Underlayer composition and method of manufacturing a semiconductor device

1. A method of manufacturing a semiconductor device, comprising:

forming a photoresist underlayer over a semiconductor substrate,

wherein the photoresist underlayer includes a polymer, comprising:

a main polymer chain having pendant target groups and pendant organic groups, or pendant target groups and pendant photoacid generator groups,

wherein the main polymer chain is selected from the group consisting of a polystyrene, a polyhydroxystyrene, a polyacrylate, a polymethylacrylate, a polymethylmethacrylate, a polyacrylic acid, a polyvinyl ester, a polymaleic ester, a poly(methacrylonitrile), and a poly(methacrylamide),

wherein the pendant target groups are one or more selected from the group consisting of a substituted or unsubstituted: C2-C30 diol group, C1-C30 aldehyde group, and C3-C30 ketone group,

wherein the pendant organic groups are C3-C30 aliphatic or aromatic groups having at least one photosensitive functional group, and

wherein the pendant photoacid generator groups are C3-C50 substituted aliphatic or aromatic groups;

forming a photoresist layer over the photoresist underlayer;

selectively exposing the photoresist layer to actinic radiation;

generating water in portions of the photoresist underlayer;

diffusing the water in the portions of the photoresist underlayer into corresponding portions of the photoresist layer exposed to the actinic radiation; and

developing the selectively exposed photoresist layer to form a photoresist pattern.

2. The method according to claim 1 , wherein the main polymer chain includes the pendant organic group having at least one photosensitive group, and the photosensitive group is selected from the group consisting of an epoxy group, an azo group, an alkyl halide group, an imine group, an alkene group, an alkyne group, a peroxide group, and combinations thereof.

3. The method according to claim 1 , wherein the main polymer chain includes the pendant photoacid generator groups, and the photoacid generator groups are selected from the group consisting of onium salts, sulfonium salts, triphenylsulfonium triflate, triphenylsulfonium nonaflate, dimethylsulfonium triflate, iodonium salts, diphenyliodonium nonaflate, norbornene dicarboximidyl nonaflate, halogenated triazines, diazonium salts, aromatic diazonium salts, phosphonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzylsulfonates, sulfonated esters, halogenated sulfonyloxy dicarboximides, α-cyanooxyamine-sulfonates, ketodiazosulfones, sulfonyldiazoesters, 1,2-di(arylsulfonyl)hydrazines, nitrobenzyl esters, and s-triazines.

4. The method according to claim 1 , wherein the photoresist underlayer further comprises a photobase generator compound.

5. The method according to claim 1 , wherein the photoresist underlayer further comprises a photoacid generator compound.

6. The method according to claim 1 , wherein the photoresist underlayer further comprises a thermal acid generator compound.

7. The method according to claim 1 , wherein the pendant target groups are substituted with one or more selected from the group consisting of —F, —Cl, —Br, —I, —NH 2 , —OH, —SH, —N 3 , a sulfonyl group, an alkene group, an alkyne group, an imine group, an ether group, an ester group, a peroxide group, an amide group, a sulfone group, a carboxyl group, a carbonyl group, an allene group, an amine group, a phosphine group, a triol group, an aniline group, a pyridine group, a pyrrole group, a cyanide group, a phosphite group, and combinations thereof.

8. The method according to claim 1 , further comprising heating the photoresist underlayer at a temperature ranging from 150° C. to 250° C. before forming the photoresist layer.

9. The method according to claim 1 , further comprising heating the selectively exposed photoresist layer and photoresist underlayer at a temperature ranging from 50° C. to 200° ° C. before the developing the selectively exposed photoresist layer.

10. A method of manufacturing a semiconductor device, comprising:

forming a photoresist underlayer over a semiconductor substrate,

wherein the photoresist underlayer includes a polymer having pendant target groups;

forming a photoresist layer over the underlayer;

selectively exposing the photoresist layer and photoresist underlayer to actinic radiation;

generating a chemical reporter molecule in the photoresist underlayer in portions of the photoresist underlayer exposed to the actinic radiation,

wherein the chemical reporter molecule is one or more selected from the group consisting of an electron, O 2 , water, H + , OH − , a cation, an anion, and a C1-C10 group substituted with a functional group,

wherein the functional group is one or more selected from the group consisting of —F, —Cl, —Br, —I, —NH 2 , —COOH, —OH, —SH, —N 3 , —S(═O)—, an alkene group, an alkyne group, a imine group, an ether group, an ester group, an aldehyde group, a ketone group, an amide group, a sulfone group, an alkylcarboxyl group, a cyanide group, a allene group, an alkyl alcohol group, an amine group, a phosphine group, a phosphite group, an aniline group, a pyridine group, and a pyrrole group;

generating a small molecule by an interaction between the chemical reporter molecule and the target group in the portions of the photoresist underlayer exposed to actinic radiation,

wherein the small molecule is one or more selected from the group consisting of an electron, O 2 , water, H + , OH − , a cation, an anion, and a C1-C10 group substituted with a functional group,

wherein the functional group is one or more selected from the group consisting of —F, —Cl, —Br, —I, —NH 2 , —COOH, —OH, —SH, —N 3 , —S(═O)—, an alkene group, an alkyne group, a imine group, an ether group, an ester group, an aldehyde group, a ketone group, an amide group, a sulfone group, an alkylcarboxyl group, a cyanide group, an allene group, an alkyl alcohol group, an amine group, a phosphine group, a phosphite group, an aniline group, a pyridine group, and a pyrrole group;

diffusing the small molecule from the photoresist underlayer to portions of the photoresist layer exposed to actinic radiation; and

developing the selectively exposed photoresist layer to form a patterned photoresist layer.

11. The method according to claim 10 , further comprising heating the photoresist underlayer at a temperature ranging from 150° C. to 250° C. before forming the photoresist layer.

12. The method according to claim 10 , wherein the diffusing the small molecule includes heating the selectively exposed photoresist layer and photoresist underlayer at a temperature ranging from 50° C. to 200° C. before the developing the selectively exposed photoresist layer.

13. The method according to claim 10 , wherein the photoresist layer comprises an organometallic material.

14. The method according to claim 10 , wherein the actinic radiation is extreme ultraviolet radiation.

15. The method according to claim 10 , wherein the small molecule and the chemical reporter molecule are different.

16. A method of manufacturing a semiconductor device, comprising:

forming a first layer over a semiconductor substrate,

wherein the first layer includes a polymer, comprising:

a main polymer chain having pendant target groups and pendant organic groups, or pendant target groups and pendant photoacid generator groups,

wherein the pendant target groups are one or more selected from the group consisting of a substituted or unsubstituted: C2-C30 diol group, C1-C30 aldehyde group, and C3-C30 ketone group,

forming a resist layer over the first layer;

generating water in first portions of first layer;

diffusing the water in the first portions of the first layer into corresponding first portions of the resist layer; and

removing second portions of the resist layer,

wherein the second portions of the resist layer are different from the first portions of the resist layer, and

wherein the first portions of the resist layer remain after the removing the second portions of the resist layer.

17. The method according to claim 16 , further comprising heating the first layer at a temperature ranging from 150° C. to 250° C. before forming the resist layer.

18. The method according to claim 16 , wherein generating water in first portions of first layer includes exposing the first portions of the first layer to extreme ultraviolet radiation.

19. The method according to claim 16 , wherein the diffusing the water includes heating the first layer and the resist layer at a temperature ranging from 50° C. to 200° C. before the removing the second portions of the resist layer.

20. The method according to claim 16 , further comprising heating the resist layer and the first layer at temperature ranging from 40° C. to 150° C. before the generating water in first portions of the first layer.