POLYMERS CONTAINING OXYGEN AND SULFUR ALICYCLIC UNITS AND PHOTORESIST COMPOSITIONS COMPRISING SAME

Abstract: The invention includes polymers that contain a heterocyclic ring, preferably an oxygen- or sulfur-containing ring. The heterocyclic ring is preferably fused to the polymer backbone. The invention also provides photoresists that contain such polymers, particularly for imaging at short wavelengths such as sub-200 nm.

Description: POLYMERS CONTAINING OXYGEN AND SULFUR ALICYCLIC UNITS PHOTORESIST COMPOSITIONS COMPRISING SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to new polymers that contain oxygen and/or alicyclic (heteroalicyclic) units and use of such polymers as a resin binder compo photoresist compositions, particularly chemically-amplified positive-acting resist, be effectively imaged at short wavelengths such as sub-200 nm, particularly 193 : 2. Background Photoresists are photosensitive films used for transfer of images to a subsl coating layer of a photoresist is formed on a substrate and the photoresist layer is exposed through a photomask to a source of activating radiation. The photomask areas that are opaque to activating radiation and other areas that are transparent tc activating radiation. Exposure to activating radiation provides a photoinduced ch transformation of the photoresist coating to thereby transfer the pattern of the phc to the photoresist-coated substrate. Following exposure, the photoresist is develo provide a relief image that permits selective processing of a substrate. A photoresist can be either positive-acting or negative-acting. For most n acting photoresists, those coating layer portions that are exposed to activating rad polymerize or crosslink in a reaction between a photoactive compound and polyn reagents of the photoresist composition. Consequently, the exposed coating porti rendered less soluble in a developer solution than unexposed portions. For a posi acting photoresist, exposed portions are rendered more soluble in a developer soh while areas not exposed remain comparatively less developer soluble. Photoresis compositions are described in Deforest, Photoresist Materials and Processes, Mc( Hill Book Company, New York, ch. 2, 1975 and by Moreau, Semiconductor Lithography, Principles, Practices and Materials, Plenum Press, New York, ch. 2 More recently, chemically-amplified-type resists have been increasingly employed, particularly for formation of sub-micron images and other high perforr applications. Such photoresists may be negative- acting or positive-acting and ger include many crosslinking events (in the case of a negative-acting resist) or depro reactions (in the case of a positive-acting resist) per unit of photogenerated acid, case of positive chemically-amplified resists, certain cationic photoinitiators have used to induce cleavage of certain "blocking" groups pendant from a photoresist t or cleavage of certain groups that comprise a photoresist binder backbone. See, f< example, U.S. Patents Nos. 5,075,199; 4,968,581; 4,883,740; 4,810,613; and 4,49 and Canadian Patent Application 2,001,384. Upon cleavage of the blocking gro through exposure of a coating layer of such a resist, a polar functional group is foi e.g., carboxyl or imide, which results in different solubility characteristics in expc unexposed areas of the resist coating layer. See also R.D. Allen et al., Proceeding SPIE, 2724:334-343 (1996); and P. Trefonas et al. Proceedings of the 11th Intern. Conference on Photopolymers (Soc. Of Plastics Engineers), pp 44-58 (Oct. 6, 19S While currently available photoresists are suitable for many applications, c resists also can exhibit significant shortcomings, particularly in high performance applications such as formation of highly resolved sub-half micron and sub-quartei features. Consequently, interest has increased in photoresists that can be photoimag short wavelength radiation, including exposure radiation of about 250 nm or less, about 200 nm or less, such as wavelengths of about 248 nm (provided by KrF lase 193 nm (provided by an ArF exposure tool). See European Published Applicatior EP915382A2. Use of such short exposure wavelengths can enable formation of s features. Accordingly, a photoresist that yields well-resolved images upon 248 nn nm exposure could enable formation of extremely small (e.g. sub-0.25 μm) featui respond to constant industry demands for smaller dimension circuit patterns, e.g. provide greater circuit density and enhanced device performance. However, many current photoresists are generally designed for imaging at relatively higher wavelengths, such as G-line (436 nm) and I-line (365 nm) are ge unsuitable for imaging at short wavelengths such as sub-200nm. Even shorter wavelength resists, such as those effective at 248 nm exposures, also are general.; unsuitable for sub-200 nm exposures, such as 193 nm imaging. More specifically, current photoresists can be highly opaque to extremely exposure wavelengths such as 193 nm, thereby resulting in poorly resolved image It thus would be desirable to have new photoresist compositions, particula resist compositions that can be imaged at short wavelengths such as sub-200 mn < wavelengths, particularly 193 nm. SUMMARY OF THE INVENTION We have now found novel polymers and photoresist compositions that coi the polymers as a resin binder component. The photoresist compositions of the ir can provide highly resolved relief images upon exposure to extremely short wave particularly sub-200 nm wavelengths such as 193 nm. Polymers of the invention contain a oxygen- and/or sulfur-containing heteroahcyclic ring that is preferably fused to the polymer backbone (i.e. at least i heteroahcyclic ring atoms as part of the polymer backbone). The heteroahcyclic one or more oxygen and/or sulfur atoms as ring members. Preferred polymers of the invention also contain a carbon alicyclic group ι group has all carbon ring members) that is fused to the polymer backbone, i.e. the alicyclic ring has at least two carbon ring members that comprise the polymer bac Preferred fused carbon alicyclic groups are provided by polymerization of cyclic ι (endocyclic double bond) compounds such as optionally substituted norbomene g We have found that incorporation of such carbon alicyclic groups into a polymer ι significantly increase plasma etch resistance of a photoresist containing the polyn Preferred heteroahcyclic polymer units may be substituted, e.g. by heteroa groups such as ethers (alkoxy) preferably having 1 to about 10 carbon atoms, alk) preferably having 1 to about 10 carbon atoms, alkylsulfinyl preferably 1 to about carbon atoms, alkylsulfonyl preferably having 1 to about 10 carbon atoms, and th It has been surprising found that such substituents can provide enhanced lithograp results, particularly enhanced substrate adhesion. For use in photoresist compositions, polymers of the invention also will cc one or more units that comprise photoacid-labile moieties. The photoacid-labile £ may be a substituent of one or more of the above-mentioned units, such as a subst of a polymerized vinyl alicyclic ether, vinyl alicyclic thioether or carbon alicyclic The photoacid labile moiety also may be present as an additional polymer unit, e.j polymerized alkyl acrylate or alkyimethacrylate, particularly an acrylate having ai alicyclic moiety such as methyladamantyl acrylate or methyladamantyl methacryl Preferred alicyclic photoacid-labile moieties are tertiary ester alicyclic hydrocarbc groups that have two or more fused or bridged rings. Preferred tertiary ester grou include optionally substituted adamantyl, particularly methyl adamantyl as mentic above; optionally substituted fencyl groups, particularly ethyl fencyl; optionally substituted pinanyl; and optionally substituted tricyclo decanyl, particularly an all substituted tricyclo decanyl such as 8-ethyl-8-tricyclodecanyl e.g. as provided by polymerization of 8-ethyl-8-tricyclodecanyl acrylate and 8-ethyl-8-tricyclodecany methacrylate. Additional alicyclic ester groups also will be suitable, including adc bicyclic, tricyclic and other polycyclic moieties. Polymers of the invention also may contain units in addition to the above j For example, polymers of the invention also may contain nitrile units such as proA polymerization of methacrylonitrile and acrylonitrile. Additional contrast enhanc groups also may be present in polymers of the invention, such as groups provided polymermization of methacrylic acid, acrylic acid, and such acids protected as pfr labile esters, e.g. as provided by reaction of ethoxyethyl methacrylate, t-butoxy methacrylate, t-butylmethacrylate and the like. Generally preferred polymers of the invention contain 3, 4 or 5 distinct ref units, i.e. preferred are terpolymers, tetrapolymers and pentapolymers that contair more heteroahcyclic groups as disclosed herein. Polymers of the invention are preferably employed in photoresists imaged nm, and thus preferably will be substantially free of any phenyl or other aromatic For example, preferred polymers contain less than about 5 mole percent aromatic more preferably less than about 1 or 2 mole percent aromatic groups, more prefer; less than about 0.1, 0.02, 0.04 and 0.08 mole percent aromatic groups and still mo preferably less than about 0.01 mole percent aromatic groups. Particularly prefeπ polymers are completely free of aromatic groups. Aromatic groups can be highly absorbing of sub-200 nm radiation and thus are undesirable for polymers used in photoresists imaged with such short wavelength radiation. The invention also provides methods for forming relief images, including methods for forming a highly resolved relief image such as a pattern of lines whei line has essentially vertical sidewalls and a line width of about 0.40 microns or les even a width of about 0.25, 0.20 or 0.16 microns or less. The invention further pr articles of manufacture comprising substrates such as a microelectronic wafer sub liquid crystal display or other flat panel display substrate having coated thereon a polymer, photoresist or resist relief image of the invention. Other aspects of the ii are disclosed infra. DETAILED DESCRIPTION OF THE INVENTION As discussed above, polymers of the invention contain a heteroahcyclic rii is preferably fused to a polymer backbone. The fused heterocyclic ring units cont or more oxygen and/or sulfur atoms. By stating herein that a cyclic group is fuse< polymer backbone, it is meant that two ring members of the cyclic group, typicall adjacent carbon atoms of the cyclic group, are also part of the polymer backbone, fused ring can be provided by polymerizing a cyclic monomer that has an endocy double bond. The oxygen and/or sulfur atoms of the heteroahcyclic ring are preferably < ring members (bi-radical linkages), rather than e.g. a multiple bond group such as or thioketo ring member. Also, less preferred are groups that contain any such sa groups such as a ketone or other carbonyl including ester, lactone, anhydride, etc. Preferred oxygen ring polymer units will be free of other hetero atoms sue sulfur (i.e. only oxygen and carbon ring members). Typically, the oxygen ring u] contain a single oxygen ring atom and may have one or more ring substituents. A discussed above, it has been found that such ring substituents can significantly en substrate adhesion. Additionally, an oxygen heteroahcyclic group will be present in a polyme: together with polymerized carbon alicyclic compounds such as optionally substiti norbornene. As referred to herein, the term "carbon alicyclic group" means each member of the non-aromatic group is carbon. The carbon alicyclic group can hav more endocyclic carbon-carbon double bonds, provided the ring is not aromatic. Preferred polymers of the invention that contain oxygen heteroahcyclic u comprise a structure of the following Formula I: wherein X, Y, and each Z are each independently carbon or oxygen, with ; one of X, Y or Z being oxygen, and preferably no more than two of X, Y and Z b< oxygen; Q represents an optionally substituted carbon alicyclic ring fused to the po backbone (i.e. two Q ring members being adjacent carbons of the polymer backbc the alicyclic ring suitably having from about 5 to about 18 carbon atoms and is su single ring (e.g. cyclopentyl, cyclohexyl or cycloheptyl), or more preferably Q is polycyclic e.g. and contain 2, 3, 4 or more bridged, fused or otherwise linlced ring preferred substituents of a substituted Q group include photoacid-labile moieties s photoacid-labile ester; each R is the same or different non-hydrogen substituent such as cyano; optionally substituted alkyl preferably having 1 to about 10 carbon atoms; option. substituted alkanoyl preferably having 1 to about 10 carbon atoms; optionally sub alkoxy preferably having 1 to about 10 carbon atoms; optionally substituted allcyri preferably having 1 to about 10 carbon atoms; optionally substituted alkylsulfmyl preferably 1 to about 10 carbon atoms; optionally substituted alkylsulfonyl prefer; having 1 to about 10 carbon atoms; optionally substituted carboxy preferably hav< about 10 carbon atoms (which includes groups such as -COOR' where R' is H or 8 alkyl, including esters that are substantially non-reactive with photoacid); a phot, labile group such as a photoacid-labile ester e.g. a tert-butyl ester and the like; etc m is 1 (to provide a fused five-membered ring), 2 (to provide a fused six- membered ring), 3 (to provide a fused seven-membered ring), or 4 (to provide a fi eight-membered ring); n is an integer of from 0 (i.e. no R ring substituents), 1 (i.e. a single R ring substituent) to the maximum possible value permitted by the valences of the ring members, and preferably n is 0, 1, 2, 3, 4 or 5 , and more preferably n is 0, 1, 2 or p is the mole fraction of the fused oxygen ring units based on total units in polymer; and r is the mole fraction of the fused carbon alicyclic ring units based o units in the polymer, and p and r are each greater than zero. As discussed above, preferred carbon alicyclic ring units are polymerized optionally substituted norbornene groups. Thus, preferred polymers that contain c heteroalicyclic units comprise a structure of the following Formula IA: wherein X, Y, Z, R, m and n are the same specified for Formula I above; R 1 and R 2 are each independently hydrogen or a non-hydrogen substituent halo (F, Cl, Br, I), nitro, cyano, optionally substituted alkyl (including cycloalkyl) preferably having from 1 to about 16 carbons; optionally substituted alkoxy prefei having from 1 to about 16 carbons; optionally substituted alkylthio preferably hav from 1 to about 16 carbons; optionally substituted carboxy preferably have 1 to ab carbon atoms (which includes groups such as -COOR' where R' is H or Cι. 8 alkyl, including esters that are substantially non-reactive with photoacid); a lactone; an anhydride such as an itaconic anhydride group; a photoacid-labile group such as a photoacid-labile ester, particularly a photoacid-labile ester moiety with a tertiary ε group or a non-cyclic group such as t-butyl; and the like, or R ! and R 2 may be talcs together to form one or more rings fused to the depicted norbomyl ring; p is the mole fraction of the fused oxygen ring units based on total units in polymer; and r is the mole fraction of the fused optionally substituted norbomene units based on total units in the polymer, and p and r are each greater than zero. Particularly preferred oxygen ring polymer units include those that have fi six ring members and an oxygen ring member adjacent to the polymer backbone. Accordingly, preferred are polymers that comprise a structure of the following Fo LB: wherein each Z' is independently oxygen, sulfur or carbon, and preferably is carbon; m' is 1, 2, 3 or 4; and R and n are each the same as defined in Formula and preferably n is 0, 1, 2, 3, 4 or 5, and more preferably n is 0, 1, 2 or 3; Q is the same as defined in Formula I; p is the mole fraction of the fused oxygen ring units based on total units in polymer; and r is the mole fraction of the fused carbon alicyclic ring units based o units in the polymer, and p and r are each greater than zero. Preferred polymers of Formula IB contain polymerized norbomene units, < polymers that comprise a structure of the following Formula IC: wherein Z', m', R, n, and p are the same as defined in Formula IB; and R 1 , R 2 and r are the same as defined in Formula IA. Preferred sulfur ring polymer units also will be free of other hetero atoms : oxygen (i.e. only sulfur and carbon ring members), or will contain only one or tw< hetero atoms such as oxygen, typically only one additional heteroatom such as ox Preferred sulfur ring polymer units include those of the following Formula wherein X, Y, and each Z are each independently carbon, oxygen or sulfui at least one of X, Y or Z being sulfur, and preferably no more than two of X, Y an being sulfur; each R is the same or different non-hydrogen substituent such as cyano; optionally substituted alkyl preferably having 1 to about 10 carbon atoms; optionε substituted alkanoyl preferably having 1 to about 10 carbon atoms; optionally sub alkoxy preferably having 1 to about 10 carbon atoms; optionally substituted alky 11 preferably having 1 to about 10 carbon atoms; optionally substituted alkylsulfinyl preferably 1 to about 10 carbon atoms; optionally substituted alkylsulfonyl prefer; having 1 to about 10 carbon atoms; optionally substituted carboxy preferably have about 10 carbon atoms (which includes groups such as -COOR' where R' is H or 8 alkyl, including esters that are substantially non-reactive with photoacid); a photc labile group such as a photoacid-labile ester e.g. a tert-butyl ester and the like; etc m is 1 (to provide a fused five-membered ring), 2 (to provide a fused six- membered ring), 3 (to provide a fused seven-membered ring) or 4 (to provide a fu eight-membered ring); n is an integer of 0 (no R substituents present), 1 (i.e. a single R ring subst to the maximum possible substitution permitted by the valences of the ring memb preferably n is 0, 1, 2, 3, 4 or 5 , and more preferably n is 0, 1, 2 or 3; and p is greater than zero and is the mole fraction of the fused sulfur ring units on total units in the polymer. Particularly sulfur ring polymer units include those that have five, six or se ring members and an sulfur ring member adjacent to the polymer backbone, such of the following Formula IIA: wherein Y is the same as specified for Formula I above; wherein each Z' is independently carbon, oxygen, or sulfur; and preferabb. is carbon; m' is 1, 2, 3 or 4; and R and n are each the same as defined in Formula and preferably n is 0, 1, 2, 3, 4 or 5, and more preferably n is 0, 1, 2 or 3; and p is greater than zero and is the mole fraction of the fused sulfur ring units on total units in the polymer. Polymers of the invention also may contain oxygen or sulfur ring groups tl spaced from the polymer backbone. The spaced oxygen or sulfur ring group suita contain a single ring, although polycyclic rings that contain one or more oxygen o ring members also will be suitable. Less preferred are groups where sulfur or oxy a bridgehead atom of a polycyclic group, particularly a bridgehead of a bicyclic gi such as a oxonorbornyl or thionorbonyl group, especially if such oxonorbornyl or thionorbonyl group is present as part of an ester moiety. For example, suitable spaced oxygen and/or sulfur ring groups of polymer invention include those of the following Formula III: wherein W is a linker; X, Y, and each Z are each independently carbon, o> or sulfur, with at least one of X, Y or Z being oxygen or sulfur; each R is the same or different non-hydrogen substituent such as those nor hydrogen substituents specified for R in Fonnula I above; m is 1, 2, 3, 4 or 5; n is an integer of from 0 to the maximum value substiti permitted by the valences of the ring members; and p is the mole percent of the ur the polymer. Typical W linker groups of Formula III include e.g. optionally substituted alkylene particularly optionally substituted d-s alkylene; optionally substituted alkenylene particularly ptionally substituted C . 8 alkenylene; optionally substitute alkynylene particularly optionally substituted C 2 . 8 alkynylene; optionally substiuri heteroalkylene particularly optionally substituted -s heteroalkylene; optionally substituted heteroalkenylene particularly optionally substituted C 2 - 8 heteroalkenyl optionally substituted heteroalkynylene particularly optionally substituted C 2 - 8 heteroalkynylene; an ester linkage (i.e. -C(=O)O); and the like. In Formula III, tl spaced oxygen or sulfur ring group may be a component of a photoacid-labile gro such as a photoacid-labile ester group. Such groups may be provided by polymer of the corresponding acrylate or methacrylate groups. Preferably, a sulfur heteroahcyclic group will be present in a polymer wit! polymerized carbon alicyclic olefin compounds. More specifically, preferred pol of the invention include those that comprise a structure of the following Formula . ' wherein X, Y, Z, R, m, n and p are each the same as defined in Formula II Q and r are the same as defined for Formula I above. Preferred carbon alicyclic ring units are polymerized optionally substitute< norbomene groups. Thus, preferred polymers that contain sulfur heteroahcyclic τ comprise a structure of the following Formula IVA: wherein X, Y, Z, R, m and n are the same specified for Formula II above; R 1 and R 2 are the same as defined in Formula IA above; p is the mole fraction of the fused sulfur ring units based on total units in t polymer; and r is the mole fraction of the fused optionally substituted norbomene units based on total units in the polymer, and p and r are each greater than zero. Particularly preferred sulfur ring polymer units include those that have fiv seven or eight ring members and a sulfur ring member adjacent to the polymer ba Accordingly, preferred are polymers that comprise a structure of the following Fo IVB: wherein each Z' is independently oxygen, sulfur or carbon, and preferably carbon; m' is 1, 2, 3 or 4; and R and n are each the same as defined in Formula I ε and preferably n is 0, 1, 2, 3, 4 or 5, and more preferably n is 1, 2 or 3; Q is the same as defined in Formula I; p is the mole fraction of the fused sulfur ring units based on total units in t polymer; and r is the mole fraction of the fused carbon alicyclic ring units based c units in the polymer, and p and r are each greater than zero. Preferred polymers of Formula IVB contain polymerized norbomene units polymers that comprise a structure of the following Formula IVC: wherein Z', m', R, n, and p are the same as defined in Formula IVB; and R 1 , R 2 and r are the same as defined in Formula I A. In the above Formulae I, IA, IB, IC, II, IIA, III, IV, IVA, IVB and IVC, ar below Formulae V, VI and VII (together sometimes referred to herein simply as " formulae" or similar phrase), preferably R substituents of the depicted heteroalicy are electron-donating groups such as optionally substituted alkyl, optionally subst alkoxy or optionally substituted allcylthio. Such electron-donating groups can fac polymerization of the corresponding vinyl heteroahcyclic monomer. Preferred polymers of the invention will contain at least about 2 to 5 mole of fused heteroahcyclic units based on total units of the polymer; more preferably about 5 to 50 mole percent of fused heteroahcyclic units based on total units of th polymer; still more preferably from about 5 or 10 to about 40 or 50 percent of fus heteroahcyclic units based on total units of the polymer. Preferred polymers of the invention will contain at least about 2 to 5 mole of carbon alicyclic units based on total units of the polymer; more preferably fron 5 to 50 mole percent of fused carbon alicyclic units based on total units of the pol still more preferably from about 5 or 10 to about 25 or 30 percent of fused carbon alicyclic units based on total units of the polymer. In polymers of the invention that contain only heteroahcyclic units and ca alicyclic units, preferably the heterocyclic units will be present in an amount of fr about 5 to about 90 or 95 mole percent based on total polymer units, and the carb< alicyclic units will be present in an amount of from about 5 to about 90 or 95 mol percent based on total polymer units. In polymers of the invention that consist of heteroahcyclic units, carbon a units and maleic anhydride units (i.e. heteroalicyclicxarbon alicyclic :maleic anfry terpolymers), preferably the heterocyclic units will be present in an amount of fro 5 to about 10, 20, 30, 40, 50, 60, 70 or 80 mole percent based on total polymer un carbon alicyclic units (such as optionally substituted norbomene) will be present i amount of from about 5 to about 10, 20, 30, 40, 50, 60, 70 or 80 mole percent bas total polymer units, and the maleic anhydride units will be present from about 5 t< 20, 30, 40 or 50 mole percent based on total polymer units; and more preferably t heterocyclic units will be present in an amount of from about 5 to about 10, 20, 3 50 or 60 mole percent based on total polymer units, the carbon alicyclic units will present in an amount of from about 5 to about 10, 20, 30, 40, 50 or 60 mole perce on total polymer units, and the maleic anhydride units will be present from about about 10, 15, 20, 25, 30, 40, or 50 mole percent based on total polymer units. In . terpolymers, suitably either or both the heteroahcyclic or carbon alicyclic units w: contain a photoacid labile substituents such as a photoacid-labile ester substituent In the above the above formulae, the R, R 1 and R 2 substituents each can be photoacid-labile groups. Photoacid-labile ester groups are generally preferred sue tert-butyl ester, or an ester containing a tertiary alicyclic group. Such photoacid-1 esters may be directly pendant from a heteroahcyclic or carbon alicyclic polymer (i.e. -C(=O)OR, where R is tert-butyl or other non-cyclic alkyl group, or a tertiaη alicyclic group), or the ester moieties may be spaced from the from a heteroalicyc carbon alicyclic polymer unit, e.g. by an optionally alkylene linkage (e.g. -(CH 2 )ι 8 C(=O)OR, where R is is tert-butyl or other non-cyclic alkyl group, or a tertiary a group). In any event, polymers of the invention preferably comprise contain one o repeat units that comprise a photoacid-labile group. As discussed with respect to substituents R, R 1 and R 2 of the above formulae, the photoacid-labile may be a substituent of a heteroahcyclic or carbon alicyclic ring member. Alternatively, am generally preferred, the photoacid-labile moiety will be a polymer repeat unit dist from repeat units containing a heteroahcyclic group. Preferred photoacid-labile groups are ester groups, particularly esters that a tertiary alicyclic hydrocarbon ester moiety. Preferred tertiary alicyclic hydrocar ester moieties are polycyclic groups such adamantyl, ethylfencyl or a tricyclo dec moiety. References herein to a "tertiary alicyclic ester group" or other similar ten indicate that a tertiary alicyclic ring carbon is covalently linked to the ester oxyge -C(=O)O-TR' where T is a tertiary ring carbon of alicyclic group R'. In at least r cases, preferably a tertiary ring carbon of the alicyclic moiety will be covalently 1 the ester oxygen, such as exemplified by the below-depicted specifically preferrec polymers. However, the tertiary carbon linked to the ester oxygen also can be exc to the alicyclic ring, typically where the alicyclic ring is one of the substituents of exocyclic tertiary carbon. Typically, the tertiary carbon linked to the ester oxyger substituted by the alicyclic ring itself, and/or one, two or three alkyl groups havin about 12 carbons, more typically 1 to about 8 carbons, even more typically 1, 2, 3 carbons. The alicyclic group also preferably will not contain aromatic substitutio alicyclic groups may be suitably monocyclic, or polycyclic, particularly bicyclic c tricyclic groups. Preferred alicyclic moieties (e.g. group TR' of -C(=O)O-TR') of photoac ester groups of polymers of the invention have rather large volume. It has been fc that such bulky alicyclic groups can provide enhanced resolution when used in copolymers of the invention. More particularly, preferred alicyclic groups of photoacid labile ester grou have a molecular volume of at least about 125 or about 130 A 3 , more preferably a molecular volume of at least about 135, 140, 150, 155, 160, 165, 170, 175, 180, 1 195, or 200 A 3 . Alicyclic groups larger than about 220 or 250 A 3 may be less pre in at least some applications. References herein to molecular volumes designate volumetric size as determined by standard computer modeling, which provides op chemical bond lengths and angles. A preferred computer program for determinin; molecular volume as referred to herein is Alchemy 2000, available from Tripos. ] further discussion of computer-based determination of molecular size, see T Omo Polymers for Advanced Technologies, volume 4, pp. 277-287. Particularly preferred tertiary alicyclic groups of photoacid-labile units inc the following, where the wavy line depicts a bond to the carboxyl oxygen of the e group, and R is suitably optionally substituted alkyl, particularly C . alkyl such ai methyl, ethyl, etc. Polymers of the invention also may contain photoacid-labile groups that d« contain an alicyclic moiety. For example, polymers of the invention may contain photoacid-labile ester units, such as a photoacid-labile alkyl ester. Generally, the carboxyl oxygen (i.e. the carboxyl oxygen as underlined as follows: -C(=O)O) of photoacid-labile ester will be covalently linked to the quaternary carbon. Branche photoacid-labile esters are generally preferred such as t-butyl and -C(CH ) 2 CH(C Polymers of the invention also may contain additional units such as cyano lactone units or anhydride units. For example, acrylonitrile or methacrylonitrile n polymerized to provide pendant cyano groups, or maleic anhydride may be polyn to provide a fused anhydride unit. Particularly preferred polymers of the invention include those that comprii structure of the following Formula V: wherein X, Y, Z, R, m and n are each the same as defined in Formula I ab< R 1 and R 2 are each independently hydrogen or a non-hydrogen substituent specified for R 1 and R 2 in Formula IA above; R 3 is hydrogen or alkyl, particularly Cι- 6 alkyl such as methyl; R 4 is a group that renders the depicted ester photoacid-labile, such as a terl alicyclic group as discussed above, or a branched non-cyclic optionally substitutei group, with the ester carboxyl group being directly bonded to a quaternary (i.e. nc hydrogen substituents) carbon atom; and a, b, c, and d are each greater than zero and are mole fractions of the respe polymer units. Preferred polymers of the invention also include those of the following Fo VI: wherein X, Y, Z, R, m and n are each the same as defined in Formula II ab R 1 and R 2 are each independently hydrogen or a non-hydrogen substituent such as specified for R 1 and R 2 in Formula IA above; R 3 is hydrogen or alkyl, particularly hydrogen or alkyl such as methyl R 4 is a group that renders the depicted ester photoacid-labile, such as a tert alicyclic group as discussed above, or a branched non-cyclic optionally substitute! group, with the ester carboxyl group being directly bonded to a quaternary (i.e. no hydrogen substituents) carbon atom; and a, b, c, and d are each greater than zero and are mole fractions of the respe polymer units. In each of above Formulae V and VI, preferably "a" (mole fraction of heterocyclic units) is from about 2 to 50 mole percent based on total polymer unit, preferably "a" is from about 2 to about 40 mole percent based on total polymer un still more preferably "a" is from about 2 to about 30 mole percent based on total p units. In each of above Formulae V and VI, preferably "b" (mole fraction of norl units) is from about 2 to 25 mole percent based on total polymer units; more prefe "b" is from about 2 to about 20 mole percent based on total polymer units; and sti preferably "b" is from about 2 to about 15 or 20 mole percent based on total polyr units. In each of above Formulae V and VI, preferably "c" (mole fraction of anh units) is from about 0 (i.e. no anhydride units) to 50 mole percent based on total p units; more preferably "c" is from about 2 to about 40 mole percent based on total polymer units. In each of above Formulae V and VI, preferably "d" (mole fraction of pho labile ester unit) is from about 2 to 70 mole percent based on total polymer units; preferably "d" is from about 5 or 10 to about 70 mole percent based on total polyr units; still more preferably "d" is from about 5 or 10 to about 50 mole percent bas total polymer units . Preferred heteroahcyclic units of Formulae V and VI are the same as desci above regarding Formulae IA and IIA respectively. As discussed above, polymers of the invention are preferably employed in photoresists imaged at short wavelengths, particularly sub-200 nm such as 193 nn 157 nm. Polymers also can be employed in photoresists imaged at higher wavelei such as 248 nm. For such higher wavelength applications, the polymer may suital contain aromatic units, e.g. polymerized styrene or hydrostyrene units. Specifically preferred polymers of the invention include those of the follow Formula VII: In Formula VII above, "Alicyclic LG" is the same as defined for alicyclic substituent R 4 in Formulae V and VI above and is preferably methyladamantyl, 8- 8-tricyclodecanyl, ethylfencyl and the like; R 1 is d- 8 alkyl, preferably d- 4 alkyl, moietty that forms a photoacid-labile group; R is suitably hydrogen or Cj- 8 alky 1 ' 9 1 1 as methyl, ethyl, propyl and the like; R and R are the same as defined for R an respectively in Formula IA above; and a, b, c and d are mole percents of the speci units in the polymer based on total polymer units. Preferably a (mole percent of o alicyclic units) is from 1 to about 5, 10, 20, 30, 40, 50 or 60 mole percent; b (mok percent of optionally substituted norbomene units) is from 1 to about 5, 10, 20, 30 or 60 mole percent; c (mole percent of maleic anhydride units) is from 1 to about 20, 30, 40, or 50 mole percent. Units d (acrylate photoacid-labile units) may be nt present (i.e. d is zero) where the heterocyclic or norbomene units contain a photoε labile units, or d may be suitably present at from about 2 to 10, 20, 30, 40 or 50 m percent based on total polymer units. As discussed, various moieties may be optionally substituted, including gr Formulae I, IA, II, IIA, III, IV, IVA, 1NB, INC, V, VI, and VII. A "substituted" substituent may be substituted at one or more available positions, typically 1 , 2, oi positions by one or more suitable groups such as e.g. halogen (particularly F, Cl o cyano; d_ 8 alkyl; d- 8 alkoxy; d- 8 alkylthio; d- 8 alkylsulfonyl; C 2 - 8 alkenyl; C 2 . 8 alkynyl; hydroxyl; nitro; alkanoyl such as a d_ 6 alkanoyl e.g. acyl and the like; et< Preferred alkanoyl groups, including as specified in the above formulae, w one or more keto groups, such as groups of the formula -C(=O)R" where R" is hydrogen or d_ 8 alkyl. Suitable lactone groups, including as specified in the abo\ formulae, include alpha-butyrolactone groups and the like. Polymers of the invention can be prepared by a variety of methods. One si method is an addition reaction which may include free radical polymerization, e.g reaction of selected monomers to provide the various units as discussed above in t presence of a radical initiator under an inert atmosphere (e.g., N 2 or argon) and at elevated temperatures such as about 70°C or greater, although reaction temperatur vary depending on the reactivity of the particular reagents employed and the boili of the reaction solvent (if a solvent is employed). Suitable reaction solvents inclu tetrahydrofuran, ethyl lactate and the like. Suitable reaction temperatures for any particular system can be readily determined empirically by those skilled in the art on the present disclosure. A variety of free radical initiators may be employed. I example, azo compounds may be employed such as azo-bis-2,4-dimethylpentanerι Peroxides, peresters, peracids and persulfates also could be employed. Other monomers that can be reacted to provide a polymer of the invention identified by those skilled in the art. For example, to provide photoacid-labile uni suitable monomers include e.g. methacrylate or acrylate that contains the appropri group substitution (e.g. tertiary alicyclic, t-butyl, etc.) on the carboxy oxygen of tl group. Maleic anhydride is a preferred reagent to provide fused anhydride polymi Itaconic anhydride also is a preferred reagent to provide anhydride polymer units, preferably where the itaconic anhydride has purified such as by extraction with chloroform prior to polymerization. Vinyl lactones are also preferred reagents, su alpha-butyrolactone. Some suitable vinyl (endocyclic double bond) heterocyclic monomers that polymerized to provide polymers of the invention include the following: Preferably a polymer of the invention will have a weight average molecula weight (Mw) of about 800 or 1,000 to about 100,000, more preferably about 2,00( about 30,000, still more preferably from about 2,000 to 15,000 or 20,000, with a molecular weight distribution (Mw/Mn) of about 3 or less, more preferably a mole weight distribution of about 2 or less. Molecular weights (either Mw or Mn) of th polymers of the invention are suitably determined by gel permeation chromatogra] Polymers of the invention used in photoresist formulations should contain sufficient amount of photogenerated acid labile ester groups to enable formation o relief images as desired. For instance, suitable amount of such acid labile ester gn will be at least 1 mole percent of total units of the polymer, more preferably about mole percent, still more typically about 3 to 30 or 40 mole percent of total polyme See the examples which follow for exemplary preferred polymers. As discussed above, the polymers of the invention are highly useful as a re binder component in photoresist compositions, particularly chemically-amplified j resists. Photoresists of the invention in general comprise a photoactive componen resin binder component that comprises a polymer as described above. The resin binder component should be used in an amount sufficient to renc coating layer of the resist developable with an aqueous alkaline developer. The resist compositions of the invention also comprise a photoacid genera "PAG") that is suitably employed in an jamount sufficient to generate a latent imaj coating layer of the resist upon exposure to activating radiation. Preferred PAGs imaging at 193 nm and 248 nm imaging include imidosulfonates such as compoui the following formula: wherein R is camphor, adamantane, alkyl (e.g. C M2 alkyl) and perfluoroalkyl sue perfluoro(Cι-ι 2 alkyl), particularly perfluorooctanesulfonate, perfluorononanesulfc and the like. A specifically preferred PAG is N-[(perfluorooctanesulfonyl)oxy]-5 norbomene-2,3-dicarboximide. Sulfonate compounds are also suitable PAGs, particularly sulfonate salts, suitable agents for 193 nm and 248 nm imaging are the following PAGS 1 and 2 Such sulfonate compounds can be prepared as disclosed in European Patei Application 96118111.2 (publication number 0783136), which details the synthes above PAG 1. Also suitable are the above two iodonium compounds complexed with ani other than the above-depicted camphorsulfonate groups. In particular, preferred a include those of the formula RSO 3 - where R is adamantane, alkyl (e.g. Cι-ι 2 alkyl perfluoroalkyl such as perfluoro (d-πalkyl), particularly perffuorooctanesulfonat perfluorobutanesulfonate and the like. Other known PAGS also may be employed in the resists of the invention. Particularly for 193 nm imaging, generally preferred are PAGS that do not contari aromatic groups, such as the above-mentioned imidosulfonates, in order to provid enhanced transparency. A preferred optional additive of resists of the invention is an added base, particularly tetrabutylammonium hydroxide (TBAH), or tetrabutylammonium lac which can enhance resolution of a developed resist relief image. For resists ima-s 193 nm, a preferred added base is a hindered amine such as diazabicyclo undecen diazabicyclononene. The added base is suitably used in relatively small amounts, about 0.03 to 5 percent by weight relative to the total solids. Photoresists of the invention also may contain other optional materials. F example, other optional additives include anti-striation agents, plasticizers, speed enhancers, etc. Such optional additives typically will be present in minor concent in a photoresist composition except for fillers and dyes which may be present in r< large concentrations, e.g., in amounts of from about 5 to 30 percent by weight of 1 weight of a resist's dry components. The resists of the invention can be readily prepared by those skilled in the example, a photoresist composition of the invention can be prepared by dissolvinj components of the photoresist in a suitable solvent such as, for example, ethyl lac ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, pro glycol monomethyl ether; propylene glycol monomethyl ether acetate and 3-etho. propionate. Typically, the solids content of the composition varies between aboui 35 percent by weight of the total weight of the photoresist composition. The resir and photoactive components should be present in amounts sufficient to provide a coating layer and formation of good quality latent and relief images. See the exar which follow for exemplary preferred amounts of resist components. The compositions of the invention are used in accordance with generally 1< procedures. The liquid coating compositions of the invention are applied to a sub such as by spinning, dipping, roller coating or other conventional coating techniqi When spin coating, the solids content of the coating solution can be adjusted to pi desired film thickness based upon the specific spinning equipment utilized, the vi: of the solution, the speed of the spinner and the amount of time allowed for spinn The resist compositions of the invention are suitably applied to substrates conventionally used in processes involving coating with photoresists. For examp ' composition may be applied over silicon wafers or silicon wafers coated with silic dioxide for the production of microprocessors and other integrated circuit compor Aluminum-aluminum oxide, gallium arsenide, ceramic, quartz, copper, glass subs and the like are also suitably employed. Following coating of the photoresist onto a surface, it is dried by heating t remove the solvent until preferably the photoresist coating is tack free. Thereafte imaged through a mask in conventional manner. The exposure is sufficient to eff activate the photoactive component of the photoresist system to produce a pattern image in the resist coating layer and, more specifically, the exposure energy typic ranges from about 1 to 100 mJ/cm 2 , dependent upon the exposure tool and the components of the photoresist composition. As discussed above, coating layers of the resist compositions of the invent preferably photoactivated by a short exposure wavelength, particularly a sub-300 sub-200 nm exposure wavelength. As discussed above, 193 nm is a particularly p exposure wavelength. 157 nm also is a preferred exposure wavelength. Howevei resist compositions of the invention also may be suitably imaged at higher wavele For example, a resin of the invention can be formulated with an appropriate PAG sensitizer if needed and imaged at higher wavelengths e.g. 248 nm or 365 nm. Following exposure, the film layer of the composition is preferably baked temperatures ranging from about 70°C to about 160°C. Thereafter, the film is dev The exposed resist film is rendered positive working by employing a polar develo preferably an aqueous based developer such as quaternary ammonium hydroxide solutions such as a tetra-alkyl ammonium hydroxide solution; various amine solut preferably a 0.26 N teframethylammonium hydroxide, such as ethyl amine, n-pro amine, diethyl amine, di-n-propyl amine, triethyl amine, or methyldiethyl amine; i amines such as diethanol amine or triethanol amine; cyclic amines such as pyrrole pyridine, etc. In general, development is in accordance with procedures recognize art. Following development of the photoresist coating over the substrate, the developed substrate may be selectively processed on those areas bared of resist, f example by chemically etching or plating substrate areas bared of resist in accord with procedures known in the art. For the manufacture of microelectronic substπ e.g., the manufacture of silicon dioxide wafers, suitable etchants include a gas etc e.g. a halogen plasma etchant such as a chlorine or fluorine-based etchant such a ι CF 4 /CHF etchant applied as a plasma stream. After such processing, resist may removed from the processed substrate using known stripping procedures. All documents mentioned herein are incorporated herein by reference. Th following non-limiting examples are illustrative of the invention. Examples 1-2: Polymer syntheses Example 1: Synthesis of tetrapolymer of: 2-(6-ethoxy)tetrahydropyran: norbornene:maleic anhydride:2-methyladmantyl (respective molar ratio of units o 10:20:30:40) Composition 10/20/30/40 A mixture of 2-methyladamantyl methacrylate (60.0 g), maleic anhydride g), norbomene (12.03 g), 3,4-dihydro-2-ethoxy-2-H-pyran (8.20 g) and V601 (photoinitiator; 3.73 g; 5 mole % of total monomers) in 99.07 g (l/l^monomer/sc of anhydride inhibitor free tetrahydrofuran was placed in a round-bottomed flask, stirring for 5 minutes (until all solids were dissolved in the solvent), the flask was a pre-heated 70°C oil bath. The reaction mixture was stirred at that temperature i hours. After cooling, 99.07 g of THF was added to the reaction mixture. The pol was isolated by precipitation into 2.0 L of hexane/isopropyl alcohol (1 : 1 wt.%). 1 suspension was stirred for 120 minutes. Then, the polymer was filtered off, and t fϊltered polymer was washed with an additionall 200 mL of hexane. The polymei dried in a vacuum oven at 40°C for overnight (about 16 hours). Yield = 76.3%. Example 2: Synthesis of tetrapolymer of: 2-(6-methoxy)tetrahydropyra norbornene:maleic anhdride:2-methyladmantyl (respective molar ratio of units of 10:20:30:40) Composition 10/20/30/40 The title polymer was prepared by the same general procedures as disclosi above in Example 1, except 7.31 g of 3,4-dihydro-2-methoxy-2-H-pyran was use< place of 3,4-dihydro-2-ethoxy-2-H-pyran. Yield of polymer was 78.4 %. Examples 3-6: Syntheses of monomers useful in preparation of polymers of the invention. Example 3 : EtTCD Methacrylate monomer synthesis 8-ethyl-8-tricyclodecanylmethacrylate (EtTCD methacrylate) was prepare following using the reagents and amounts thereof as specified in the following tal Material Amt (g) Amt (ml) Moles Sour TCD 150.22 ' 1.00 TC. Ethylmagnesiumchloride(25%) 339900..8855 -379.5 -1.10 ACR< Methacryloyl chloride 120.22 -112.4 -1.15 Aldri Tetrahydrofuran 480 540 Aldri All reaction glassware was dried in the oven overnight at 100°C. The glas: was set up and cooled under a stream of nitrogen. The reaction was carried out ur blanket of nitrogen. To a 2L 3N-RB flask fitted with a gas inlet, thermometer, overhead stirrer rubber septum was added 400g of ethylmagnesium chloride, 25 wt% solution in tetrahydrofuran (clear, amber solution) via a double tipped needle using nitrogen pressure. The mixture was cooled to -25 to -30°C using a dry ice/isopropanol bat] the ethylmagnesium chloride solution was cooling the 153.6g of tricyclodecane ( r was dissolved in 480g of tetrahydrofuran. To a 1L 3N-RB flask equipped with a g glass stopper and a rubber septum was added the 153.6g of TCD. The anhydrous, inhibitor free tetrahydrofuran was transferred to the 1L flask via a double tipped r using nitrogen pressure. When the ethylmagnesium chloride was at -25 to -30°C, TCD/THF solution was transferred over a 2hr period to the 2L 3N-RB flask contε the ethylmagnesium chloride via a double tipped needle using nitrogen pressure. ' cooling bath was removed and the reaction mixture was stirred for 2 hr. After stir 2 hr the mixture was again cooled to -25 to -30°C using a dry ice/isopropanol bat methacryloyl chloride (120.22g) was then added dropwise over a 1 hour period us 125ml pressure equalizing dropping funnel. The reaction was allowed to come to temperature with overnight stirring. A white precipitate developed from the clear colored reaction solution. Water (DI) was added until all of the salts had dissolve! (~500ml) and two distinct layer were seen. The layers were separated and the org (upper) layer was washed with 2x400ml DI water then dried over magnesium sul: THF was removed leaving 258g of an orange oil. The orange oil was dissolved in hexane then passed through a 400g silica gel plug which had been pre-conditionei hexane. The silica was washed with hexane until all of the product was removed ( filtrate on a TLC plate and illuminate under short UN). The hexane was removed 202.8g of an clear, colorless oil. Theoretical yield: 248.4g; yield: 81.6% Example 4: Synthesis of Norbomene Valerolactone A solution of valerolactone (50.1 g) in 150 mL of anhydrous THF was pla three-neck-bottomed flask at -78°C (Dry Ice/acetone). To it, solution of LDA (2. 2M) in 250 mL anhydrous THF was added dropwise. The reaction mixture was s this temperature for 4 hours. Then, the thermal cracking of paraformaldehyde (3( excess) was bubbled into the reaction mixture. After the paraformaldehyde was a cracked, the reaction mixture was stirred at the same bath and stirred for overnigh Then, the solvent was removed by rotary pump and the residue was added 500 ml CH2CI2 and washed with NaHCO3 ( ac l > sat & wa er several times (3 x 500mL combination organic solvent was dried over MgSO4 and the solvent was removec rotary pump. The desired product was distilled under vacuum (135-140°C/8mmF The methylene- valerolactone was dissolved in dichloromethane and fresh! cracked cyclopentadiene was added. The reaction mixture was stirred at room temperature for 3 hours, then heated to 40°C, and held at 40°C overnight. The reε mixture was then slowly cooled to room temperature. The methylene chloride wa removed under reduced pressure, leaving an oil. The crude oil was then distilled 1 reduced pressure to afford pure product. Example 5: Synthesis of 8-methyltricyclodecanyl methacrylate: A solution of 125 ml of 1.4 M methyl lithium (in ethyl ether)in 100 ml of was decanted into a three neck round-bottom flask at an ice- water bath. To it, a s of 24.00 g of tricyclo[5.2.1.0]decan-8-one in hexane was added dropwise. After ; the reaction mixture was stirred for 4 hours at 0°C. Then, a solution of 16 ml of methacroyl chloride in 100 ml of hexane was added dropwise at 0°C. After additi reaction mixture was stirred at the same bath for overnight (16 hours). After filte white salts, the organic layer was washed with water three times (3 x 300 ml). Tl washed organic layer was dried over anhydrous MgSO . The organic solvent was removed by a rotary pump to give the crude title monomer (23.5 g). The monom< purified by a flash column chromatography (purity >98%, silica gel with hexane). NMR: 6.05 (IH), 5.50 (IH), 1.95 (3H), 1.65 (3H), 2.25-0.85 (14H). Example 6: Synthesis of pinanyl methacrylate cis-Pinan-2-ol Pinanyl methacrylate (PinMA) Materials used: Procedure: All reaction glassware and needles were dried and flushed with dry N 2 bef and the reaction was carried out under nitrogen atmosphere. 1) Into a 500 mL 3-neck round-bottom-flask equipped with an addition funnel ar magnetic stirrer were added 15.43 g of cis-pinan-2-ol and 200 mL of dry CH 2 < (Stirred over CaH 2 overnight, then distilled and stored over activated molecul; sieves). The resulting colorless solution was cooled with an ice-water bath. 2) Triethylamine (12.14 g) was added through the addition funnel to the cooled ( solution over 10 min. After added, the resulting solution was kept in a dry-ice bath (-67 °C). 3) A CH 2 C1 2 (30 mL) solution of methacryloyl chloride (13.07 g) was added dπ over 20 min. The resulting orangish suspension was allowed to warm to room temperature and stirred for 2 h. 4) The chloride salts were filtered off. The filtrate was washed with saturated Nε solution (2 x 200 mL), then DI water (3 x 200 mL) , and dried over anhydrou; MgSO 4 . 5) The slightly yellow CH 2 C1 2 solution was concentrated on a rotary evaporator temperature kept below 35°) to yield a clear slightly yellow liquid product. Y 79%. The product was judged pure by NMR. Example 7: Photoresist preparation and lithographic processing A photoresist of the invention is prepared by mixing the following compo with amount expressed as weight percents based on total weight of the resist composition: Resist components Amount (wt. % based on totε Resin binder 28.2 Photoacid generator 0.52 Basic additive 0.03 Surfactant 0.03 The resin binder is the polymer of Example 2 above. The photoacid genei triphenylsulfonium triflate. The basic additive is triisopropnaol amine. The surfa Silwet (Dow Chemical). Those resist components were formulated at 16 wt. % s< a solvent of 2-heptatone. The formulated resist composition is spin coated onto HMDS vapor prime silicon wafers and softbaked via a vacuum hotplate at 130°C for 60 seconds. The coating layer is exposed through a photomask at 193 nm using an ISI microsteppe then the exposed coating layers are post-exposure baked (PEB) at about 130°C. 1 coated wafers are then treated with 0.26N aqueous tetramethylammonium hydrox solution to develop the imaged resist layer and provide a relief image. Highly resolved 0.13 μm equal lines and spaces (1 :1) were obtained. Example 8: Comparative example A resist formulation was prepared of essentially the same components and amounts thereof as in Example 7 above, but where the polymer (resin binder) did contain a polymerized ether, or other heteroahcyclic unit. The resist was process* described in Example 7. The smallest resolved equal lines and spaces (1:1) that c obtained were 0.14 μm. Example 9: Plasma etch tests Oxide plasma etch rates of polymers of the invention were examined. A first (comparative) terpolymer was tested for etch rates. That terpolyme contained polymerized units of p-hydroxystyrene, styrene and t-butylacrylate in respective molar ratios of 65:20:15. Three tetrapolymers of the invention (referred to below as Polymers 1, 2 ; respectively) having the following structure were then tested for etch rates. In Polymer 1, the molar ratio of polymer units a:b:c:d was 10 20 30 40. In Polymer 2, the molar ratio of polymer units a:b:c:d was 10 15 25 50. In Polymer 3, the molar ratio of polymer units a:b:c:d was 10 10 20 60. Polymer 1 exhibited three percent greater oxide etch rate resistance than tl comparative hydroxystyrene/styrene/t-butylacrylate terpolymer. Polymer 2 exhibi percent greater oxide etch rate resistance than the comparative hydroxystyrene/sty butylacrylate terpolymer. Polymer 3 exhibited eight percent greater etch rate resis than the comparative hydroxystyrene/styrene/t-butylacrylate terpolymer. The foregoing description of the invention is merely illustrative thereof, ar understood that variations and modification can be made without departing from t or scope of the invention as set forth in the following claims.

Claims: What is claimed is: 1. A photoresist composition comprising a photoactive component ar polymer that comprises: i) a heteroahcyclic group fused to the polymer backbone contains one or more oxygen or sulfur ring members; ii) a carbon alicyclic group the polymer backbone; and iii) a photoacid-labile moiety. 2. The photoresist of claim 1 wherein the heteroahcyclic group has ar oxygen ring member. 3. The photoresist of claim 1 wherein the heteroahcyclic group has a ring member. 4. The photoresist of any one of claims 1 through 3 wherein the carbc alicyclic group is a polymerized norbomene group. 5. The photoresist of any one of claims 1 through 4 wherein the heteroahcyclic group has a non-hydrogen ring substituent. 6. The photoresist of any one of claims 1 through 5 wherein the photc labile moiety is a substituent of the heteroahcyclic group and/or the carbon alicyc group. 7. The photoresist of any one of claims 1 through 6 wherein the phote labile moiety is a polymer unit separate from the heteroahcyclic group or the carb alicyclic group. 8. The photoresist of claim 7 wherein the polymer comprises a polym acrylate that comprises a photoacid-labile moiety. 9. The photoresist of any one of claims 1 through 8 wherein the polyr further comprises lactone and/or anhydride units. 10. The photoresist of any one of claims 1 through 9 wherein the poly; further comprises maleic anhydride units. 11. The photoresist of any one of claims 1 through 10 wherein the heteroahcyclic group fused to the polymer backbone does not contain an unsatur. oxygen. 12. The photoresist of any one of claims 1 through 11 wherein the heteroahcyclic group fused to the polymer backbone does not contain an unsaturε sulfur. 13. The photoresist of any one of claims 1 through 11 wherein the heteroahcyclic group fused to the polymer backbone is not an anhydride or lactor " 14. The photoresist of claim 1 wherein the polymer comprises a struct the following Formula I: wherein X, Y, and each Z are each independently carbon or oxygen, with one of X, Y or Z being oxygen; Q represents an optionally substituted carbon alicyclic ring with two ring members being adjacent carbons of the polymer backbone; each R is the same or different non-hydrogen substituent; m is 1, 2, 3 or 4; n is an integer of from 0 to the maximum value permitted by the valences * ring members; p is the mole fraction of the fused oxygen ring units based on total units in polymer; and r is the mole fraction of the fused carbon alicyclic ring units based o units in the polymer, and p and r are each greater than zero. 15. The photoresist of claim 1 wherein the polymer comprises a struct! the following Formula IA: wherein X, Y, and each Z are each independently carbon or oxygen, with ; one of X, Y or Z being oxygen; each R is the same or different non-hydrogen substituent; m is 1, 2, 3 or 4; n is an integer of from 0 to the maximum value permitted by the valences ring members; R 1 and R 2 are each independently hydrogen or a non-hydrogen substituent p is the mole fraction of the fused oxygen ring units based on total units in polymer; and r is the mole fraction of the fused optionally substituted norbomene units based on total units in the polymer, and p and r are each greater than zero. 16. The photoresist of claim 1 wherein the polymer comprises a strud the following Formula IB: wherein Z' is oxygen, sulfur or carbon; m' is 1, 2, 3 or 4; Q represents an optionally substituted carbon alicyclic ring with two ring members being adjacent carbons of the polymer backbone; each R is the same or different non-hydrogen substituent; n is an integer of from 0 to the maximum value permitted by the valences ring members; p is the mole fraction of the fused oxygen ring units based on total units ii polymer; and r is the mole fraction of the fused carbon alicyclic ring units based ' units in the polymer, and p and r are each greater than zero. 17. The photoresist of claim 1 wherein the polymer comprises a strucl the following Formula IC: wherein Z' is oxygen, sulfur or carbon; m' is 1, 2, 3 or 4; each R is the same or different non-hydrogen substituent; n is an integer of from 0 to the maximum value substitution permitted by valences of the ring members; R 1 and R 2 are each independently hydrogen or a non-hydrogen substituen p is the mole fraction of the fused oxygen ring units based on total units ii polymer; and r is the mole fraction of the fused carbon alicyclic ring units based < units in the polymer, and p and r are each greater than zero. 18. The photoresist of claim 1 wherein the polymer comprises units o: following Formula III: wherein W is a linker; wherein X, Y, and each Z are each independently carbon, oxygen, or sulfi at least one of X, Y or Z being oxygen or sulfur; each R is the same or different non-hydrogen substituent; m is 1, 2, 3, 4 or 5; n is an integer of from 0 to the maximum value substil peπnitted by the valences of the ring members; and p is the mole percent of the u the polymer. 19. The photoresist of claim 1 wherein the polymer comprises a struct the following Formula IV: wherein X, Y, and each Z are each independently carbon or sulfur, with a one of X, Y or Z being sulfur; Q represents an optionally substituted carbon alicyclic ring with two ring members being adjacent carbons of the polymer backbone; each R is the same or different non-hydrogen substituent; m is 1, 2 or 3; n is an integer of from 0 to the maximum value permitted by the valences ring members; p is the mole fraction of the fused oxygen ring units based on total units n polymer; and r is the mole fraction of the fused carbon alicyclic ring units based < units in the polymer, and p and r are each greater than zero. 20. The photoresist of claim 1 wherein the polymer comprises a struct the following Formula IVA: wherein X, Y, and each Z are each independently carbon, oxygen, or sulfj at least one of X, Y or Z being sulfur; each R is the same or different non-hydrogen substituent; m is 1, 2 or 3; n is an integer of from 0 to the maximum value permitted by the valences ring members; R 1 and R 2 are each independently hydrogen or a non-hydrogen substituen p is the mole fraction of the fused oxygen ring units based on total units ii polymer; and r is the mole fraction of the fused optionally substituted norbomene units based on total units in the polymer, and p and r are each greater than zero. 21. The photoresist of claim 1 wherein the polymer comprises a struct the following Formula IVB: wherein each Z' is oxygen, sulfur or carbon; m' is 1, 2, 3 or 4; Q represents an optionally substituted carbon alicyclic ring with two ring members being adjacent carbons of the polymer backbone; each R is the same or different non-hydrogen substituent; n is an integer of from 0 to the maximum value permitted by the valences ring members; p is the mole fraction of the fused oxygen ring units based on total units ir polymer; and r is the mole fraction of the fused carbon alicyclic ring units based ( units in the polymer, and p and r are each greater than zero. 22. The photoresist of claim 1 wherein the polymer comprises a stmct the following Formula IVC: wherein Z' is oxygen, sulfur or carbon; m' is 1, 2, 3 or 4; each R is the same or different non-hydrogen substituent; n is an integer of from 0 to the maximum value substitution permitted by 1 valences of the ring members; l * • R and R are each independently hydrogen or a non-hydrogen substituent p is the mole fraction of the fused oxygen ring units based on total units ir polymer; and r is the mole fraction of the fused carbon alicyclic ring units based c units in the polymer, and p and r are each greater than zero. 23. The photoresist of any one of claims 1 through 22 wherein the pol; a tetrapolymer or a pentapolymer. 24. The photoresist of any one of claims 1 through 23 wherein the pol; completely free of aromatic groups. 25. A photoresist composition comprising a photoactive component ar polymer that comprises i) a heteroahcyclic group that contains one or more sulfur members; and ii) a photoacid-labile moiety. 26. The photoresist of claim 25 wherein the photoacid-labile moiety is polymer unit separate from the heteroahcyclic group. 27. The photoresist of claim 25 wherein the polymer comprises a poly acrylate that comprises a photoacid-labile moiety. 28. The photoresist of claim 25 wherein the polymer contains units of following Formula II: wherein X, Y, and each Z are each independently carbon, oxygen or sulfu at least one of X, Y or Z being sulfur; each R is the same or different non-hydrog substituent; m is 1, 2, 3 or 4; n is an integer of 0 to the maximum value permitted valences of the ring members; and p is greater than zero and is the mole percent c units in the polymer. 29. The photoresist of claim 25 wherein the polymer contains units of following Formula IIA: -) P IIA Y. ..S > m . ( R )π wherein Y and Z' are each independently carbon, oxygen or sulfur; m' is or 4; each R is the same or different non-hydrogen substituent; n is an integer of ( maximum value permitted by the valences of the ring members; and p is greater t and is the mole percent of the units in the polymer. 30. The photoresist of claim 25 wherein the polymer comprises units e following Formula III: III wherein W is a linker; wherein X, Y, and each Z are each independently carbon, oxygen, or sulfi at least one of X, Y or Z being oxygen or sulfur; each R is the same or different non-hydrogen substituent; m is 1, 2, 3, 4 or 5; n is an integer of from 0 to the maximum value substi permitted by the valences of the ring members; and p is greater than zero and is tl percent of the units in the polymer. 31. The photoresist of any one of claims 25 through 30 wherein the pc further comprises one or more units selected from the group consisting of carbon alicyclic, lactone, and anhydride. 32. The photoresist of any one of claims 25 through 31 wherein the pc comprises norbomene units. 33. The photoresist of any one of claims 25 through 32 wherein the pc a tetrapolymer or a pentapolymer. 34. The photoresist of any one of claims 25 through 33 wherein the pc completely free of aromatic groups. 35. A method of forming a positive photoresist relief image, comprisii (a) applying a coating layer of a photoresist of any one of claims 1 thr on a substrate; and (b) exposing and developing the photoresist layer to yield a relief ima 36. The method of claim 35 wherein the photoresist layer is exposed ' radiation having a wavelength of less than about 200 nm. 37. The method of claim 35 wherein the photoresist layer is exposed ' radiation having a wavelength of about 193 nm. 38. A method of forming a positive photoresist relief image, comprisii (a) applying a coating layer of a photoresist of any one of claims 25 tl 34 on a substrate; and (b) exposing and developing the photoresist layer to yield a relief ima 39. The method of claim 38 wherein the photoresist layer is exposed ' radiation having a wavelength of less than about 200 nm. 40. The method of claim 38 wherein the photoresist layer is exposed ' radiation having a wavelength of about 193 mn. 41. An article of manufacture comprising a microelectronic wafer sub flat panel display substrate having coated thereon a layer of the photoresist compi of any one of claims 1 through 24. 42. An article of manufacture comprising a microelectronic wafer sub flat panel display substrate having coated thereon a layer of the photoresist compi of any one of claims 25 through 34. 43. A polymer that comprises: i) a heteroahcyclic group fused to the p backbone and that contains one or more oxygen or sulfur ring members; ii) a cart alicyclic group fused to the polymer backbone; and iii) a photoacid-labile moiety 44. A polymer that comprises: i) a heteroahcyclic group that contains more sulfur ring members; and ii) a photoacid-labile group. 45. A polymer that comprises units of the following Formula III: wherein W is a linker; wherein X, Y, and each Z are each independently carbon, oxygen, or sulf at least one of X, Y or Z being oxygen or sulfur; each R is the same or different non-hydrogen substituent; m is 1, 2, 4 or 5; n is an integer of from 0 to the maximum value substitut permitted by the valences of the ring members; and p is the mole percent of the u the polymer.

Inventors: BARCLAY GEORGE G, YUEH WANG, BARCLAY, GEORGE, G., YUEH, WANG
Applicants: BARCLAY GEORGE G, SHIPLEY CO LLC, YUEH WANG, BARCLAY, GEORGE, G., SHIPLEY COMPANY, L.L.C., YUEH, WANG
Application year: 2001
Main classification: G03F7
IPC codes: C08F220, G03F7, H01L21