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 , such as and/or , alone or in combination With an additional organic (51) Int. Cl. solvent, such as , 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 B2E 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)};CD2Deveioper=

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. Pat. No. 7,851,140 B2 to resist ?lm of step (d); (f) developing the resist ?lm with the Tsubaki); however, there are few examples of organic devel 50 organic developer solvent described herein to dissolve opers for positive tone chemically ampli?ed resists. The exposed regions of the ?lm and produce a positive-tone image present invention addresses this need in the art. on the substrate; and (g) optionally rinsing the ?lm with water after development. SUMMARY OF THE INVENTION 55 In one embodiment, the resist polymer composition of step The present invention provides a method comprising (a) further includes a photoacid generator (PAG). In a pre developing a positive tone image in a chemically ampli?ed ferred embodiment, the PAG is triphenylsulfonium per?uoro resist with an organic developer solvent comprising a poly 1 -butanesulfonate (TPS-N). hydric alcohol, wherein the organic developer solvent has no In another embodiment, the resist polymer composition of more than 2.6><10_4 M hydroxide ions. In one embodiment, 60 step (a) further includes a quencher, which may be selected the organic developer solvent has no more than 1.0><10_4 M from the group consisting of base quenchers and radiation hydroxide ions and in another embodiment, the organic sensitive quenchers. In a preferred embodiment, the radiation developer solvent is free of hydroxide ions. sensitive quencher is the photodecomposable base (PDB), In further embodiments of the invention, the polyhydric triphenylsulfonium hepta?uorobutyrate (TPS-HFB). In alcohol is selected from the group consisting of ethylene 65 another embodiment, the radiation sensitive quencher is a glycol and glycerol. The developer may comprise the poly PDB selected from the group consisting of Structures (1) hydric alcohol solvent alone (neat) or in combination with (10): US 8,900,802 B2 4 -continued (1) >

(7)

mm 20 (2) 00% (3) 25 mmo mm 30

wherein n is 1, 2, or 3 (9)

(3) 00% 35 mam 40

(10)

wherein n is 1, 3, or 4 00$)QQK 45 m (4) O H

HO O'+S ( C s H 5)3 WEE 50 HO HO Ow In another embodiment, the casting solvent of step (a) is HO O-+S(C6H5)3 selected from the group consisting of propylene glycol 55 methyl ether acetate (PGMEA), propylene glycol monometh O ylether (PGME), and a combination of PGMEA and PGME. In a further embodiment, the radiation of step (d) is (5) selected from the group consisting of deep ultraviolet (DUV) F F F F radiation, extreme ultraviolet (EUV) radiation, electron beam 60 (e-beam) radiation, and ion-beam radiation. Additional aspects and embodiments of the invention will be provided, without limitation, in the detailed description of 0 the invention that is set forth below. BRIEF DESCRIPTION OF THE DRAWINGS FFFF F 65 FIG. 1 shows structures for the photoresist compositions developed according to the methods of the present invention US 8,900,802 B2 5 6 with the following solvents: ethylene glycol (EG), EG/iso The terms “positive tone resist” refers to a photoresist that propyl alcohol (IPA), and EG/water, and glycerol/ IPA. produces a positive tone image upon development, i.e., FIGS. 2A-2D show KrF imagining results for molecular exposed regions are removed during the development pro glass NORIA-MAdMA resists developed with IPA (100); EG cess. (100), EG/IPA (70/30); and EG/water (90/10). The term “polyhydric alcohol” is used in its traditional FIG. 3 shows KrF contrast curve data for molecular glass sense to refer to an alcohol molecule that has more than one NORIA-MAdMA resists developed with EG (100); EG/IPA hydroxyl group. (70/30 and 50/50); EG/water (90/ 10); and tetramethyl ammo The term “DUV” or “deep ultraviolet” refers to radiation at nium hydroxide (TMAH 0.26N). wavelengths of 300 nm or shorter, with typical DUV exposure FIGS. 4A-4D show e-beam imaging results for molecular wavelengths for lithography techniques being 248 nm (5 eV) glass NORIA-MAdMA resists developed with TMAH with krypton ?uoride (KrF) excimer lasers and 193 nm (6.4 eV) with argon ?uoride (ArF) excimer lasers. (0.26N) and EG (100). The term “EUV” or “extreme ultraviolet” refers to radia FIGS. 5A-5C show EUV imaging results for molecular tion at wavelengths of 50 nm or shorter. Typical EUV expo glass NORIA-MAdMA resists developed with EG (100). sure currently occurs at 10 to 13 nm with 13.5 nm being the FIG. 6 shows KrF contrast curve data for polyhydroxysty most commonly used EUV wavelength. rene PHS-MAdMA resists developed with EG (100); EG/wa The term “chemically ampli?ed resist” is used in its tradi ter (90/10, 85/15, and 75.25); and TMAH (0.26N). tional sense to refer to a photoresist that is based on acid FIGS. 7A and 7B show EUV imaging results for polyhy catalyzed deprotection and is comprised of a polymer, cata droxystyrene PHS-MAdMA resists developed with EG 20 lyst, additive, and casting solvent. Chemically ampli?ed (100). resists are designed for DUV and shorter wavelengths and FIG. 8 shows KrF contrast curve data for methacrylate have increased sensitivity to exposure energy as a conse ?uoroalcohol NBHFA-MAdMA and NBHFA-EcEdMA quence of the chemical ampli?cation. resists developed with TMAH (0.26N), EG (100), and The present invention is directed to the use of an organic EG/IPA (70/30 and 50/ 50). FIG. 8 also shows methacrylate 25 developer solvent comprising a polyhydric alcohol to develop Hd-MCpMA resists developed with EG/IPA (70/30 and high resolution positive tone images in chemically ampli?ed 50/50). resists. The polyhydric alcohol based developer solvent will FIG. 9 shows ArF contrast curve data for methacrylate necessarily have hydroxide ions in the range of zero to 2.6x ?uoroalcohol NBHFA-MAdMA, NBHFA-MAdMA/NB 10'4 M. In one embodiment, the solvent has no more than HFA-MCpMA (1 0/ 90), and NBHFA-EcEdMA resists devel 30 1.0><10_4 M hydroxide ions and in another embodiment, the oped with EG/IPA (70/30). FIG. 9 also shows methacrylate solvent is free of hydroxide ions. Hd-MCpMA resists developed with EG/IPA (70/30 and Examples of polyhydric alcohols that may be used to pre 50/50). pare the developer solvent of the present invention include, FIGS. 10A-10C show EUV imaging results for methacry without limitation, ethylene glycol, glycerol, , threi late-?uoroalcohol NBHFA-MAdMA/NBHFA-MCpMA (10/ 35 tol, , , , , , , 90) resists developed with EG/IPA (70/ 30). , , , , , , , FIG. 11 shows ArF contrast curve data for methacrylate maltotriitol, maltotetraitol, polyglycidol. The polyhydric ?uoroalcohol NFHFA-MAdMA and NBHFA-MAdMA/NB alcohol may be used alone (i.e., neat) to develop the positive HFA-MCpMA (10/90) resists developed with glycerol/IPA tone resist or it be used in combination with water or with (50/50). FIG. 11 also shows the methacrylate HdMCpMA 40 other solvents, such as for example, aliphatic alcohols, diols, resist developed with glycerol/IPA (50/ 50). and/or triols. A preferred organic solvent for use with the FIG. 12 shows KrF contrast curve data for NORIA organic polyhydric alcohol solvent of the present invention is MAdMA resists developed with glycerol (100), glycerol/ isopropyl alcohol. Examples of other organic solvents that water (80/20), glycerol/IPA (70/30), and glycerol/IPA (50/ may be used in combination with the organic polyhydric 50). 45 alcohol solvent of the present invention include, without limi tation, propanediols, propanetriols, butanediols, butanetriols, DETAILED DESCRIPTION OF THE INVENTION pentanediols, pentanetriols, hexanediols, hexanetriols, octanediols, octanetriols, cyclopropanol, cyclobutanol, Set forth below is a description of what are currently cyclopentanol, phenylmethanol, and phenylethanol. One of believed to be preferred embodiments of the claimed inven 50 skill in the art will appreciate that the formulation of the tion. Any alternates or modi?cations in function, purpose, or organic solvent developer of the present invention will be set structure are intended to be covered by the claims of this in such a way as to optimize the RLS response of the resist. application. As used in this speci?cation and the appended The RLS response may be optimized by comparing the LER claims, the singular forms “a,” “an,” and “the” include plural of the resist, at a given resolution and imaging dose, after referents unless the context clearly dictates otherwise. The 55 development with an aqueous base and with the organic terms “comprises” and/or “comprising,” as used in this speci developer solvent of the present invention. ?cation and the appended claims, specify the presence of The positive tone chemically ampli?ed resists described stated features, integers, steps, operations, elements, and/or herein may be prepared from resist polymers selected from components, but do not preclude the presence or addition of the group consisting of molecular glasses, polyhydroxysty one or more other features, integers, steps, operations, ele 60 renes, styrenes having one or more pendant hexa?uoroalco ments, components, and/or groups thereof. hol groups, acrylates, methacrylates, and methacrylate ?uo As used herein, the terms “resist” and “photoresist” are roalcohols. An example of a molecular glass resist polymer meant to refer to the same composition and thus, the terms are that may be used to prepare a positive tone molecular glass used interchangeably herein. resist is NORIA molecular glass protected with 2-methyl-2 The term “negative tone resist” refers to a photoresist that 65 adamantyl methacrylate (N ORIA-MAdMA). An example of produces a negative tone image upon development, i.e., unex a polyhydroxystyrene (PHS) resist polymer that may be used posed regions are removed during the development process. to prepare a positive tone PHS resist is poly(4-hydroxysty US 8,900,802 B2 7 8 rene-co-2-methyl-2-adamantyl methacrylate) (PHS invention. Examples 2, 4, 5, 7, and 10 describe the experi MAdMA). An example of a methacrylate resist polymer that mental procedures associated with the generation of the SEM may be used to prepare a methacrylate resist is poly((1-me images. thylcyclopentyl methacrylate)-co-(2-methyltricyclo FIGS. 2A-2D show SEM line/space (LS) patterns at 200 [3.3. 1 . 13,7] decan-2-yl methacrylate)-co-(3-(2-hydroxy nm critical dimension (CD) for high performance positive ethoxy)tricyclo[3.3.1.13,7]decan-1-yl methacrylate)-co-(4 tone NORIA-MAdMA molecular glass resists imaged with a oxa-5-oxotricyclo [4 .2 .1 .03 ,7]nonan-2 -yl methacrylate)) KrF excimer laser and developed with the following solvents: (Hd-MCpMA). Examples of methacrylate-?uoroalcohol IPA (100), EG (100), EG/ IPA (70/ 30), and EG/water (90/10). resist polymers that may be used to prepare methacrylate FIGS. 2A-2D clearly show that the NORIA-MAdMA resists ?uoroalcohol resists include poly(5-acryloyloxy-2,6-norbor developed with the solvents containing EG show far greater nanecarbolactone-co-2-methyl-2-adamantyl methacrylate contrast images than the resist developed with IPA alone. FIGS. 4A-4D show SEM L/ S patterns at 40 nm and 60 nm co-2-[1',1',1'-tri?uoro-2'-(tri?uoromethyl)-2'-hydroxy) CD for NORIA MAdMA positive tone resists imaged with propyl-3 -norbornyl methacrylate) (N BHFA-MAdMA); poly e-beam radiation and developed with either 0.26 N TMAH (5-acryloyloxy-2,6-norbornanecarbolactone-co-2-methyl-2 standard base (FIGS. 4A and 4B) or 100% EG (FIGS. 4C and cyclopentayl methacrylate-co-2-[1',1',1'-tri?uoro-2' 4D). FIGS. 4A-4D show that the EG solvent of the present (tri?uoromethyl)-2'-hydroxy)propyl-3-norbornyl invention is equally as effective at developing positive tone methacrylate) (NBHFA-MCpMA); and poly(5-acryloyloxy resists as the standard TMAH solvent. 2,6-norbomanecarbolactone-co-2-ethyl-2-cyclopentayl FIGS. 5A-5C show SEM L/ S patterns at 28 nm, 30 nm, and methacrylate-co-2-ethyl-2-adamantyl methacrylate-co-2-[1', 20 32 nm CD for NORIA-MAdMA positive tone resists imaged 1',1'-tri?uoro-2'-(tri?uoromethyl)-2'-hydroxy)propyl-3 -nor with EUV radiation and developed with EG (100). bomyl methacrylate) (NBHFA-EcEdMA). FIGS. 7A and 7B show SEM L/S patterns at 32 nm and 36 Preparation of the positive tone organic solvent developed nm CD for PHS-MAdMA polyhydroxystyrene positive tone chemically ampli?ed resists described herein involves the resists imaged with EUV radiation and developed with EG. generation of acidic substituent groups, such as carboxylic 25 FIGS. 10A-10C show SEM L/S patterns at 30 nm, 32 nm, acids or phenols, which render the exposed areas of the resist and 36 nm CD for NBHFA-MAdMA/NBHFA-MCpMA (10/ soluble in polar organic solvents while the unexposed ?lm 90) methacrylate-?uoroalcohol positive tone resists imaged remains insoluble. The polarity differences between the with EUV radiation and developed with an EG/IPA (70/30). exposed and unexposed regions of the ?lm cause the disso FIGS. 3, 6, 8, 9, 11, and 12 show contrast curve data for lution contrast of the organic solvent developed positive tone 30 styrenic molecular glass (FIGS. 3 and 12), polyhydroxysty photoresists of the present invention. This type of polarity rene (FIG. 6), and methacrylate and methacrylate-?uoroal based dissolution differs from the ionization-dissolution that cohol (FIGS. 8, 9, and 11) based positive tone resists, which occurs in aqueous base developed resists, a process that is were developed using the organic solvent method of the more akin to chemical etching than the polymer solubiliza present invention. Examples 3, 6, 8 and 9 describe the experi tion that occurs with solvent development. As the presence of 35 mental procedures associated with the generation of the con hydroxide ions in the developer solvent risks the introduction trast curve data. of ionization/dissolution processes, rather than the polarity FIG. 3 shows KrF contrast curve data for positive tone based dissolution described herein, it is preferred that the NORIA-MAdMA molecular glass resists developed with EG developer solvent of the present invention has a concentration (100), EG/IPA (70/30), EG/IPA (50/50), EG/water (90/ 10), of hydroxide ions that is as low as possible. 40 and 0.26 N TMAH for comparative purposes. As shown The polarity based dissolution describes herein also differs therein, the NORIA-MAdMA resists were developed into from the dissolution process that occurs in non-chemically very high contrast resists suitable for high performance imag ampli?ed resists, such as PMMA resists, where the dissolu ing with all solvents. The EG neat and EG/IPA (both 70/30 tion contrast derives from changes in molecular weight and is and 50/50) developers produced resists with contrast data typically very poor due to the chemical similarity of the 45 comparable to that of the TMAH developed resists. The exposed and unexposed regions of the resist ?lm. EG/water (90/10) developer produced resists with lightly less As a result of the improved polarity-based dissolution pro contrast than EG/ IPA and TMAH developed resists. cess described herein, the positive tone organic solvent devel FIG. 12 shows KrF contrast curve data for positive tone oped chemically ampli?ed resists of the present invention NORIA-MAdMA molecular glass resists developed with have the potential to address RLS challenges in a way that 50 glycerol (100), glycerol/water (80/20); glycerol/IPA (70/30); other resist development systems cannot. For example, the and glycerol/ IPA (50/ 50). As shown therein, the neat glycerol resists and methods of the present invention overcome prob and glycerol/water solvents did not produce high contrast lems that are caused when alkaline developers are used for resists whereas the glycerol/IPA solvents produced very high non-semiconductor lithographic processes, such as the fabri contrast positive tone molecular glass resists. cation of chips patterned with arrays of biomolecules (e.g., 55 FIG. 6 shows KrF contrast curve data for positive tone proteins and oligonucleotides). PHS-MAdMA polyhydroxystyrene positive tone resists FIGS. 2-12 show imaging results and contrast curve data developed with EG, EG/water (90/ 10), EG/water (85/15), for positive tone resists developed with ethylene glycol (EG) EG/water (75/25), and TMAH for comparative purposes. The alone, isopropyl alcohol (IPA) alone, EG in combination with EG neat developer produced the highest contrast PHS resist IPA, glycerol in combination with IPA, and EG in combina 60 from among the tested developers. tion with water. Positive tone resists developed with TMAH FIG. 8 shows KrF contrast curve data for NBHFA are included for comparative purposes. MAdMA and NBHFA-EcEdMA methacrylate-?uoroalcohol FIGS. 2, 4, 5, 7, and 10 show scanning electron micrograph positive tone resists developed with 0.26 N TMAH (for com (SEM) imaging results for styrenic molecular glass (FIGS. 2, parative purposes), EG (100), and EG/IPA (70/30 and 50/ 50). 4, 5), polyhydroxystyrene (FIG. 7), and methacrylate-?uoro 65 Optimization of the EG neat developer to incorporate IPA alcohol (FIG. 10) based positive tone resists, which were increased the contrast for the NBHFA-MAdMA resist to developed with the organic solvent method of the present where it was comparable or better than that seen with TMAH.