Feb.4,2021  107  US 2021/0033970 Al  [0156]  The resist composition is used in the fabrication of  various integrated circuits. Pattern formation using the resist  composition may be performed by well-known lithography  processes. The process generally involves coating, exposure,  and development.  If  necessary, any additional steps may be  added.  Pattern Forming Process  [0157]  For example, the resist composition is first applied  onto a substrate on which an integrated circuit is to be  formed (e.g., Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, ~OG,  or organic antireflective coating) or a substrate on wh1c~ a  mask circuit is to be formed (e.g., Cr, CrO, CrON, MoS12,  or SiO ) by a suitable coating technique such as spin  coating~ roll coating, flow coating, dipping, spraying or  doctor coating. The coating is prebaked on a hot plate at a  temperature of 60 to 150°  C. for 10 seconds to 30 minutes,  preferably at 80 to 120°  C. for 30 seconds to 20 m~nutes. The  resulting resist film is generally 0.01 to 2 µm  thick.  [0160]  After the exposure or PEB, the resist film is de~el› oped in a developer in the form of an aqueous base so!ut10n  for 3 seconds to 3 minutes, preferably 5 seconds to 2 mmutes  by conventional techniques such as dip, puddle and spray  techniques. A typical developer is a 0.1 to 10 wt %,  preferably 2 to 5 wt  % aqueous solution of tet~amethylam› moniumhydroxide (TMAH), tetraethylanimomum hydrox› ide (TEAH), tetrapropylammonium hydroxide (TPAH), or  tetrabutylanimonium hydroxide (TBAH). In t~e _case of  positive resist, the resist film in the exposed area 1s dissolved  in the developer whereas the resist film in the unexposed  area is not dissolved. In this way, the desired positive pattern  is formed on the substrate. Inversely in the case of negative  resist, the exposed area of resist film is insolubilized and the  unexposed area is dissolved in the developer.  [0161]  In an alternative embodiment, a negative p~ttern  may be formed via organic solvent development usmg a  positive resist composition comprising a base polymer_ha~› ing an acid labile group. The developer used herem 1s  preferably selected from among 2-octanone, 2-nonanone,  2-heptanone,  3-heptanone,  4-heptanone,  2-hexanone,  3-hexanone,  diisobutyl  ketone,  methylcyclohexanone,  acetophenone, methylacetophenone, propyl acetate, butyl  acetate, isobutyl acetate, pentyl acetate, butenyl acetate,  isopentyl acetate, propyl formate, butyl formate, isobutyl  formate, pentyl formate, isopentyl formate, methyl valerate,  [0165]  Examples of the invention are given below b~ ~ay  of illustration and not by way of limitation. The abbrevrnt10n  "pbw" is parts by weight.  [0166]  Quenchers 1 to 35 used in resist compositions have  the following structure.  [0164]  A hole or trench pattern after development may be  shrunk by the thermal flow, RELACSfi or DSA process. A  hole pattern is shrunk by coating a shrink agent theret?, ~nd  baking such that the shrink agent may undergo crosslmking  at the resist surface as a result of the acid catalyst diffusing  from the resist layer during bake, and the shrink agent may  attach to the sidewall of the hole pattern. The bake is  preferably at a temperature of 70 to 180°  C., more preferably  80 to 170°  C., for a time of 10 to 300 seconds. The extra  shrink agent is stripped and the hole pattern is shrunk.  [0163]  Rinsing is effective for mini~izing the risks_ of  resist pattern collapse and defect format10n. However, nns› ing is not essential.  If  rinsing is omitted, the amount of  solvent used may be reduced.  methyl pentenoate, methyl crotonate, ethyl crotonat~,  methyl propionate, ethyl propionate, ethyl 3-ethoxypropi› onate, methyl lactate, ethyl lactate, propyl lactate, butyl  lactate, isobutyl lactate, pentyl lactate, isopentyl lactate,  methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate,  methyl benzoate, ethyl benzoate, phenyl acetate, benzyl  acetate, methyl phenylacetate, benzyl formate, phen~lethyl  formate  methyl 3-phenylpropionate, benzyl prop10nate,  ethyl phenylacetate, and 2-phenylethyl acetate, and mixtures  thereof.  [0162]  At the end of development, the resist film is ~insed.  As the rinsing liquid, a solvent which is miscible with the  developer and does not dissolve the resist film is preferred.  Suitable solvents include alcohols of 3 to 10 carbon atoms,  ether compounds of 8 to 12 carbon atoms, alkanes, alkenes,  and alkynes of 6 to 12 carbon atoms, and aromatic solvents.  Specifically, suitable alcohols of 3 to 10 carbon atoms  include n-propyl alcohol, isopropyl alcohol, I-butyl alcohol,  2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-penta› nol, 2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl  alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl- 3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexai:iol,  2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dim› ethyl-2-butanol,  2-ethyl-1-butanol,  2-methyl-1-pentanol,  2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pen› tanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl- 1-pentanol,  4-methyl-2-pentanol,  4-methyl-3-pentanol,  cyclohexanol, and 1-octanol. Suitable ether compounds of 8  to 12 carbon atoms include di-n-butyl ether, diisobutyl ether,  di-s-butyl ether, di-n-pentyl ether, diisopentyl ether, di-s› pentyl ether, di-t-pentyl ether, and di-n-hexyl ether. Suitable  alkanes of 6 to 12 carbon atoms include hexane, heptane,  octane, nonane, decane, undecane, dodecane, methylcyclo› pentane, dimethylcyclopentane, cyclohexane, methylcyclo› hexane, dimethylcyclohexane, cycloheptane, cyclooctane,  and cyclononane. Suitable alkenes of 6 to 12 carbon atoms  include hexene, heptene, octene, cyclohexene, methylcyclo› hexene,  dimethylcyclohexene,  cycloheptene,  and  cyclooctene. Suitable alkynes of 6 to 12_ carbon ato~s  include hexyne, heptyne, and octyne. Smtable aromatic  solvents include toluene, xylene, ethylbenzene, isopropyl› benzene, t-butylbenzene and mesitylene. The solvents may  be used alone or in admixture.  EXAMPLES  [0159]  After the exposure, the resist film may be baked  (PEB) on a hot plate at 60 to 150°  C. for 10 seconds to 30  minutes, preferably at 80 to 120°  C. for 30 seconds to 20  minutes.  [0158]  The resist film is then exposed to a desired pattern  of high-energy radiation such as UV, deep-UV, EB, EUV,  x-ray, soft x-ray, excimer laser light, y-ray or synchrotro_n  radiation. When UV, deep-UV, EUV, x-ray, soft x-ray, exc1- mer laser light, y-ray or synchrotron radiation is used as the  high-energy radiation, the resi~t film is ex~osed thereto  through a mask having a desJred pattern m a dose of  preferably about 1 to 200 mJ/cm 2 , more pr~ferably about _10  to 100 mJ/cm 2 . When EB is used as the high-energy radrn› tion, the resist film is exposed thereto through a mask having  a desired pattern or directly in a dose of preferably about 0.1  to 100 µC/cm 2 , more preferably about 0.5 to 50 µC/cm 2 .  It  is appreciated that the inventive resist composition is s1:’ited  in micropatterning using KrF excimer laser, ArF exc1mer  laser, EB, EUV, x-ray, soft x-ray, y-ray or synchrotron  radiation, especially in micropatterning using EB or EUV. 