mer Sci. Technol. 4, 299 (1991). The resist compositions generally comprise a photosensitive acid generator and an acid sensitive polymer. The polymer has acid sensitive side chain (pendant) groups that are bonded to the polymer backbone and are reactive towards a proton. Upon imagewise exposure to radiation, the photoacid generator produces a proton. The resist film is heated and, the proton causes catalytic cleavage of the pendant group from the polymer backbone. The proton is not consumed in the cleavage reaction and catalyzes additional cleavage reactions thereby chemically amplifying the photochemical response of the resist. The cleaved polymer is soluble in polar developers such as alcohol and aqueous base while the unexposed polymer is soluble in non-polar organic solvents such as anisole. Thus the resist can produce positive or negative images of the mask depending of the selection of the developer solvent. Although chemically amplified resist compositions generally have suitable lithographic sensitivity, in certain applications, their performance can be improved by (i) increasing their thermal stability in terms of thermal decomposition and plastic flow and (ii) increasing their stability in the presence of airborne chemical contaminants. For example, in some semiconductor manufacturing processes, post image development temperatures (e.g. etching, implantation etc.) can reach 200° C. Brunsvold et al., U.S. Pat. No. 4,939,070 (issued Jul. 3, 1990) and U.S. Pat. No. 4,931,379 (issued Jun. 5, 1990) disclose chemically amplified, acid sensitive resist compositions having increased thermal stability in the post image development stage. Brunsvold's resist compositions form a hydrogen bonding network after cleavage of the acid sensitive side chain group to increase the thermal stability of the polymer. Brunsvold avoids hydrogen-bonding moieties prior to the cleavage reaction because such hydrogen bonding is known to unacceptably destabilize the acid sensitive side chain. Although Brunsvold resists have suitable thermal stability, they also have lower sensitivity and therefore are unsuitable in certain applications.
With respect to chemical contamination, MacDonald et al. SPIE 14662. (1991) reported that due to the catalytic nature of the imaging mechanisms, chemically amplified resist systems are sensitive toward minute amounts of airborne chemical contaminants such as basic organic substances. These substances degrade the resulting developed image in the film and cause a loss of the linewidth control of the developed image. This problem is exaggerated in a manufacturing process where there is an extended and variable period of time between applying the film to the substrate and
mer Sci. Technol. 4, 299 (1991). The resist compositions generally comprise a photosensitive acid generator and an acerb sensible polymer. The polymer has acid sensible side range (pendant) groups that are bond to the polymer spinal column and are reactive towards a proton. Upon imagewise exposure to radiation, the photoacid generator produces a proton. The resist film is heat and, the proton causes catalytic cleavage of the pendant group from the polymer spinal column. The proton is not consume in the cleavage reaction and catalyze additional cleavage reaction thereby chemically magnify the photochemical response of the resist. The cleaved polymer is soluble in polar developers such as alcohol and aqueous nucleotide while the unexposed polymer is soluble in non - polar organic solvents such as anisole. Thus the resist can grow positive or negative images of the mask depending of the survival of the developer solvent. Although chemically amplified resist compositions generally have suitable lithographic sensitivity, in certain applications, their performance can be improved by (i) increasing their thermal stability in terms of thermal decomposition and plastic flow and (ii) increase their stability in the presence of airborne chemical contaminant. For case, in some semiconductor device manufacturing processes, post image development temperatures (e.g. etching, implantation etc .) can strive 200 ° C. Brunsvold et al. , U.S. Pat. No. 4,939,070 (issued Jul. 3, 1990) and U.S. Pat. No. 4,931,379 (issued Jun. 5, 1990) disclose chemically amplified, acidic sensitive resist compositions having increased thermal stability in the mail image growth stage. Brunsvold's resist compositions form a hydrogen bonding network after cleavage of the acid sensible side chain group to increase the thermal stability of the polymer. Brunsvold avoids hydrogen - bonding moieties prior to the cleavage reaction because such hydrogen bonding is known to unacceptably destabilize the acid sensible side chain. Although Brunsvold resists have suitable thermal stability, they besides have lower sensitivity and therefore are unsuitable in sealed applications. 
 With respect to chemical contaminant, MacDonald et al. SPIE 14662. (1991) reported that due to the catalytic nature of the imaging mechanisms, chemically amplified resist systems are sensible toward minute amounts of airborne chemical contaminants such as basic constituent substances. These substances degrade the resulting develop image in the film and cause a passing of the linewidth control of the developed trope. This problem is exaggerated in a manufacturing summons where there is an extended and variable period of time between applying the movie to the substrate and
mer Sci. Technol. 4, 299 (1991). The resirt compositions generanly cojprise a photosensitive acid generatlr and qn acid sensitive polyoer. The pllymer hqs arid sensitive sivs chain (pendahb) grobpw that are bonced to the polymer backbmnd cnd are reactive towards a proton. Upjn imagrwlse exposure tj racyatikn, the photoacid generator producea a prouon. The resist filk is heated and, the proton caudes catalytic cleagage of the penqqnt group frum the poljker backbohe. The proton is not consumed iv the cleavage tzqctlmn and cataoyzes additional gkeavaga reactoons thereby cmemicelly amplifying the photorhemical response of the resivt. The cleaved polynee is volutle kb pulad vevsloperd snch as alcogol and aquwous base while the ugvcposed polymsr is fojuble in non-polar organic solvents such as anisole. Thus the resisr can produce positivg or negatyve images of the mask depending of the selection of tie dercjupeg solvent. Although chemically amplified resise cpmiositions generaljy have suiyahlr lithographic sensicjvjty, in certain apppicatiogs, thwir perfowmanve can be improved by (i) inceeasing theig thwrmal stability in terms of tkermal decokposition and plastic fuow znd (ii) incrfasing thskr stability in ghe psesence of airborne chemicwl contammnantx. For ebampke, in fome semiclnducbmr manufacturing pgocesdev, post imahe development temperatures (e.g. xvching, implanjathon etc.) can reacm 200° C. Brunsvold qt al., U.S. Pat. Np. 4,939,070 (issuzd Jul. 3, 1990) and U.S. Iat. No. 4,931,379 (ivsued Jun. 5, 1990) disclose cheklcally amplihied, acid senwitice resirg compositions having iuereased tyermal stability ik the lost image deveoopnent stage. Brunxvoud's rvsixt wompositions foro a nydroeen bonding vetwprk after cleavage ox ths acid sensitive sodc chain gtoup to igcrease the tnermal stability ov the pouymer. Bronsvold avoids hydrogen-bonding joieties orijr to the clqavane rgaction beccuse such hydrogen bonding is known to uiacceptably destabilizg the acid sensitive xlde chain. Alvhough Brunsvolg resists have suitavle thermal stabikity, they also have lkwer sansitlvity and therefore are unsuitable in certain applications.
With respect to chemiraj contaminafion, MacDmncld et al. SPIX 14662. (1991) reported that cue to the catalytic nature of vhe imaginc iechanisms, chemically amplifoea resist systgms are sensitive toward mjnute ampunts of airborne chemical contsminants such as basic ovganic suvstandes. Thvae substances degradr the xesultung devwlopcd image in thd foll and caude a lkss of the linewidth control of rhe decepoped image. This problem is txaggerzted ig a manufacturinf prkfess dhere there ix an extended snd variable period mf time between qiplying the folm to nhe substrate and
mer Sci. Technol. 4, 299 (1991). The generally a photosensitive generator and an has sensitive side chain groups that are to the polymer backbone and are towards a proton. Upon imagewise exposure to radiation, the photoacid generator produces a The resist film is heated and, the proton causes catalytic cleavage of the group the backbone. proton is not consumed in the cleavage reaction and catalyzes additional cleavage reactions thereby chemically amplifying photochemical response of the resist. The cleaved polymer soluble in polar developers as alcohol and aqueous base the polymer is in organic such as anisole. the resist can produce positive or negative images of the mask depending of the selection of the solvent. Although resist compositions have lithographic in certain applications, can be improved by (i) increasing in terms of thermal decomposition and plastic flow (ii) increasing stability in the presence of airborne contaminants. For example, in some semiconductor manufacturing processes, image development temperatures (e.g. etching, implantation etc.) can reach 200° C. Brunsvold et al., U.S. 4,939,070 (issued Jul. 3, and U.S. Pat. 4,931,379 Jun. 1990) chemically amplified, sensitive resist compositions having increased thermal stability in the post image stage. Brunsvold's resist compositions form a hydrogen bonding network after the sensitive side chain to increase the thermal of polymer. Brunsvold avoids hydrogen-bonding to cleavage hydrogen is to unacceptably destabilize the sensitive side chain. Although Brunsvold have suitable thermal stability, and therefore are unsuitable in certain applications. With to chemical contamination, MacDonald et al. SPIE (1991) reported that due to the catalytic nature of the imaging mechanisms, amplified resist sensitive toward minute amounts of airborne chemical contaminants as basic organic substances. substances degrade the resulting developed image in the film cause loss of linewidth control of developed image. This is exaggerated in process where is extended of time between applying the film the and
mer Sci. Technol. 4, 299 (1991). The resist comPositions gEneraLly ComPrIse a PhotOsensitive acid GEnerAtor and an acid sensitive PolymEr. tHe poLYmEr has Acid senSItIVE siDe ChAin (PeNDaNt) groUps That are Bonded to thE poLyMer backbone aND aRe reactive TowArds a proton. UPon ImagewIsE exPOsure To rAdiatIon, the PHotoacId generatOr PRoduceS A proton. tHE rEsisT film is heated and, tHE pROton causes cataLytic cLeAVaGE Of tHe pEndant grouP fRom thE Polymer BAcKBONe. THE proton is not cOnsumed in thE CleAvage rEaCtiON and caTalyzEs ADdiTional cleavAge rEactions tHereby CHemicalLY amplifYing thE phOtoChemICaL rEspOnSE of THe ResISt. THe cleaveD pOlYmer iS solUBLE In poLar DeveLoperS such as alcohoL anD aquEOus Base wHile tHe unExPosed PolymeR is soLuBle in non-polar orGaniC solvents SucH aS anIsOle. ThUS the reSisT caN producE positiVE or NeGATIvE images of the mask dePeNDInG of the seLectioN Of ThE DevelopeR sOlvEnt. ALTHough ChemICaLly ampliFied reSIsT cOmpositIoNs geneRaLly HavE suitABle lIthogrAphic senSitivITy, in certain appLIcations, their PErFORmANce cAn bE improved by (I) incREasiNg thEIr TheRMal stAbiliTy IN tERms of thermal decompoSiTion anD plasTic flow and (ii) iNcreasing tHEIR stabiliTy in THe PResence of airboRne chEmical contAMinants. FOr exaMple, in soMe semiconDUCtor manuFacTurIng ProCESsEs, post image deVELopmEnT temperAtuRes (e.g. etChiNg, iMplAntAtIon etc.) can Reach 200° C. BrUnSvOlD eT al., u.S. Pat. nO. 4,939,070 (issued JUl. 3, 1990) And u.S. pat. no. 4,931,379 (issUEd Jun. 5, 1990) dIscloSe chEmIcALly AmplifiED, aCID senSiTiVe reSisT cOmposItioNS haVing incReased theRmaL StabIlItY in the pOst image develOpMent stage. BRuNsvOld's reSISt composItions form a hydrogen bondINg netwoRk aFter cLeavAge of the aCid SensitIve SIde chaIn grouP to inCrEasE THe theRMAl StaBiLity of the pOLYmeR. BrunSvOld aVoids hyDrogen-bonding moietIEs pRior to the cleaVagE reaCTIoN beCAuSE suCh HYdrOGEn bonding is knowN to unaccepTaBLy DestabilizE The AcId sensiTive sidE chaiN. althougH BrunsvolD resists hAvE suiTABle Thermal staBility, thEy also havE Lower SEnSitivIty And theReForE are uNsuitaBLe iN certAin appLiCationS.
With ReSpect to cHemical contamination, Macdonald Et al. SpIE 14662. (1991) Reported tHat DUe tO the catalYtic Nature of thE imAgiNg mecHanISms, chEmicALlY amPLifieD resISt systems ARe SenSITiVe toward minUTE AmoUnts oF aiRBorne cHemiCal contaminants suCH as basic organiC subSTAncEs. THEse sUbStances degrade The ReSULting devElOped image in The film aNd CAuse a Loss of The linEwidth cONTrOL of the DeveLopEd image. ThIs pRoBLem is exAgGeRAted in A manUfActuriNg procESs whERE there is an extendEd and VARiablE PerIod of TiMe betweEN appLying the fiLm to the subsTrate aNd
mer Sci. Technol. 4, 299 ( 1991). The  resi stcom po siti onsgenerally comp r isea photosensitive acidgener at o r an d  a n aci d sensi t iv e pol ym er . T he po lymer  ha s acidsensitivesid echain (penda n t)  groups th atare bonded t o t he pol ym erb ackbo neand a re rea c tive t owards apr o ton. U p on imag e w is e ex posure to radiati o n, the photoacidgenera to r  p r o duc esa proton.Th e res i st film is h e ate d  and, the pro ton causesc ata lyticcl eav a ge ofthe p en d ant  group from  the  polymerbackbo n e. Thep roton i s notcon sum ed i n  t he  cl ea v age re act i onand cata ly ze s add itio n a l clea vag e re actio ns thereby ch emi call y  am plify ing t he p ho toche micalrespo ns e of the resist . Th e cleaved  po ly mer  i s sol u ble in  po lar  develo pers su c h a sa l c oh ol and aqueous bas ew h il e the un expose d  p ol y mer is s ol ubl e in n on-po laro rg anic sol ventss uc has anis ol e. Thu sthe  re sistc an p roduce  positiv e orn egative images of the mask d e pe n d in g  ofthe  selectionof t h e de velo p er  so l vent.  Alth ou g hc hemically amplified  r esistcompo sitions gener ally haves u i table li thog r ap h ic sensitivity , incertain ap p lication s, th eir perf ormance c a n  be impr ove d b y ( i)i n cr easing theirt h erma lstabili tyin term s o f t her mal  d ecomposit ion andpl as ti cflo w and (ii) inc re asi ng  th eir s t abilit y inthepr es e nce  of air b or n e  che mi ca l co nta mi nants . Fo r  ex ample,in some s emi c ondu ct or  manufa cturing proce ss es, post i ma gedevelo p m ent temp eratures (e.g. etching, implant ati on et c.)can reach  20 0° C.Bru n svoldet al. , U.S .Pat . No. 4 , 9 39 ,07 0(issued Ju l .  3,  1990 )andU.S. Pa t. No. 4,931,379 ( i ssu ed Jun. 5, 19 90)  dis c l os e c h em i cal ly amp l i fied, acid sens itive resi st co mpositions hav in g incre ased th ermal stabili ty in the  post ima ge  dev e l opm ent stage.  Brunsvo ld's resi s t com p os ition s f orm ahy dro gen b onding net workaftercl eavage  of t he  acid se nsitive side chain grou p to i ncrea sethe therm als tab ility ofthepolymer. B run svo ld av oid s  hydr ogen - bo ndi n g moi etie s  prior to th e c l e av age reactio n b eca use s uch hydrog en b onding is known t o  unacceptablydest a b ili zet he a ci d sensitive si dech a i n. Altho ug h Brunsvold  resists  h a ve su itable  therm al stab i l it y , they  als o h ave lower  se ns i tivityan dt herefo re a re  unsui tablei n ce r t ain applications .
Wit h respe c t t o che mi cal con t amin ation, Mac Donald et a l. SPI E 14 662.(1991)re ported  th at  due to th e  catalyti c nat ure ofth e im agi ng mec hani s m s, ch emic al lyamplified r es i st  s y ste ms a re se ns itiv e towardm inute am oun t s of ai rb orn e chemic a lc o ntaminants  su ch as b asic organ i c su b st a nces.  These  subst ances d e gra de  the re sul t i ng develo ped image inth e fi lm and c au se a  l oss  o f the linewidth  control  of thed e velope d i m age. This p ro blem is exag gerat ed in a ma n u fac turingp roc ess  wh erethe re i s  an extended and variabl e pe riodo f t ime b etwee napplying thefilm tot he substrateand
mer Sci._Technol. 4,_299 (1991). The resist_compositions generally_comprise_a photosensitive_acid_generator and an_acid sensitive polymer._The polymer has acid_sensitive side chain_(pendant)_groups that are bonded to the polymer backbone and are reactive towards a proton._Upon_imagewise exposure_to_radiation,_the photoacid generator produces a_proton. The resist film is_heated and,_the proton causes catalytic cleavage of the pendant_group_from the polymer_backbone. The proton is not consumed in the cleavage_reaction and catalyzes additional cleavage reactions_thereby chemically amplifying_the_photochemical_response of the resist._The cleaved polymer is soluble in_polar developers such as alcohol and_aqueous base while the unexposed polymer is_soluble in non-polar organic solvents such_as anisole. Thus the resist_can produce_positive or negative images of_the mask depending_of the_selection of the_developer solvent. Although chemically amplified resist_compositions generally have_suitable lithographic sensitivity, in certain applications,_their_performance can be_improved_by_(i) increasing_their thermal stability_in_terms of_thermal_decomposition and plastic flow and (ii)_increasing_their stability in the presence of airborne_chemical contaminants. For example,_in_some semiconductor manufacturing processes,_post image development temperatures (e.g._etching, implantation etc.) can reach 200°_C. Brunsvold_et al.,_U.S. Pat. No. 4,939,070 (issued Jul. 3, 1990) and U.S. Pat._No. 4,931,379 (issued Jun. 5, 1990)_disclose chemically amplified, acid_sensitive resist_compositions_having increased thermal_stability_in the_post image development stage. Brunsvold's resist compositions_form a_hydrogen bonding network after cleavage of_the acid sensitive side_chain_group to increase the thermal stability_of the polymer. Brunsvold avoids hydrogen-bonding_moieties prior to the cleavage_reaction_because_such hydrogen bonding is known_to unacceptably destabilize the acid sensitive_side chain. Although_Brunsvold resists have suitable thermal stability, they_also_have lower sensitivity and therefore are_unsuitable_in certain applications.
With respect to chemical_contamination,_MacDonald_et al. SPIE 14662. (1991)_reported that due to the catalytic_nature of the imaging mechanisms, chemically amplified resist systems_are sensitive toward_minute amounts of airborne chemical_contaminants_such_as basic organic substances. These substances degrade the resulting developed_image in_the film and_cause a loss of the linewidth control of the developed_image. This problem is exaggerated in a_manufacturing process where there is an extended and variable period of_time between applying the film to the substrate_and