Gap-filling method
A method of manufacturing a semiconductor device comprising: providing a semiconductor device substrate having a relief image on a surface of the substrate, the relief image having a plurality of gaps to be filled; applying a coating composition to the relief image to provide a coating layer, wherein the coating composition comprises (i) a polyarylene oligomer comprising as polymerized units one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties; wherein the polyarylene oligomer has a M w of 1000 to 6000 Da, a PDI of 1 to 2, and a molar ratio of total first monomers to total second monomers of 1:>1; and (ii) one or more organic solvents; curing the coating layer to form a polyarylene film; patterning the polyarylene film; and transferring the pattern to the semiconductor device substrate.
1. A method comprising: (a) providing a semiconductor device substrate having a relief image on a surface of the substrate, the relief image having a plurality of gaps to be filled; (b) applying a coating composition to the relief image and filling the gaps to provide a coating layer, wherein the coating composition comprises (i) a polyarylene oligomer comprising as polymerized units one or more first monomers having two or more cyclopentadienone moieties and one or more second monomers having an aromatic moiety and two or more alkynyl moieties; wherein the polyarylene oligomer has a M w of 1000 to 6000 Da, a polydispersity index (PDI) of 1 to 2, and a molar ratio of total first monomers to total second monomers of 1:>1; and (ii) one or more organic solvents; (c) curing the coating layer to form a polyarylene film; (d) disposing a layer of an inorganic hardmask on the polyarylene film; (e) disposing a layer of a photoresist on the inorganic hardmask layer; (f) patterning the photoresist layer; (g) transferring the pattern from the photoresist layer to the polyarylene film; and (h) then transferring the pattern to the semiconductor device substrate.
2. The method of claim 1 wherein the polyarylene oligomer has a M w of 2000 to 3500 Da.
3. The method of claim 2 wherein the polyarylene oligomer has a PDI of 1.25 to 1.75.
4. The method of claim 1 wherein the polyarylene oligomer has a degree of polymerization of 2 to 3.75.
5. The method of claim 1 wherein the molar ratio of total first monomers to total second monomers is 1:1.01 to 1:1.5.
6. The method of claim 1 further comprising disposing a layer of an organic antireflectant between the hardmask layer and the photoresist layer.
7. The method of claim 1 wherein the polyarylene oligomer further comprises as polymerized units one or more end-capping monomers.
8. The method of claim 1 wherein at least one first monomer has the structure shown in formula (1)
wherein each R 10 is independently chosen from H, C 1-6 -alkyl, and optionally substituted C 5-20 -aryl; and Ar 3 is an aryl moiety having from 5 to 60 carbons.
9. The method of claim 1 wherein at least one second monomer has the structure shown in formula (5)
wherein each Ar 1 and Ar 2 is independently a C 5-30 -aryl moiety; each R is independently chosen from H, and optionally substituted C 5-30 -aryl; each R 1 is independently chosen from C 1-10 -alkyl, C 1-10 -haloalkyl, C 1-10 -hydroxyalkyl, C 1-10 -alkoxy, CN, and halo; each Y is independently a single covalent chemical bond or a divalent linking group chosen from —O—, —S—, —S(═O)—, —S(═O) 2 —, —C(═O)—, —(C(R 9 ) 2 ) z —, C 6-30 -aryl, and (C(R 9 ) 2 ) z1 —(C 6-30 -aryl)-(C(R 9 ) 2 ) z2 —; each R 9 is independently chosen from H, hydroxy, halo, C 1-10 -alkyl, C 1-10 -haloalkyl, and C 6-30 -aryl; a1=0 to 4; each a2=0 to 4; b1=1 to 4; each b2=0 to 2; a1+each a2=0 to 6; b1+each b2=2 to 6; d=0 to 2; z=1 to 10; z1=0 to 10; z2=0 to 10; and z1+z2=1 to 10.
10. The method of claim 1 further comprising the step of removing the polyarylene film.