of ethylene glycol and isopro RESIST pyl alcohol. In another embodiment, the developer comprises a mixture of ethylene glycol and water. In a further embodi JOINT RESEARCH AGREEMENT ment, the developer comprises a mixture of glycerol and isopropyl alcohol. The invention described herein is subject to a joint research In another embodiment, the chemically ampli?ed resist agreement between International Business Machines Corpo comprises a composition selected from the group consisting ration and J SR Corporation. of molecular glasses, polyhydroxystyrenes, styrenes having one or more pendant hexa?uoroalcohol groups, acrylates, TECHNICAL FIELD methacrylates, and methacrylate ?uoroalcohols. The present invention relates generally to photoresists. In one embodiment, the chemically ampli?ed resist com More speci?cally, the present invention relates to positive prises styrenic NORIA molecular glass protected with a tone resists that are capable of being developed with polyhy 2-methyl-2-adamantyl group (NORIA-MAdMA). dric alcohol-based solvents for high resolution imaging. In another embodiment, the chemically ampli?ed resist comprises the polyhydroxystyrene polymer, poly(4-hy BACKGROUND OF THE INVENTION droxystyrene-co-2-methyl-2-adamantyl methacrylate) As semiconductor device features continue to shrink in 20 (PHS-MAdMA). size, the task of meeting photoresist performance require In a further embodiment, the chemically ampli?ed resist ments for high resolution, low line edge roughness (LER) and comprises a methacrylate-?uoroalcohol polymer selected high photo speed grows increasingly dif?cult. The challenges from the group consisting of poly(5-acryloyloxy-2,6-norbor in simultaneously meeting the requirements for resolution, nanecarbolactone-co-2-methyl-2-adamantyl methacrylate LER, and sensitivity are known in the art as the “RLS 25 co-2-[1',1',1'-tri?uoro-2'-(tri?uoromethyl)-2'-hydroxy)pro Tradeoff.” Current generation chemically ampli?ed photore pyl-3 -norbornyl methacrylate) (N BHFA-MAdMA) ; poly(5 - sists, designed to be developed in alkaline base, are capable of acryloyloxy-2,6-norbornanecarbolactone-co-2-methyl-2 high photo speeds, but exhibit unsatisfactory resolution and cyclopentayl methacrylate-co-2-[1',1',1'-tri?uoro-2' LER as feature sizes approach 20 nm. In comparison, high (tri?uoromethyl)-2'-hydroxy)propyl-3-norbomyl performance solvent-developed non-chemically ampli?ed 30 methacrylate) (NBHFA-McPMA); and poly(5-acryloyloxy resists, such as PMMA (poly methyl methacrylate) resists, have excellent resolution and LER, but have unacceptably 2,6-norbornanecarbolactone-co-2-ethyl-2-cyclopentayl poor photospeed in optical imaging. methacrylate-co -2-ethyl-2-adamantyl methacrylate-co-2-[1', The use of solvent development in lithography is not a new 1', 1'-tri?uoro-2'-(tri?uoromethyl)-2'-hydroxy)propyl-3 -nor idea. In the 1950s, the earliest photoresist systems used 35 bornyl methacrylate) (N BHFA-EcEdMA). organic solvents for developing resist ?lms. See, e.g., William In another embodiment, the chemically ampli?ed resist S. DeForest, Photoresist: Materials and Processes, McGraw comprises the methacrylate polymer, poly((1-methylcyclo Hill, NewYork, 1975. The ?rst generation 248 nm chemically pentyl methacrylate)-co-(2 -methyltricyclo [3 .3 .1 . 13 ,7]de ampli?ed resist, the TBOC (t-butyloxycarbonyloxy) styrene can-2-yl methacrylate)-co-(3-(2-hydroxyethoxy)tricyclo resist, was described 25 years ago for development in an 40 [3 .3 . 1 . 13,7]decan-1 -yl methacrylate)-co-(4-oxa-5 organic solvent. See, e.g., Ito et al., SPIE 0771, 24 (1987); and oxotricyclo[4.2.1.03,7]nonan-2-yl methacrylate)) (Hd Maltabes et al., SPIE 1262, 2 (1990). Since the development MCpMA). of the TBOC resist, virtually all chemically ampli?ed resists In a further embodiment, there is provided a method com have been designed to be developed in aqueous base solu prising the steps of: (a) dissolving, in a casting solvent, a tions; consequently, development of solvent-based resists has 45 composition comprising a resist polymer; (b) coating a sub been largely ignored as an option for modern high resolution strate with the dissolved composition of step (a) to produce a chemically ampli?ed resists. Today, there is an on-going resist ?lm; (c) optionally baking the resist ?lm of step (b); (d) interest in organic developers for negative tone chemically exposing the resist ?lm to radiation; (e) optionally baking the ampli?ed resists (see, e.g., US.
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