Underlayer film-forming composition and pattern forming process
In lithography, a composition comprising a novolak resin comprising recurring units derived from a phenolphthalein, Phenol Red, Cresolphthalein, Cresol Red, or Thymolphthalein is used to form a photoresist underlayer film. The underlayer film is strippable in alkaline water, without causing damage to ion-implanted Si substrates or SiO 2 substrates.
1. A photoresist underlayer film-forming composition for use in lithography, consisting of a novolak resin, and at least one selected from the group consisting of an organic solvent and a crosslinker, the novolak resin comprising recurring units of at least one type selected from the group consisting of a substituted or unsubstituted phenolphthalein, Phenol Red, Cresolphthalein, Cresol Red, and Thymolphthalein, wherein
the recurring units have the general formula (1):
wherein R 1 and R 2 are independently hydrogen or a straight, branched or cyclic C 1 -C 10 alkyl, acyl, alkoxycarbonyl or glycidyl group,
R 3 , R 4 and R 6 are independently hydrogen, or a straight, branched or cyclic C 1 -C 10 alkyl, C 2 -C 10 alkenyl, or C 6 -C 10 aryl group, which may have a hydroxyl, alkoxy, acyloxy, ether or sulfide moiety, or a halogen atom, hydroxyl group or C 1 -C 4 alkoxy group,
R 5 is hydrogen, or a straight, branched or cyclic C 1 -C 6 alkyl, a straight, branched or cyclic C 2 -C 10 alkenyl, or C 6 -C 12 aryl group, which may have a hydroxyl, alkoxy, ether, thioether, carboxyl, alkoxycarbonyl, acyloxy, —COOR or —OR moiety, wherein R is a lactone ring, acid labile group, or —R′—COOR″, wherein R′ is a single bond or alkylene group, and R″ is an acid labile group,
X is —C(═O)— or —S(═O) 2 —, m, n, p, q and r each are 1 or 2.
2. The underlayer film-forming composition of claim 1 , wherein the crosslinker is selected from the group consisting of melamine compounds, guanamine compounds, glycoluril compounds and urea compounds having substituted thereon at least one group selected from among alkoxymethyl and acyloxymethyl groups, epoxy compounds, isocyanate compounds, azide compounds, and compounds having a double bond.
3. The underlayer film-forming composition of claim 1 , wherein R 5 is a C 6 -C 12 aryl group which may have a hydroxyl, alkoxy, ether, thioether, carboxyl, alkoxycarbonyl, acyloxy, —COOR or —OR moiety, wherein R is a lactone ring, acid labile group, or —R′—COOR″, wherein R′ is a single bond or alkylene group, and R″ is an acid labile group.
4. The underlayer film-forming composition of claim 1 wherein R 1 and R 2 are hydrogen, and R 3 , R 4 and R 6 are independently hydrogen, a straight, branched or cyclic C 1 -C 10 alkyl group, or a hydroxyl group.
5. The underlayer film-forming composition of claim 1 wherein the novolak resin has a weight average molecular weight of 400 to 20,000.
6. A process for forming a pattern in a substrate by lithography, comprising the steps of
applying the underlayer film-forming composition of claim 1 onto a substrate to form an underlayer film,
forming a photoresist film on the underlayer film,
forming a photoresist pattern via exposure and development, and
processing the underlayer film and the substrate with the photoresist pattern serving as mask.
7. A process for forming a pattern in a substrate by lithography, comprising the steps of
applying the underlayer film-forming composition of claim 1 onto a substrate to form an underlayer film,
forming a photoresist film on the underlayer film,
forming a photoresist pattern via exposure and development,
processing the underlayer film with the photoresist pattern serving as mask, and
implanting ions into the substrate.
8. A process for forming a pattern in a substrate by lithography, comprising the steps of
applying the underlayer film-forming composition of claim 1 onto a substrate to form an underlayer film,
forming a silicon-containing intermediate film on the underlayer film,
forming a photoresist film on the intermediate film,
forming a photoresist pattern via exposure and development,
processing the intermediate film with the photoresist pattern serving as mask,
processing the underlayer film with the intermediate film serving as mask, and
processing the substrate with the underlayer film serving as mask.
9. A process for forming a pattern in a substrate by lithography, comprising the steps of
applying the underlayer film-forming composition of claim 1 onto a substrate to form an underlayer film,
forming a silicon-containing intermediate film on the underlayer film,
forming a photoresist film on the intermediate film,
forming a photoresist pattern via exposure and development,
processing the intermediate film with the photoresist pattern serving as mask,
processing the underlayer film with the intermediate film serving as mask, and
implanting ions into the substrate with the underlayer film serving as mask.
10. The pattern forming process of claim 6 , further comprising the step of stripping the underlayer film in alkaline water before or after the step of processing the substrate.
11. The pattern forming process of claim 7 , further comprising the step of stripping the underlayer film in alkaline water after the ion implantation step.
12. The pattern forming process of claim 7 , further comprising the step of stripping the underlayer film in alkaline water at pH 9 or higher after the ion implantation step.
13. The pattern forming process of claim 10 wherein the alkaline water contains 1 to 99% by weight of at least one member selected from the group consisting of ammonia, ammonia hydrogen peroxide water, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU, DBN, hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquathydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, and guanidines.